JP6436487B2 - Manufacturing method for manufacturing transparent conductive film - Google Patents

Description

A manufacturing method for manufacturing a transparent conductive film according to the present invention is a transparent conductive film in which a transparent conductive film made up of a collection of transparent conductive fine particles bonded by metal fine particles is manufactured integrally with a transparent substrate. It is a manufacturing method which manufactures . That is, a metal compound in which a metal is precipitated by thermal decomposition is dispersed in alcohol, and this dispersion is mixed with an organic compound having a boiling point lower than the temperature at which the metal compound is thermally decomposed to prepare a mixed solution. Further, a suspension is prepared by mixing the liquid mixture with a collection of transparent conductive fine particles whose particle size is 1/10 or less of the wavelength of visible light. This suspension is applied or printed on the surface of the transparent substrate, and then the transparent substrate is heat-treated to thermally decompose the metal compound. As a result, metal fine particles having a size corresponding to 1/10 of the wavelength of visible light are deposited on the surface of the transparent substrate and the surface of the transparent conductive fine particles, and the metal fine particles are metal-bonded and metal-bonded. A collection of metal fine particles enters the irregularities on the surface of the transparent substrate to form a surface layer, and bonds the transparent conductive fine particles together. As a result, a transparent conductive film composed of a collection of transparent conductive fine particles bonded by metal fine particles is manufactured integrally with the transparent substrate.

In recent years, touch panels that have been used mainly for industrial devices such as station ticket machines, bank ATMs, and POS cash registers at convenience stores have come to be widely used in consumer devices such as smartphones, car navigation systems, and digital cameras. . There are four types of touch operation detection methods on the touch panel: a resistance film method, a surface capacitance method, a projection capacitance method, an optical method, and an ultrasonic method. The method is the current mainstream.
The resistance film method has a structure in which a film on which a transparent conductive film is formed is bonded to glass with a slight gap. When the film surface is pressed with a finger, the film comes into contact with the electrode film on the lower glass surface to cause a current to flow, thereby causing a voltage change, and detecting the voltage change to detect the touch position. Since it is pressure-sensitive, it can handle pen input, and its structure is simple, which makes it cheap to manufacture.
On the other hand, the capacitance method is a method in which a slight change in capacitance occurs when the panel is touched with a finger, and the touch position is detected from the change in capacitance. There are two types: surface type and projection type. . In the surface type capacitance method, a uniform electric field is generated from the electrodes at the four corners of the panel over the entire panel. When the panel is touched with a finger, the capacitance changes, and a weak current corresponding to the distance to the touch position is generated at the electrodes at the four corners, and the touch position is detected from this weak current. The surface capacitance method is used for large panels and the like, but cannot support multi-touch that simultaneously detects a plurality of touch positions. The projection capacitive type that cleared this disadvantage and made multi-touch possible, and the panel had a structure in which two transparent conductive films with electrode patterns in the X-axis direction and Y-axis direction overlapped Have When a finger touches the panel, the capacitances of the conductive films arranged in a lattice pattern change simultaneously, and the touch position is detected by measuring this. The projection type has a more complicated structure than the surface type, but can detect the position with high accuracy, and can also handle multi-touch operations such as enlarging / reducing and rotating the photo on the screen with two fingers. It has been adopted for mobile devices such as smartphones and tablet PCs, and has become the mainstream of touch panels along with resistive film systems.
As described above, there are various types of touch panels, and a transparent conductive film is an indispensable member for any of the methods. Many of the transparent conductive films that have already been put into practical use are made of an ITO layer (abbreviation of Indium Tin Oxide, a semiconductor material that is transparent in the visible light region in which indium oxide is doped with tin) on the surface of a transparent substrate by sputtering. This is a technique for film formation.

However, when the ITO film is patterned on the surface of the transparent substrate, the ITO film pattern may be visually recognized. Various efforts have been made to improve the transparency of the ITO film. For example, in Patent Document 1, a film is formed with less oxygen in the film, and then heated in an oxygen atmosphere in the atmosphere to convert from an amorphous film to a crystalline film, thereby improving the conductivity of the ITO film. A technique for reducing the thickness of the ITO film and improving the transparency has been proposed.
Furthermore, with the increase in demand for a large touch panel and improved response speed, there is an increasing demand for a transparent conductive film including an ITO film having a lower resistance than a conventional ITO film. However, the conventional ITO film has a problem that the resistance is not sufficiently lowered even by crystallization, and it takes a long time to crystallize to realize low resistance, resulting in poor productivity.
As a method for solving such a problem, for example, Patent Document 2 discloses the surface roughness of a transparent substrate, the ratio of indium and tin of a sputtering target, the ultimate vacuum (moisture pressure) during sputtering, and the substrate. There has been proposed a technique in which an ITO film that can be crystallized and reduced in resistance by heating in a short time by setting the temperature within a predetermined range is formed.

However, the formation of a transparent conductive film by sputtering has various problems and problems described below, and if new treatments are added to solve these problems and problems, the manufacturing cost of the film is formed. Increases further. For this reason, a technique for manufacturing a transparent conductive film at a low cost by a simple manufacturing method other than sputtering is required.
Film formation by sputtering is a method in which ions are made to collide with a target at high speed, atoms constituting the target are knocked out, the knocked-out atoms enter the substrate, and atoms are deposited to form a film. . The atoms knocked out of the target travel straight toward the transparent substrate, so that defects such as protrusions called nodules are likely to occur depending on the surface of the substrate, and it is necessary to perform crystallization (annealing) treatment by heat treatment. There is. Note that targets made of a transparent conductive material typified by ITO are extremely expensive materials because they grow crystals to a predetermined size. In addition, the processing in a vacuum bell jar to which a high voltage is applied is not mass-productive in forming a film, and the manufacturing cost of the film is high.
Further, in film formation by sputtering, recoil particles are generated on the target when atoms are knocked out from the target, and when the recoil particles enter the substrate, the film is damaged. For this reason, it is necessary to reduce the discharge voltage by using a magnetron sputtering apparatus and lowering the magnetron impedance to alleviate damage caused by recoil particles. Furthermore, when the target is ITO, the necessary conductive film can be obtained by raising the temperature of the transparent substrate to near 300 ° C. and leaving it for a long time. For this reason, it becomes difficult to form a film on an inexpensive synthetic resin transparent film having poor heat resistance and dimensional stability.
Further, in the sputtering method, the vacuum chamber is once evacuated and then sputtering is performed. During evacuation, moisture and foreign matter are gasified from the transparent substrate and released into the film forming atmosphere, which is an obstacle to forming a low resistance film. For this reason, it is necessary to evacuate the transparent base material sufficiently and vacuum clean the surface of the transparent base material. This increases the manufacturing cost of the film formation.
Moreover, when forming an electrode pattern on a transparent substrate, after forming a transparent conductive film on the transparent substrate by a sputtering method, the electrode pattern is formed by etching. For this reason, it is limited to the transparent base material with chemical resistance with respect to an etching liquid. Further, the manufacturing cost for forming the electrode pattern is further increased by the etching process.
Furthermore, since the transparent conductive film formed by the sputtering method does not have sufficient conductivity, it is necessary to further heat-treat after forming the film by the sputtering method to promote crystallization of the transparent conductive material. For this reason, the transparent conductive material is allowed to stand for a long time in a high temperature state composed of an atmosphere in which oxygen gas does not exist, and crystallization proceeds. This limits the material of the transparent substrate on which the transparent conductive film is formed, and makes it difficult to reduce the thickness of the transparent substrate. For this reason, it becomes difficult to integrate the transparent base material on which the transparent conductive film is formed into various base materials and components.
Further, in the sputtering method, the resistivity of the formed transparent conductive film is high at a position away from a position directly below the target center by a certain distance or more. For this reason, when producing a large-area electrode substrate, a square electrode or a rectangular electrode substrate close to a square is arranged in a grid pattern to create a large-area electrode plate. In this case, the power supply line for supplying power to each electrode substrate has a complicated net shape, and wiring becomes difficult. Moreover, it becomes a complicated multilayer wiring, which further increases the manufacturing cost. Further, in order to make the potential of the transparent conductive film uniform, it is necessary to form a large number of auxiliary electrodes and conductive paths in the electrode substrate. However, in the process of forming the auxiliary electrode and the conductive path, defects such as foreign matter are likely to occur, and the manufacturing cost is further increased.
As described above, there are many problems and problems in forming a transparent conductive film by sputtering, and there is a technique for forming an inexpensive transparent conductive film by a simple manufacturing method other than sputtering. There is a strong demand.

JP 2006-202756 A JP 2012-134085 A

All of the problems related to the production of the transparent conductive film described above are based on the principle of film formation by sputtering. Therefore, the above-described problem cannot be solved unless a transparent conductive film is produced by a new method. Therefore , the manufacturing requirements for manufacturing a transparent conductive film by a new manufacturing method become a problem to be solved by the present invention.
The first manufacturing requirement is that a transparent conductive film can be manufactured at a low manufacturing cost. This further expands the applications of the touch panel. For this reason, the new manufacturing method firstly involves applying a high voltage, accompanied by a high temperature treatment, accompanied by a chemical treatment, accompanied by a reaction under a high pressure, accompanied by a treatment in a high vacuum atmosphere or a high pressure atmosphere, etc. , Without reaction or special treatment under special circumstances. Second, expensive materials are not used. Thirdly, it is a manufacturing method in which the transparent conductive film is continuously manufactured by continuously performing the manufacturing process with a short manufacturing process and simple manufacturing process.
The second manufacturing requirement is that there are no restrictions on the material and material form of the transparent conductive material constituting the transparent conductive film. Thus, a transparent conductive film can be manufactured using an inexpensive transparent conductive material as a raw material. In addition, since the raw material of the transparent conductive material by sputtering is a target made of a transparent conductive material crystal-grown to a predetermined size, the manufacturing cost of the target is high. In particular, a target made of ITO obtained by doping tin with an oxide of indium, which is a rare metal, is an extremely expensive material.
The third manufacturing requirement has no restriction on the material of the transparent substrate on which the transparent conductive film is formed. Thereby, a transparent conductive film can be formed on various transparent substrates. For example, an inexpensive synthetic resin transparent film can be used as the transparent substrate without high-temperature treatment or chemical treatment.
The fourth manufacturing requirement is not limited in the size of the transparent substrate on which the transparent conductive film is formed. As a result, a touch panel having a large area can be manufactured.
The fifth manufacturing requirement is that no pretreatment of the transparent substrate is required when forming the transparent conductive film. Thereby, a transparent conductive film can be formed on the transparent substrate at a low production cost. For example, no pretreatment such as cleaning or modification of the surface of the transparent substrate is necessary.
The sixth manufacturing requirement does not require further reprocessing after forming the transparent conductive film. Thereby, a transparent conductive film can be formed at a low manufacturing cost. Note that since film formation by sputtering is low in crystallinity, a second heat treatment is required to increase film formation conductivity.
The seventh manufacturing requirement is that the electrode pattern can be directly formed on the surface of the transparent substrate without etching, and there is no restriction on the pattern shape or line width. Thereby, a projected capacitive touch panel can be manufactured at a low manufacturing cost, and the use of the touch panel is further expanded.
The eighth manufacturing requirement is that the transparent base material on which the transparent conductive film is formed can be easily joined or bonded to various base materials and parts. Thereby, transparency and conductivity can be easily imparted to various substrates and parts, and the use of the touch panel is further expanded.
If the transparent conductive film can be manufactured by satisfying the eight requirements described above, the use of the touch panel is further expanded.

In the production method for producing a transparent conductive film integrated with a transparent substrate in the present invention, a metal compound in which a metal having a refractive index of 2.0 or less is precipitated by thermal decomposition is dispersed in alcohol to obtain an alcohol dispersion. The first step to be prepared, the first property dissolved or mixed in alcohol, the solution dissolved in alcohol or the mixed solution mixed with alcohol, the second property having a higher viscosity than the alcohol, and the metal The organic compound having these three properties, which has a third property whose boiling point is lower than the temperature at which the compound is thermally decomposed, is mixed with the alcohol dispersion prepared in the first step to prepare a mixed solution . creating a second step, a collection of the transparent conductive fine particles the size of the grain element is made from a less well wavelengths of visible light, the suspension is mixed to the mixed solution prepared in the second step A third step, the surface of the permeable BenQ material, and a fourth step of applying or printing a suspension created in the third step, the suspension created in the fourth step has been applied or printed It consists of a fifth step of thermally decomposing the metal compound by heat-treating the transparent substrate, and a manufacturing method in which these five steps are carried out continuously produces a transparent conductive film integrated with the transparent substrate . is a manufacturing method to be.

That is, a transparent conductive film made up of a collection of transparent conductive fine particles bonded with metal fine particles is manufactured integrally with a transparent substrate by a manufacturing method in which five steps are continuously performed. The five-step process consists of a simple process, and secondly, it is a process that only vaporizes alcohol and organic compounds and applies a thermal load to thermally decompose the metal compound. A transparent conductive film integrated with a substrate can be manufactured at low cost .
That is, the first step is a step of dispersing the metal compound in the alcohol, the second step is a step of mixing the organic compound in the alcohol dispersion, and the third step is transparent conductive in the mixture. These are simply steps of mixing the fine particles, both of which are very simple processes consisting of weighing and mixing the raw materials. In the fourth step, the suspension is simply applied or printed. The fifth step is only a heat treatment .
As described above, the transparent conductive film integrated with the transparent base material can be manufactured at low cost by the manufacturing method in which the five steps consisting of extremely simple processes are continuously performed .
In other words, when the suspension prepared according to this production method is applied or printed on a transparent substrate and heat-treated, the alcohol is first vaporized, then the organic compound is vaporized, and then the metal compound is thermally decomposed and visible. Granular metal fine particles with a size of 40-60 nm corresponding to 1/10 of the wavelength of light (380-780 nm) are deposited on the surface of the transparent substrate and the surface of the transparent conductive fine particles. At this time, since the metal fine particles are in an active state having no impurities, adjacent metal fine particles are metal-bonded, and a collection of metal particles that are metal-bonded enters the irregularities on the surface of the transparent substrate to form a surface layer. Bonding transparent conductive fine particles. As a result, a transparent conductive film composed of a collection of transparent conductive fine particles bonded with metal fine particles is formed integrally with the transparent substrate. The deposited metal fine particles are larger than the transparent conductive fine particles.
That is, when a metal compound that deposits metal by pyrolysis is dispersed in alcohol, the metal compound is in a molecular state and uniformly dispersed in the alcohol. The solvent in which the metal compound is dispersed is preferably an alcohol that is the most general-purpose organic solvent. Further, since the metal compound is dispersed in a molecular state in the alcohol, when the alcohol is vaporized, crystals of the metal compound are precipitated. This phenomenon is similar to the phenomenon in which fine powder of sugar is precipitated when water is vaporized from sugar water. On the other hand, the viscosity of the alcohol dispersion of the metal compound is equivalent to the viscosity of the alcohol. Therefore, even if transparent conductive fine particles are mixed with an alcohol dispersion to prepare a suspension, the viscosity of the suspension does not increase because the transparent conductive fine particles are solid. For this reason, an organic compound which has a property of being dissolved in alcohol or miscible with alcohol and a property of a solution dissolved in alcohol or a solution mixed with alcohol having a viscosity higher than that of alcohol is used as an alcohol dispersion. When mixed, the viscosity of the mixed solution is higher than that of alcohol. When a suspension is prepared by mixing transparent conductive fine particles with such a mixed solution and this suspension is applied or printed on a transparent substrate, the coating or coating corresponding to the viscosity of the suspension becomes transparent. Formed on the material. That is, in order to form a coating film or a film, a viscosity corresponding to the film thickness of the coating film or the film is required. For this purpose, an organic compound was mixed in the alcohol dispersion. In the suspension thus produced, the metal compound is uniformly dispersed in a molecular state, and the transparent conductive fine particles are also uniformly dispersed. In addition, the transparent conductive film manufactured by this manufacturing method consists of a thin film thickness of a coating film or a film to a micron level or less in order to ensure transparency. Therefore, the viscosity of the suspension is low.
When such a suspension is applied to or printed on a transparent substrate, a part of the suspension enters the irregularities on the surface of the transparent substrate to form a coating film or film on the surface of the transparent substrate. When this transparent substrate is heat-treated, the alcohol is first vaporized and then the organic compound is vaporized. Thus, a thin film made of a metal compound is formed on the surface layer including the irregularities on the surface of the transparent substrate and the surface of the transparent conductive fine particles. That is, in order to form a thin film made of a metal compound on the surface of the transparent substrate and the surface of the transparent conductive fine particles, the metal compound was uniformly dispersed in a molecular state in alcohol. As a result, the surface of all the transparent conductive fine particles is covered with a thin film of a metal compound. When the temperature is further increased, the metal compound is thermally decomposed, and a collection of granular metal fine particles having a size of 40 to 60 nm is deposited on the surface layer of the transparent substrate and the surface of the transparent conductive fine particles. Since the deposited metal fine particles are in an active state having no impurities, adjacent metal fine particles are metal-bonded to each other. As a result, a collection of metal fine particles that are metal-bonded enters the irregularities on the surface of the transparent substrate to form a surface layer. Further, the transparent conductive fine particles are bonded by metal fine particles.
The transparent conductive film integrated with the transparent base material manufactured by this manufacturing method is composed of a collection of two kinds of fine particles, and the transparent conductive fine particles are dispersed in a collection of metal fine particles bonded with metal. It becomes a structure. In order to ensure the transparency of the transparent conductive film, the number of metal fine particles to be deposited is smaller than the number of transparent conductive fine particles, and the transparent conductive material is formed by the metal fine particles discretely deposited on the surface of the transparent conductive fine particles. Fine particles are bound. For this reason, the number of moles of the metal compound in the suspension is less than the number of moles of the transparent conductive fine particles mixed in the suspension. Further, since the transparent conductive fine particles are bonded through metal-bonded metal fine particles, the conductivity is closer to the metal than a conventional transparent conductive film, for example, a transparent conductive film made of ITO having the highest conductivity. have. Accordingly, even a film thinner than the conventional transparent conductive film has necessary conductivity, and the transparency of the transparent conductive film increases. Furthermore, even if transparent conductive fine particles which are inferior in conductivity to ITO but cheaper are used, the conductivity is improved as compared with the conventional transparent conductive film made of ITO. On the other hand, the collection of metal fine particles entering the irregularities on the surface of the transparent substrate exhibits an anchor effect, so that the transparent conductive film does not separate from the transparent substrate. Further, since the transparent conductive fine particles are bonded by the metal bonded metal fine particles, the bond of the transparent conductive fine particles is not broken. For this reason, the transparent base material in which the transparent conductive film is formed is rich in handling properties and can be applied to various applications.
On the other hand, the transparent conductive film manufactured by this manufacturing method has high transmittance with respect to incident light. That is, when light enters the transparent conductive film, surface reflection (also referred to as Fresnel reflection) occurs due to a difference from the refractive index of air on the surface of the transparent conductive film. Although the surface of the transparent conductive film is composed of metal fine particles and transparent conductive fine particles, the size of the metal fine particles is larger than the size of the transparent conductive fine particles. Causes surface reflection according to the difference in refractive index. The surface reflectance is the square of the value obtained by dividing the difference in refractive index between metal and air by the sum of the two. Further, the transmittance of the light that enters the surface of the transparent conductive film is the square of the value obtained by subtracting the surface reflectance from 1 when the entire incident light is 1. In this manufacturing method , the metal constituting the metal fine particles has a refractive index close to 2.0 or less of air, so that the transmittance of incident light has a value close to the transmittance of glass. A detailed description of surface reflection and total light transmittance will be given in the following nine paragraphs.
Furthermore, the light that has passed through the surface of the transparent conductive film enters the transparent conductive film made up of two kinds of fine particles and scatters the light. The scattering of light in the collection of fine particles is scattered based on the Rayleigh scattering formula. The Rayleigh scattering coefficient greatly depends on the fourth power of the ratio of the particle size to the wavelength of incident light, and also depends on the square of the size of the fine particles. For this reason, the scattering coefficient in a transparent conductive film becomes a very small value, and a transparent conductive film shows high transparency. A detailed description of Rayleigh scattering will be given in the following 10 paragraphs.
That is, the transparent conductive film has a configuration in which the transparent conductive fine particles are bonded by the metal fine particles deposited by the thermal decomposition of the metal compound, and the refractive index of the metal constituting the metal fine particles is set to 2.0 or less. By setting the size of the metal fine particles to one tenth of the wavelength of visible light and the size of the transparent conductive fine particles to one tenth or less of the wavelength of visible light, high transmittance for visible light and high for visible light A transparent conductive film having these three properties consisting of transparency and higher conductivity than the material of the transparent conductive fine particles can be manufactured integrally with the transparent substrate.
On the other hand, the manufacturing method of the transparent conductive film integrated with the transparent base material in this manufacturing method has various features described below. First, the raw material treatment is only a heat treatment for thermally decomposing a metal compound. If a metal compound that is thermally decomposed at a low temperature of about 200 ° C. in a short time is used, a transparent substrate having low heat resistance can be used. . For this reason, there is no restriction on the material of the transparent substrate.
Secondly, the manufacturing process consists of a process of manufacturing a suspension, a process of applying or printing the suspension on a transparent substrate, and a process of heat-treating the transparent substrate, and only three simple processes. It consists of a process. By carrying out these steps continuously, even a transparent substrate having a large area can continuously produce a large amount of transparent substrate integrated with a transparent conductive film. For example, a suspension is continuously applied or printed on a moving transparent substrate, the substrate is continuously passed through a baking furnace, and then the transparent substrate is continuously cut to a required size. For example, a transparent substrate having a large area integrated with a transparent conductive film can be continuously manufactured at a significantly low manufacturing cost.
Thirdly, both the metal compound and the organic compound, which are materials for the suspension, are general-purpose industrial chemicals. Furthermore, a suspension can be produced regardless of the material of the transparent conductive fine particles. For this reason, not only expensive ITO mainly composed of an oxide of indium, which is a rare metal, but also transparent conductive fine particles made of various materials cheaper than ITO can be used.
Fourthly, since the transparent conductive film is formed by means for applying or printing the suspension on the transparent substrate, it is not necessary to pre-treat the surface of the transparent substrate. Further, the viscosity of the suspension can be freely changed according to the concentration of the low-boiling organic compound in the suspension, and the thickness of the coated or printed suspension can be freely changed. As a result, the thickness of the transparent conductive film can be freely changed. Moreover, there is no restriction | limiting of the magnitude | size of the transparent base material which apply | coats or prints a suspension. Furthermore, if the electrode pattern can be directly formed on the surface of the transparent substrate by screen printing of the suspension, and the viscosity of the suspension is reduced, there is no restriction between the shape of the electrode pattern and the line width.
As described above, according to the present manufacturing method , the transparent conductive film is integrated with the transparent substrate by satisfying the seven requirements except for the eighth requirement among the eight requirements described in the sixth paragraph. Can be manufactured.

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 air and the substrate. Accordingly, loss due to surface reflection occurs even in transparent glass, and the total light transmittance does not reach 100%. By the way, with the thickness of 2 mm of the most common float glass, the total light transmittance is about 90% in the wavelength region of visible light. The surface reflectance R at the surface of light perpendicularly incident on the substrate is calculated by Equation 1 consisting of the refractive index n of the substrate and the refractive index m of air. Further, the total light transmittance T is calculated by Equation 2 consisting of the surface reflectance R. The surface of the transparent conductive film in the present invention is composed of metal fine particles and transparent conductive fine particles. However, since the metal fine particles protruding from the surface are larger than the transparent conductive fine particles, most of the incident light is refracted by the metal. Causes surface reflection according to the difference between the refractive index and the refractive index of air. The refractive index of the metal constituting the metal fine particles in the present invention is 2.0 or less. For example, when the refractive index of the metal is 1.5, the surface reflectance R is 4%, and the total light transmittance T is 92%. When the refractive index of the metal is 0.6, the surface reflectance R is 6% and the total light transmittance T is 88%, both of which have a light transmittance comparable to that of float glass. In addition, the refractive index of soda-lime glass which is a general glass is 1.51 close to the refractive index of the above-mentioned metal, the surface reflectance is 4%, and the total light transmittance is 92%.
Formula 1
R = (n−m) ² / (n + m) ²
Formula 2
T = (1-R) ²

Next, light scattering will be described. When visible light is irradiated onto particles dispersed in a medium, if the size of the particles is sufficiently smaller than the wavelength of visible light (380-780 nm), the Rayleigh scattering formula shown in Equation 3 is applied for light scattering. it can. In Equation 3, S is the scattering coefficient, λ is the wavelength of incident light, D is the particle diameter, and m is the ratio of the refractive index of the particle to the refractive index of the medium. The transparent conductive film in the present invention has a structure in which a collection of metal fine particles serves as a medium, and the transparent conductive fine particles are dispersed in the medium. Therefore, m is a conductive fine particle with respect to the refractive index of the metal constituting the metal fine particles. The ratio of the refractive index of the material. Further, π is a circumference ratio. The scattering coefficient S in Equation 3 greatly depends on the fourth power of the ratio D / λ of the particle diameter D to the wavelength λ of incident light, and also depends on the square of the particle diameter D. Since the particle diameter D in the present invention is 1/10 or less of the wavelength λ of incident light, the scattering coefficient S becomes a very small value. As a result, the transparent conductive film in the present invention exhibits high transparency.
Formula 3
S = 4/3 · π ⁵ / λ ⁴ · D ⁶ {(m ² −1) / (m ² +1)} ²

A manufacturing method for manufacturing a substrate or a part to which the properties of the transparent conductive film described above are imparted is as follows.
The above-described manufacturing method transparent conductive film together with the transparent substrate produced in, applying a compressive load put on the substrate or part products, the transparent conductive layer using the substrate or the component The bonding method is a manufacturing method for manufacturing a substrate or a part to which the properties of the transparent conductive film described above are imparted .

That is, the surface of the transparent conductive film integrated with the transparent substrate manufactured by the above-described manufacturing method has fine irregularities made up of a collection of transparent conductive fine particles bonded with metal fine particles. The unevenness is an order of magnitude smaller than the unevenness on the surface of the base material or component to be pressed. Further, when compressive stress is applied to the transparent conductive film, the collection of metal particles easily plastically deforms due to the malleability of the metal, and the bonds of the transparent conductive particles are not broken. Therefore, when a transparent base material with a transparent conductive film is placed on a different base material or a different part and a compressive load is applied, the transparent conductive film is plastically deformed and becomes uneven on the surface of the base material or part. As a result, the transparent conductive film is combined with the base material or component. Also, the transparent conductive film that has been pressure-bonded does not separate from the base material or parts due to the anchor effect. As a result, the properties of the transparent conductive film are newly imparted to different base materials and different parts by an extremely simple means of pressure bonding.
As a result, according to the present manufacturing method , the eighth manufacturing requirement described in the sixth paragraph is satisfied, and all the eight manufacturing requirements described in the sixth paragraph are satisfied.

In the manufacturing method for manufacturing the transparent conductive film described above, the transparent conductive fine particles in the manufacturing method for manufacturing the transparent conductive film described above are fine particles in which indium oxide is doped with tin, and fine particles in which tin oxide is doped with antimony or phosphorus. The transparent conductive fine particles are composed of at least one kind of fine particles of these four kinds of fine particles obtained by doping zinc oxide with aluminum or gallium, or fine particles obtained by doping titanium oxide with niobium . It is a manufacturing method which manufactures a transparent conductive film .

In other words, the transparent conductive film integrated with the transparent base material manufactured by the above-described manufacturing method is composed of a collection of transparent conductive fine particles bonded with metal fine particles, so that the conductivity is higher than that of the conventional transparent conductive film. Is expensive. Moreover, there is no restriction | limiting of the material of transparent conductive fine particles in producing suspension. Therefore, the material of the transparent conductive fine particles is not limited to expensive ITO in which tin is doped with an indium oxide of a rare metal, and fine particles made of a transparent conductive material that is inferior in conductivity but cheaper than ITO are used. it can. Examples of such transparent conductive fine particles include fine particles obtained by doping tin oxide with antimony or phosphorus, fine particles obtained by doping zinc oxide with aluminum or gallium, or fine particles obtained by doping titanium oxide with niobium. Accordingly, at least one kind of fine particles among these four kinds of fine particles can be used to constitute transparent conductive fine particles.
As described above, according to this production method , a transparent conductive film that is cheaper than a conventional transparent conductive film can be produced by using transparent conductive fine particles that are cheaper than ITO as well as ITO.

Method of manufacturing a transparent conductive film described above is prepared transparent base material in the method of manufacturing the transparent conductive film described above is the temperature at which thermal decomposition begins the synthetic resin, a transparent conductive film described above In this manufacturing method , the transparent conductive film is a transparent film made of a synthetic resin having a property higher than the temperature at which the metal compound is thermally decomposed.

In other words, according to this production method , the temperature at which the synthetic resin begins to thermally decompose is higher than the temperature at which the metal compound thermally decomposes. Therefore, even after the metal compound is thermally decomposed to deposit metal fine particles, The properties of the resin remain unchanged. Therefore, a transparent film made of a synthetic resin having such properties can be used as an inexpensive transparent base material in the production method for producing the transparent conductive film .
That is, when the temperature of the synthetic resin is raised, the molecular structure in the synthetic resin is gradually cut off from a predetermined temperature, and gradually becomes a low molecular weight synthetic resin, and the properties of the synthetic resin are irreversibly changed. The temperature at which the change in the molecular structure of such a synthetic resin starts is a temperature at which the weight change of the synthetic resin begins, and is measured by thermogravimetry (TG). Therefore, even if the synthetic resin is exposed to a high temperature, if the molecular structure of the synthetic resin does not change, that is, if no weight change occurs, the properties of the synthetic resin do not change.
The temperature in the air atmosphere where the weight change of the synthetic resin starts is, for example, 230 ° C for polyvinyl alcohol resin, 250 ° C for polyvinyl chloride resin, 300 ° C for acrylic resin, 300 ° C for polyacetate resin, polystyrene Resin is 320 ° C, polypropylene resin is 380 ° C, low density polyethylene resin is 400 ° C, polyethylene terephthalate (PET) resin is 440 ° C, polyethersulfone (PES) resin is 480 ° C, polytetrafluoroethylene (PTFE) resin is 480 ° C. and polycarbonate resin is 500 ° C.
Therefore, if the temperature at which the metal compound is thermally decomposed is 220 ° C. or less, a transparent film made of a polyvinyl alcohol film, a polyvinyl chloride film, an acrylic film, a polyacetate film, or the like can be used as the transparent substrate. Moreover, if the temperature at which the metal compound is thermally decomposed is 300 ° C. or lower, a transparent film made of an unstretched polypropylene film, a stretched polystyrene film, a PET film, a PES film, a PTFE film, a polycarbonate film, or the like is used as a transparent substrate. Can do.
As explained above, according to this manufacturing method , a transparent conductive film can be formed on the surface of an inexpensive transparent film made of a synthetic resin.

Method of manufacturing a transparent conductive film described above, the metal compound in the method of manufacturing the transparent conductive film described above is a copper compound to precipitate copper by thermal decomposition, producing a transparent conductive film described above the organic compounds in the manufacturing method, the copper compound is an organic compound having a boiling point lower nature than the thermal decomposition temperature, a method of manufacturing the transparent conductive film described above.

In other words, Oite the method of manufacturing the transparent conductive film described above, the alcohol dispersion of the copper compound, the liquid mixture of organic compounds, when mixed set of transparent conductive particles, the suspension is created The When this suspension is applied to or printed on a transparent substrate and the transparent substrate is heat-treated, after the alcohol and the organic compound are vaporized, the copper compound is thermally decomposed and a collection of transparent conductive fine particles bonded with copper fine particles. A transparent conductive film made of is integrally formed with the transparent substrate.
Copper has a refractive index of 0.60, which is close to the refractive index 1 of air. For this reason, the surface reflectance R described in the ninth paragraph is 6.25%, the total light transmittance T described in the tenth paragraph is 88%, and the total light transmittance close to a float glass having a thickness of 2 m is obtained. Have. Therefore, it is suitable for the material of the metal fine particles constituting the transparent conductive film having high transparency.
Copper has the next highest conductivity after silver, and has an electrical resistivity of 1.68 × 10 ⁻⁸ Ωm. It has the highest conductivity among the transparent conductive materials, and the electrical properties of ITO that has been sufficiently crystal-grown by heat treatment. The conductivity is 120 times higher than the resistivity 2 × 10 ⁻⁶ Ωm. Accordingly, a transparent conductive film made of a collection of transparent conductive fine particles bonded with copper fine particles has necessary conductivity even if the film thickness is smaller than that of a conventional transparent conductive film. This increases the transparency of the transparent conductive film and facilitates pressure bonding to other substrates and parts. Furthermore, since the film thickness of the suspension in printing becomes thin, the viscosity of the suspension is low. For this reason, there is no restriction on the shape and line width of the electrode pattern formed directly on the surface of the transparent substrate.
Furthermore, copper has excellent thermal conductivity after silver, has a thermal conductivity of 401 W / mK, and is 134 times higher in thermal conductivity than the thermal conductivity of ITO, 3.05 W / mK. For this reason, since the thermal conductivity is superior to the conventional transparent conductive film and the heat storage is inferior, the service life is longer than that of the conventional transparent conductive film.
Copper is a general-purpose metal after iron and aluminum, and a copper compound that precipitates copper by thermal decomposition can be easily generated. Moreover, since the metal is rich in malleability, it is easy to press the transparent base material on which the transparent conductive film is formed to other base materials or parts.
As described above, precipitated Oite the method of manufacturing the transparent conductive film described above, the alcohol dispersion of a metal compound, a mixed solution obtained by mixing an organic compound, a metal compound, a copper pyrolysis Consists of a copper compound, and the organic compound is composed of an organic compound whose boiling point is lower than the temperature at which the copper compound is thermally decomposed . The film provides various excellent effects.

In the manufacturing method for manufacturing the transparent conductive film described above, the copper compound in the manufacturing method for manufacturing the transparent conductive film described above is a copper complex in which a ligand composed of an inorganic molecule or ion is coordinated to a copper ion. It is a manufacturing method which manufactures an above described transparent conductive film which is a copper complex which has ion.

That is, the copper complex in this production method is thermally decomposed by exposing it to a reducing atmosphere of 180 to 220 ° C. for about 5 to 10 minutes to precipitate copper. Therefore, a transparent conductive film can be formed on the surface of the transparent film made of the synthetic resin of various materials described in the 16th paragraph.
As such a copper complex, ammonia NH ₃ serves as a ligand to form an ammine complex that coordinates to a copper ion, chlorine ion Cl ⁻ , or chlorine ion Cl ⁻ and ammonia NH ₃ serve as a ligand. A chloro complex that coordinates to a copper ion is easier to synthesize than other copper complexes, and can be produced at a low production cost among copper complexes. These copper complexes have a small ligand molecular weight, so when heat-treated in a reducing atmosphere such as ammonia gas or hydrogen gas, the coordination bond site is first fragmented and thermal decomposition is completed at a low temperature of 180-220 ° C. To do. Moreover, it has the property to disperse | distribute to near 10 weight% in alcohol, such as methanol and n-butanol.
That is, a copper complex is dispersed in alcohol, an organic compound having a low boiling point is mixed with this dispersion, and a collection of transparent conductive fine particles is mixed with this mixture to prepare a suspension. This suspension is applied or printed on the surface of a synthetic resin transparent film, and the transparent film is heat-treated in a reducing atmosphere. When the alcohol and the organic compound are vaporized, when exposed to 180 to 220 ° C. for about 5 to 10 minutes, the copper complex is thermally decomposed to precipitate granular copper particles having a size of 40 to 60 nm. Metal bond. As a result, a transparent conductive film composed of a collection of transparent conductive fine particles bonded with copper fine particles is formed integrally with the transparent film.
As described above, according to the present manufacturing method , the transparent conductive film composed of a collection of transparent conductive fine particles bonded with copper fine particles is formed integrally with the transparent film.

Method of manufacturing a transparent conductive film described above, the organic compound in the method of manufacturing the transparent conductive film described above, the carboxylic acid esters, or Ru any organic compound der consisting glycol ethers, wherein This is a manufacturing method for manufacturing a transparent conductive film .

In other words, according to this manufacturing method, the alcohol dispersion of the copper compound, when mixed with any of the organic compounds in the manufacturing method, the viscosity of the mixture increases with the mixing ratio of the organic compound. When a collection of transparent conductive fine particles is mixed with this mixed liquid, a suspension can be produced. When this suspension is applied or printed on a transparent substrate, a film having a thickness corresponding to the viscosity of the suspension is formed on the transparent substrate. When this transparent substrate is heat-treated, the alcohol is first vaporized, then the organic compound is vaporized, and the copper compound is further thermally decomposed. As a result, a transparent conductive film composed of a collection of transparent conductive fine particles bonded with copper fine particles is formed integrally with the transparent substrate. Therefore, the organic compound in this manufacturing method becomes a regulator which adjusts the viscosity of the suspension in which the copper compound is dispersed.
As such an organic compound, among organic compounds composed of carboxylic acid esters or glycol ethers, an organic compound having a relatively low molecular weight has a boiling point lower than the temperature at which the copper compound is thermally decomposed. Has properties . Such organic compounds are all general industrial chemicals.
As explained above, the organic compound in this production method becomes an inexpensive regulator that adjusts the viscosity of the suspension in which the copper compound is dispersed.

Method of manufacturing a transparent conductive film described above, the metal compound in the method of manufacturing the transparent conductive film described above is an aluminum compound to deposit aluminum in the pyrolysis, to produce transparent conductive film described above the organic compounds in the manufacturing method, the Aruminimu compound is an organic compound having a boiling point lower nature than the thermal decomposition temperature, a method of manufacturing the transparent conductive film described above.

In other words, Oite the method of manufacturing the transparent conductive film described above, the alcohol dispersion of the aluminum compound, the liquid mixture of organic compounds, the suspension to create a mixed a collection of the transparent conductive microparticles When the suspension is applied or printed on a transparent substrate, and the transparent substrate is heat-treated, the alcohol and the organic compound are vaporized, and then the aluminum compound is thermally decomposed to form transparent conductive fine particles bonded with aluminum fine particles. A transparent conductive film made of a group is formed integrally with a transparent substrate.
Aluminum has a refractive index of 1.48 which is close to the refractive index 1 of air. Therefore, the surface reflectance R described in the ninth paragraph is 3.7%, the total light transmittance T described in the tenth paragraph is 93%, and the total light transmittance is higher than that of the float glass having a thickness of 2 mm. Have. Therefore, it is suitable for the material of the metal fine particles constituting the transparent conductive film having high transparency.
Aluminum has the second highest conductivity after silver, copper, and gold, and has an electrical resistivity of 2.82 × 10 ⁻⁸ Ωm. The electrical resistivity of ITO sufficiently grown by heat treatment is 2 × 10 ⁻⁶ Ωm. The conductivity is 71 times higher. Therefore, the transparent conductive film made up of a collection of transparent conductive fine particles bonded with aluminum fine particles has the necessary conductivity even with a thinner film thickness than the conventional transparent conductive film. This increases the transparency of the transparent conductive film and facilitates pressure bonding to other substrates and parts. Moreover, the film thickness of the suspension in printing is thin, and the viscosity of the suspension is low. For this reason, there is no restriction on the shape and line width of the electrode pattern formed directly on the surface of the transparent substrate.
Furthermore, aluminum has excellent thermal conductivity next to silver, copper, and gold, has a thermal conductivity of 237 W / mK, and is 78 times higher in thermal conductivity than the thermal conductivity of ITO, 3.05 W / mK. For this reason, it has better thermal conductivity than conventional transparent conductive films and inferior heat storage, and its service life is longer than that of conventional transparent conductive films.
Aluminum is a general-purpose metal next to iron, and an aluminum compound that precipitates aluminum by pyrolysis can be easily generated. Further, since the metal is rich in malleability, it is easy to press the transparent base material on which the transparent conductive film is formed to other base materials or parts. Furthermore, the density is as small as 2.70 g / cm ³ , which is about twice the density of the synthetic resin, and becomes a lightweight transparent conductive film.
As described above, precipitated Oite the method of manufacturing the transparent conductive film described above, the alcohol dispersion of a metal compound, a mixed solution obtained by mixing an organic compound, a metal compound, an aluminum pyrolysis It is composed of an aluminum compound, and the organic compound is composed of an organic compound whose boiling point is lower than the temperature at which the aluminum compound is thermally decomposed. By using this mixed liquid, the transparent conductivity integrated with the transparent substrate The film provides various excellent effects.

Method of manufacturing a transparent conductive film described above is an aluminum compound in the method of manufacturing the transparent conductive film described above has a first aspect the oxygen ions constituting the mosquitoes carboxyl group is covalently bonded to the aluminum ions, It is an aluminum carboxylate compound that has these two characteristics, consisting of a second characteristic composed of a carboxylic acid composed of a saturated fatty acid.
And a manufacturing method for manufacturing the transparent conductive film described above .

That is, the aluminum carboxylate compound in the present production method is thermally decomposed by exposing it to an air atmosphere at 290 to 400 ° C. for about 1 minute to precipitate aluminum. Therefore, a transparent conductive film can be formed on the surface of glass made of various materials. Further, among the synthetic resins described in paragraph 16, a transparent film made of a synthetic resin having a property that the thermal decomposition starts at a temperature higher than the thermal decomposition temperature of the aluminum carboxylate compound can be used as a transparent substrate.
That is, aluminum ions are the largest among the ions constituting the aluminum carboxylate compound. Therefore, in the carboxylate aluminum compound in which the oxygen ion constituting the carboxyl group is covalently bonded to the aluminum ion, the distance between the oxygen ion constituting the carboxyl group and the aluminum ion is longer than the distance between the other ions. When an aluminum carboxylate compound with these characteristics is heat-treated in an air atmosphere, at the temperature exceeding the boiling point of the carboxylic acid, the bond between the oxygen ion and aluminum ion constituting the carboxyl group is broken and separated into carboxylic acid and aluminum. To do. In addition, when the carboxylic acid is composed of saturated fatty acids, the carboxylic acid takes the heat of vaporization and vaporizes because there is no unsaturated structure in which the carbon atoms are excessive relative to the hydrogen atoms, and all the carboxylic acids are vaporized. After that, aluminum precipitates. Examples of such an aluminum carboxylate compound include aluminum carboxylate compounds such as aluminum octylate, aluminum laurate, and aluminum stearate in the order of decreasing thermal decomposition temperature. In addition, since the carboxylic acid aluminum compound consisting of unsaturated fatty acid has an excess of carbon atoms relative to the hydrogen atom as compared with the carboxylic acid metal compound consisting of saturated fatty acid, aluminum oxide is deposited by thermal decomposition.
Further, the above-described aluminum carboxylate compound is an inexpensive industrial chemical that can be easily synthesized. That is, when a carboxylic acid is reacted with a strong alkali, a carboxylic acid alkali metal compound is produced. Thereafter, when an alkali metal carboxylate compound is reacted with an inorganic aluminum compound, an aluminum carboxylate compound is synthesized.
An aluminum carboxylate compound having such properties is dispersed in alcohol, and an organic compound having a boiling point lower than the temperature at which the aluminum carboxylate compound is thermally decomposed is mixed with this dispersion, and transparent conductive fine particles are gathered in the mixture. To make a suspension. This suspension is applied or printed on the surface of a glass or synthetic resin transparent film, and then the glass or synthetic resin transparent film is heat-treated in an air atmosphere. When the alcohol and the organic compound are vaporized, when exposed to 290-400 ° C. for about 1 minute, the aluminum carboxylate compound is thermally decomposed, and granular aluminum fine particles having a size of 40-60 nm are precipitated, and the adjacent granular particles Aluminum fine particles are metal-bonded to each other. As a result, a transparent conductive film composed of a collection of transparent conductive fine particles bonded with aluminum fine particles is formed integrally with a transparent film of glass or synthetic resin.
As described above, according to the present manufacturing method , a transparent conductive film composed of a collection of transparent conductive fine particles bonded with aluminum fine particles is formed as an inexpensive transparent conductive film on a transparent film of glass or synthetic resin. it can.

In the manufacturing method for manufacturing the transparent conductive film described above, the organic compound in the manufacturing method for manufacturing the transparent conductive film described above is any organic compound composed of carboxylic acid esters, glycol ethers, or glycols. This is a manufacturing method for manufacturing the transparent conductive film .

In other words, according to this manufacturing method, the alcohol dispersion of the aluminum compound, is mixed with any of the organic compound in the manufacturing process, the viscosity of the mixture increases with the mixing ratio of the organic compound. When a collection of transparent conductive fine particles is mixed with this mixed liquid, a suspension can be produced. When this suspension is applied or printed on a transparent substrate, a film having a thickness corresponding to the viscosity of the suspension is formed on the transparent substrate. When this transparent substrate is heat-treated, the alcohol is first vaporized, then the organic compound is vaporized, and the aluminum compound is further thermally decomposed. As a result, a transparent conductive film composed of a collection of transparent conductive fine particles bonded with aluminum fine particles is formed integrally with the transparent substrate. Therefore, the organic compound in the present production method becomes a regulator for adjusting the viscosity of the suspension in which the aluminum compound is dispersed.
As such an organic compound, among organic compounds composed of carboxylic acid esters or glycol ethers, an organic compound having a relatively large molecular weight has a boiling point lower than the temperature at which the aluminum compound is thermally decomposed. Has properties . That is, carboxylic acid esters definitive paragraph 22, or, an organic compound consisting of glycol ethers, the molecular weight is large, a high boiling point. In addition, the boiling point of many glycols is lower than the temperature at which the aluminum compound is thermally decomposed. Such organic compounds are all general industrial chemicals.
As explained above, the organic compound in this production method becomes an inexpensive regulator that adjusts the viscosity of the suspension in which the aluminum compound is dispersed.

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It is a figure which illustrates typically a part of transparent conductive film | membrane with which ATO fine particle was couple | bonded by the coupling | bonding of the copper fine particle discretely deposited on the surface of ATO fine particle. FIG. 2 is a diagram schematically illustrating a state where the transparent conductive film shown in FIG. 1 is integrally formed with an acrylic resin film.

Embodiment 1
This embodiment is an embodiment of a copper compound that thermally decomposes at a low temperature to deposit copper, and as such a substance, a ligand composed of an inorganic molecule or ion is coordinated and bonded to a copper ion. Explain that copper complexes with complex ions are suitable. That is, it is an embodiment of a copper compound that can form a transparent conductive film on a transparent film of a synthetic resin having low heat resistance.
The copper complex can be prepared first by dispersing it in alcohol, and second, when the suspension applied or printed on the transparent substrate is heat-treated, the copper complex is formed on the surface of the transparent substrate. The complex is thermally decomposed and precipitates a collection of copper fine particles.
First, a copper compound having a property of being dispersed in alcohol will be described. Inorganic copper compounds such as copper chloride, copper sulfate, and copper nitrate dissolve in alcohol, and copper ions are eluted, so that many copper ions cannot participate in the precipitation of copper fine particles. Accordingly, it is necessary that the copper compound does not dissolve in the solvent but has a property of being dispersed in the solvent. In addition, inorganic copper compounds such as copper oxide, copper chloride, and copper sulfide are not dispersed in alcohols, which are the most general-purpose solvents. For this reason, these inorganic copper compounds are not suitable as copper compounds having the property of being dispersed in alcohol.
Next, a copper compound having the property of depositing copper by thermal decomposition will be described. Among the chemical reactions in which copper is produced from a copper compound, one of the simplest chemical reactions is a thermal decomposition reaction. That is, only by raising the temperature of the copper compound, the copper compound is thermally decomposed and copper is deposited. Furthermore, if the thermal decomposition temperature of a copper compound is low, a transparent conductive film can be formed on a transparent film made of a synthetic resin having low heat resistance. A copper complex having a copper complex ion coordinated to a copper ion located in the center of the molecular structure, with a molecule or ion consisting of an inorganic substance as a ligand, can be thermally decomposed in a reducing atmosphere if the molecular weight of the inorganic substance is small. The temperature is lower than a temperature at which an organic copper compound in which an organic substance having a higher molecular weight forms a ligand thermally decomposes in an air atmosphere. For this reason, such a copper complex is a relatively expensive substance than an organic copper compound, but deposits a collection of copper fine particles at a lower heat treatment temperature, so that it is transparent on the surface of a transparent film made of an inexpensive synthetic resin. A conductive film can be formed, and as a result, a transparent film on which a transparent conductive film is formed can be manufactured at low cost.
That is, the copper ion is the largest among the molecules constituting the copper complex. Incidentally, the covalent bond radius of copper atoms is 132 ± 4 pm, while the covalent bond radius of nitrogen atoms is 71 ± 1 pm, and the covalent bond radius of oxygen atoms is 66 ± 2 pm. For this reason, in the molecular structure of a copper complex, the distance of the coordinate bond part in which a ligand coordinates-bonds to a copper ion is the longest. Therefore, in the heat treatment in a reducing atmosphere, the coordination bond is first divided and decomposed into copper and an inorganic substance, and copper is deposited after the vaporization of the inorganic substance is completed.
A copper complex having such properties is dispersed in alcohol, an organic compound having a low boiling point is dissolved or mixed in the dispersion, and a collection of transparent conductive fine particles is mixed to prepare a suspension. When this suspension is applied or printed on a transparent substrate and heated in a reducing atmosphere, the alcohol is first vaporized and then the organic compound is vaporized. Thereby, a thin film of the copper complex is formed on the surface layer including the irregularities on the surface of the transparent substrate and on the surface of the transparent conductive fine particles. When the temperature rises further, thermal decomposition of the thin film-like copper complex begins, the copper complex decomposes into copper and inorganic matter, and after the vaporization of the inorganic matter is complete, copper forms granular fine particles and finishes the thermal decomposition reaction . At this time, a collection of copper fine particles is deposited according to the molar concentration of the copper complex dispersed in the alcohol. Since the copper fine particles are in an active state, they are metal-bonded at contact points that contact each other. As a result, a transparent conductive film composed of a collection of transparent conductive fine particles bonded with copper fine particles is formed integrally with the transparent substrate.
Among such copper complexes, ammonia NH ₃ serves as a ligand to form an ammine complex that coordinates to a copper ion, chlorine ion Cl ⁻ , or chlorine ion Cl ⁻ and ammonia NH ₃ serve as a ligand. Thus, the chloro complex coordinated to the copper ion is relatively easy to synthesize compared to other copper complexes, and therefore can be produced at a relatively low production cost. Further, when such a copper complex is heat-treated in a reducing atmosphere such as ammonia gas or hydrogen gas, the coordination bond site is first divided and thermal decomposition is completed at a relatively low temperature of about 200 ° C. Furthermore, it disperse | distributes to alcohol, such as methanol and n-butanol, to the dispersion concentration of about 10 weight%. Examples of such a copper complex ion include tetraammine copper complex ion [Cu (NH ₃ ) ₄ ] ²⁺ or hexaammine copper complex ion [Cu (NH ₃ ) ₆ ] ²⁺ , and examples of the copper complex include tetraammine copper. There is nitrate [Cu (NH ₃ ) ₄ ] (NO ₃ ) ₂ or hexaammine copper sulfate [Cu (NH ₃ ) ₆ ] SO ₄ .
As described above, a copper complex having a copper complex ion in which a ligand composed of an inorganic molecule or ion is coordinated to a copper ion as a material for thermally decomposing a copper compound at a low temperature to precipitate copper. Is appropriate. Thereby, a transparent conductive film can be formed on the surface of a transparent film made of a synthetic resin having low heat resistance.

Embodiment 2
This embodiment is an embodiment of an aluminum compound in which the thermal decomposition temperature is higher than that of the copper complex described above, but is cheaper than the copper complex, and aluminum is precipitated by thermal decomposition. As such a substance, aluminum carboxylate is used. Explain that the compound is suitable. That is, as the most general-purpose transparent substrate, there is glass in addition to the above-described synthetic resin transparent film. Therefore, if a transparent conductive film can be formed on heat resistant glass, an inexpensive transparent conductive film can be formed for applications in which glass is appropriate as a transparent substrate. As a result, the transparent conductive film composed of the aluminum fine particles described in the 24th paragraph can be manufactured. The maximum use temperature of the heat-resistant glass is 500 ° C. or higher, which is higher than the thermal decomposition temperature of the aluminum carboxylate compound, and heat-resistant glass can be used as a transparent substrate. Moreover, if the temperature at which the thermal decomposition of the synthetic resin described in paragraph 16 starts is higher than the thermal decomposition temperature of the aluminum carboxylate compound, a synthetic resin transparent film can be used as the transparent substrate.
Similar to the copper complex described above, the aluminum compound has the two properties of first being dispersed in alcohol and secondly precipitating aluminum by pyrolysis.
First, an aluminum compound dispersed in alcohol will be described. Aluminum chloride dissolves in water and hydrolyzes into aluminum hydroxide and hydrochloric acid. Aluminum hydroxide is not dispersed in alcohol. Furthermore, aluminum sulfate is dissolved in alcohol, and aluminum ions are eluted. Aluminum oxide is not dispersed in alcohol. For this reason, these inorganic aluminum compounds are not dispersed in alcohol. Note that an aluminum complex having an aluminum complex ion coordinated and bonded to an aluminum ion located in the center of the molecular structure is a thermal decomposition because aluminum oxide precipitates aluminum oxide. It does not become a raw material for depositing aluminum by decomposition. For this reason, an inorganic aluminum compound does not become a raw material of aluminum.
Next, the organoaluminum compound has a property of depositing aluminum by thermal decomposition. Among chemical reactions in which aluminum is produced from an organoaluminum compound, one of the simplest chemical reactions is a thermal decomposition reaction. That is, aluminum is deposited only by raising the temperature of the organoaluminum compound. Furthermore, if the synthesis of the organoaluminum compound is easy, it can be manufactured at low cost. An organoaluminum compound having such properties is an aluminum carboxylate compound.
That is, the largest ion among the ions constituting the aluminum carboxylate compound is an aluminum ion. Accordingly, if the oxygen ion constituting the carboxyl group in the aluminum carboxylate compound is covalently bonded to the aluminum ion, the distance between the aluminum ion and the oxygen ion constituting the carboxyl group is the longest among the distances between the ions. When the temperature of the aluminum carboxylate compound having such molecular structure characteristics is raised in the atmosphere, it decomposes into carboxylic acid and aluminum at the boiling point of the carboxylic acid constituting the aluminum carboxylate compound. When the temperature is further increased, if the carboxylic acid is composed of a saturated fatty acid, the carboxylic acid takes the heat of vaporization and vaporizes, and aluminum is deposited after the vaporization of the carboxylic acid is completed. Note that the thermal decomposition of the aluminum carboxylate compound in the reducing atmosphere proceeds at a higher temperature than the thermal decomposition in the air atmosphere, and therefore the heat decomposition cost in the air atmosphere is lower. Further, if the carboxylic acid is an unsaturated fatty acid, the carbon atoms are excessive with respect to the hydrogen atoms, so that when the carboxylic acid aluminum compound composed of the unsaturated fatty acid is thermally decomposed, an aluminum oxide is deposited. In addition, an aluminum carboxylate compound in which the oxygen ion constituting the carboxyl group becomes a ligand and approaches the aluminum ion to form a coordinate bond, the distance between the aluminum ion and the oxygen ion is shortened. The distance between the ion and the ion bonded on the opposite side is the longest. In such a thermal decomposition reaction of an aluminum carboxylate compound, a bonded portion between an oxygen ion and an ion bonded on the opposite side of the aluminum ion is first divided, and as a result, aluminum oxide is precipitated.
An aluminum carboxylate compound is an organic aluminum compound that is easy to synthesize and inexpensive. That is, when a carboxylic acid is reacted in a strong alkali solution such as sodium hydroxide, a carboxylic acid alkali metal 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. Hereinafter, embodiments of the aluminum carboxylate compound will be described.
The composition formula of the aluminum carboxylate compound is expressed by Al (COOR) ₃ . R is a hydrocarbon, and this compositional 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 at 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. This is because the covalent bond radius of aluminum ion atoms is 121 ± 4 pm, the covalent bond radius of oxygen ion atoms is 66 ± 2 pm, and the covalent bond radius of carbon atoms is 73 pm. Therefore, an aluminum carboxylate compound in which an aluminum ion and an oxygen ion constituting a carboxyl group are covalently bonded has a bonding portion between the aluminum ion having the longest bond distance and the oxygen ion constituting the carboxyl group at the boiling point of the carboxylic acid. It is divided first and separated into aluminum and carboxylic acid. When the temperature is further increased, if the carboxylic acid is a saturated fatty acid, the carboxylic acid takes the heat of vaporization and vaporizes, and aluminum is deposited after the vaporization of the carboxylic acid is completed. Examples of such an aluminum carboxylate compound include aluminum octylate, aluminum laurate, and aluminum stearate. Many of such aluminum carboxylate compounds are inexpensive industrial chemicals marketed as metal soaps.
Furthermore, regarding the carboxylate aluminum compound composed of saturated fatty acid, if the boiling point of the saturated fatty acid is relatively low, the aluminum carboxylate compound is thermally decomposed at a relatively low temperature, and the heat treatment cost for depositing 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 higher the molecular weight of the saturated fatty acid, the higher the boiling point of the saturated fatty acid. Incidentally, the boiling point at atmospheric pressure of lauric acid having a molecular weight of 200.3 is 296 ° C., and the boiling point of stearic acid having a molecular weight of 284.5 at 361 ° C. is 361 ° C. Therefore, an aluminum carboxylate compound composed of a saturated fatty acid having a relatively low molecular weight is desirable as a raw material for depositing aluminum because the thermal decomposition temperature is relatively low.
Further, when the saturated fatty acid has a branched chain structure, the chain length is shorter than that of the saturated fatty acid having a linear structure, and the boiling point is relatively low. As a result, the aluminum carboxylate compound comprising a saturated fatty acid having a branched chain structure undergoes a thermal decomposition temperature at a relatively low temperature. In addition, since saturated fatty acids having a branched chain structure are polar, aluminum carboxylates composed of saturated fatty acids having a branched chain structure are also polar and disperse in a relatively high proportion in organic solvents having a polarity such as alcohol. . Octyl acid is a saturated fatty acid having such a branched structure. That is, octylic acid has a structural formula represented by CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) COOH, and is branched into an alkane of CH ₃ (CH ₂ ) ₃ and C ₂ H ₅ with CH. Carboxyl group COOH binds. The boiling point of octylic acid at atmospheric pressure is 228 ° C., which is 68 ° C. lower than that of lauric acid. For this reason, aluminum octylate having a low thermal decomposition temperature is desirable as a raw material for depositing aluminum. Aluminum octylate is thermally decomposed at 290 ° C. in an air atmosphere to precipitate aluminum, and is dispersed up to 10% by weight in methanol, n-butanol or the like.
As described above, by using aluminum octylate as a raw material for aluminum fine particles, an inexpensive transparent conductive film can be formed on a heat-resistant glass or a transparent film of synthetic resin.

Embodiment 3
In the present embodiment, firstly, it is dissolved or mixed in alcohol, secondly, the alcoholic solution or alcoholic mixture has a higher viscosity than alcohol, and thirdly, at least one of a copper complex and an aluminum carboxylate compound. It is an embodiment relating to an organic compound having these three properties, the boiling point of which is lower than the temperature at which one metal compound is thermally decomposed. In other words, if the boiling point of the organic compound is lower than the temperature at which the copper complex is thermally decomposed, the organic compound forms a suspension together with the alcohol dispersion of the copper complex, and the boiling point of the organic compound is thermally decomposed by the aluminum carboxylate compound. If it is lower than the temperature, it forms a suspension together with an alcohol dispersion of an aluminum carboxylate compound, and the organic compound becomes a regulator for adjusting the viscosity in these suspensions. On the other hand, if the boiling point of the organic compound is higher than the temperature at which the copper complex is thermally decomposed and lower than the temperature at which the aluminum carboxylate compound is thermally decomposed, the organic compound forms a suspension together with the alcohol dispersion of the aluminum carboxylate compound. To do. By the way, the copper complex is thermally decomposed at 180-220 ° C. and the aluminum carboxylate compound is thermally decomposed at 290-400 ° C.
Examples of the organic compound having the above three properties include carboxylic acid esters, glycols, and glycol ethers.
Carboxylic acid esters are obtained by condensation reaction of carboxylic acid and alcohol or phenol, and are acetic acid esters, propionic acid esters, butyric acid esters, bivalic acid esters, caproic acid esters, caprylic acid esters, capric acid. Esters, lauric acid esters, myristic acid esters, palmitic acid esters, stearic acid esters, saturated carboxylic acid esters, acrylic acid esters, crotonic acid esters, methacrylic acid esters, olein There are enormous numbers of carboxylic acid esters such as esters with unsaturated carboxylic acids composed of acid esters and the like, and esters with aromatic carboxylic acids composed of benzoic acid esters and phthalic acid esters.
Further, among the saturated carboxylic acids, acetates which are esters of acetic acid and alcohol or phenol having a low molecular weight include methyl acetate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, octyl acetate, heptyl acetate, acetic acid. There are acetates such as benzyl, phenyl acetate and vinyl acetate. Acetic esters other than methyl acetate have a higher boiling point than methanol and a lower boiling point than n-butanol. Moreover, it melt | dissolves in methanol and a methanol solution has a viscosity higher than methanol. For this reason, a conductive paste is manufactured by dispersing a copper complex or an aluminum carboxylate compound in methanol and mixing any one of acetates excluding methyl acetate with this dispersion.
For example, vinyl acetate (monomer) is dissolved in methanol, has a higher viscosity than methanol, and has a boiling point of 72.7 ° C. higher than that of methanol. Therefore, when a copper complex or an aluminum carboxylate compound is dispersed in methanol and vinyl acetate is mixed with this dispersion, the viscosity of the dispersion increases according to the amount of the mixed vinyl acetate to form a suspension. Vinyl acetate is a general-purpose organic compound used as a raw material used for the synthesis of polyvinyl acetate.
Further, methyl laurate is an ester of lauric acid and alcohol having a large molecular weight among saturated fatty acids. Methyl laurate dissolves in n-butanol, has a higher viscosity than n-butanol, has a boiling point higher than that of n-butanol, is higher than the temperature at which the copper complex is thermally decomposed, and the aluminum carboxylate compound is thermally decomposed It is 262 ° C. lower than the temperature. Therefore, when an aluminum carboxylate compound is dispersed in n-butanol and methyl laurate is mixed with this dispersion, the viscosity of the dispersion increases in accordance with the amount of the mixed methyl laurate to form a suspension. Note that methyl laurate is a general-purpose organic compound used as a raw material for synthetic fiber oils, metal oils, synthetic lubricants, synthetic resins, cosmetics, and surfactants.
As described above, the esters obtained by the condensation reaction of the saturated fatty acid and the alcohol have been described with respect to acetate esters having a small molecular weight and lauric acid esters having a large molecular weight. Many saturated fatty acid esters, such as acetates, with low molecular weight are soluble in methanol, have a higher viscosity than methanol, have a boiling point higher than that of methanol, and lower than the temperature at which the copper complex thermally decomposes. And a suspension using a copper complex or an aluminum carboxylate as a metal raw material. In addition, many saturated fatty acid esters having a large molecular weight such as lauric acid dissolve in n-butanol, have a higher viscosity than n-butanol, have a boiling point higher than that of n-butanol, and thermally decompose the copper complex. Although the temperature is higher than the temperature but lower than the temperature at which the aluminum carboxylate compound is thermally decomposed, a suspension using the aluminum carboxylate compound as an aluminum raw material is formed.
On the other hand, acrylic acid esters obtained by condensation reaction of acrylic acid and alcohol, which is an unsaturated carboxylic acid having a low molecular weight, include methyl acrylate having a boiling point of 80 ° C., ethyl acrylate having a boiling point of 100 ° C., and boiling point of 132 ° C. Isobutyl acrylate, butyl acrylate having a boiling point of 148 ° C., and 2-ethylhexyl acrylate having a boiling point of 214 ° C. Methyl acrylate and ethyl acrylate are dissolved in methanol, have a higher viscosity than methanol, and have a boiling point higher than that of methanol. For this reason, a copper complex or an aluminum carboxylate compound is dispersed in methanol, and methyl acrylate or ethyl acrylate is mixed with this dispersion to form a suspension. The boiling point of butyl acrylate and isobutyl acrylate is higher than the boiling point of n-butanol and lower than the temperature at which the copper complex is thermally decomposed. For this reason, a copper complex or an aluminum carboxylate compound is dispersed in n-butanol, and butyl acrylate or isobutyl acrylate is mixed with this dispersion to form a suspension.
Further, butyl acrylate is dissolved in n-butanol and has a boiling point of 148 ° C. higher than that of n-butanol. Therefore, when a copper complex or an aluminum carboxylate compound is dispersed in n-butanol and butyl acrylate is mixed with this dispersion, the viscosity of the dispersion increases according to the amount of the mixed butyl acrylate, Configure. Note that butyl acrylate is an inexpensive organic compound used as a raw material for fiber treatment agents, adhesives, paints, synthetic resins, acrylic rubbers, and emulsions.
In addition, esters with crotonic acid and methacrylic acid, which are unsaturated carboxylic acids having a molecular weight greater than that of acrylic acid, have the same properties as the acrylic esters described above.
On the other hand, the glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like.
Ethylene glycol is a liquid monomer that dissolves in methanol and n-butanol and has a boiling point of 197 ° C. Further, diethylene glycol is a liquid monomer having a boiling point of 244 ° C. dissolved in methanol and n-butanol. Further, propylene glycol is a liquid monomer that is miscible with methanol and n-butanol and has a boiling point of 188 ° C. Further, dipropylene glycol is a liquid monomer that is miscible with methanol and n-butanol and has a boiling point of 232 ° C. Tripropylene glycol is a liquid monomer that is miscible with methanol and n-butanol and has a boiling point of 265 ° C. Thus, the boiling point of glycols is higher than the temperature at which the copper complex is thermally decomposed and is lower than the thermal decomposition temperature of the aluminum carboxylate compound. Therefore, a suspension using an aluminum carboxylate compound as a raw material for aluminum is formed. Glycols are not only used as intermediate raw materials for resins, but also have excellent properties as a solvent, and also take advantage of features such as wetting, moisturizing, preserving, emulsifying, high boiling point, low freezing point, foods, pharmaceuticals, cosmetics, It is a general-purpose organic compound that is widely used in heating media, refrigerants, antifreezes, and the like.
On the other hand, glycol ethers include ethylene glycol ethers, propylene glycol ethers, and dialkyl glycol ethers in which hydrogen at the terminals of ethylene glycol, diethylene glycol, and triethylene glycol is substituted with an alkyl group.
Ethylene glycol ethers are methyl glycol, methyl diglycol, methyl triglycol, methyl polyglycol, isopropyl glycol, isopropyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, hexyl glycol, hexyl Examples include diglycol, 2-ethylhexyl glycol, 2-ethylhexyl diglycol, allyl glycol, phenyl glycol, phenyl diglycol, benzyl glycol, and benzyl diglycol.
Among them, methyl glycol having a boiling point of 125 ° C, isopropyl glycol having a boiling point of 142 ° C, butyl glycol having a boiling point of 171 ° C, isobutyl glycol having a boiling point of 161 ° C, and allyl glycol having a boiling point of 159 ° C are n -Dissolves in butanol, has a higher viscosity than n-butanol, has a boiling point higher than that of n-butanol and lower than the temperature at which the copper complex is thermally decomposed. For this reason, a mixed solution in which a copper complex or an aluminum carboxylate compound is dispersed in n-butanol and any one of these ethylene glycol ethers is mixed with this dispersion constitutes a suspension.
In addition, ethylene glycol ethers other than the above five types of ethylene glycol ethers dissolve in n-butanol, have a higher viscosity than n-butanol, have a boiling point higher than that of n-butanol, and the copper complex is thermally decomposed. Is lower than the temperature at which the aluminum carboxylate compound is thermally decomposed. For this reason, a mixed liquid in which an aluminum carboxylate compound is dispersed in n-butanol and any one of these ethylene glycol ethers is mixed with this dispersion constitutes a suspension.
Butyl triglycol (hereinafter referred to as BTG) is dissolved in n-butanol and has a boiling point of 271 ° C., which is lower than the temperature at which the aluminum carboxylate compound is thermally decomposed. Therefore, when an aluminum carboxylate compound is dispersed in n-butanol and BTG is mixed with this dispersion, the viscosity of the dispersion increases in accordance with the amount of the mixed BTG, thereby forming a suspension. BTG is a general-purpose organic compound used as a raw material for paints, inks, dyes, photographic copying liquids, cleaning agents, electrolytic solutions, soluble oils, hydraulic fluids, brake fluids, refrigerants, antifreezing agents, and the like.
The propylene glycol ethers include methyl propylene glycol, methyl propylene diglycol, methyl propylene triglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, butyl propylene diglycol, butyl propylene triglycol, phenyl propylene glycol, Examples include methylpropylene glycol acetate.
Among them, methyl propylene glycol having a boiling point of 121 ° C., propyl propylene glycol having a boiling point of 150 ° C., butyl propylene glycol having a boiling point of 170 ° C., and methyl propylene glycol acetate having a boiling point of 146 ° C. are dissolved in n-butanol. It has a higher viscosity than n-butanol and has a boiling point higher than that of n-butanol and lower than the temperature at which the copper complex is thermally decomposed. For this reason, a mixed solution in which a copper complex or an aluminum carboxylate compound is dispersed in n-butanol and any one of these ethylene glycol ethers is mixed with this dispersion constitutes a suspension.
In addition, propylene glycol ethers other than the four types of propylene glycol ethers described above are dissolved in n-butanol, have a higher viscosity than n-butanol, have a boiling point higher than that of n-butanol, and the copper complex is thermally decomposed. Is lower than the temperature at which the aluminum carboxylate compound is thermally decomposed. For this reason, a mixed liquid in which an aluminum carboxylate compound is dispersed in n-butanol and any one of these ethylene glycol ethers is mixed with this dispersion constitutes a suspension.
Further, dialkyl glycol ethers include dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl diglycol, dibutyl diglycol, dimethylpropylene diglycol and the like. Among them, dimethyl glycol is dissolved in methanol, has a higher viscosity than methanol, and has a boiling point of 85 ° C. higher than that of methanol. For this reason, a mixed solution in which a copper complex or an aluminum carboxylate compound is dispersed in methanol and dimethyl glycol is mixed with this dispersion constitutes a suspension. Also, dimethyldiglycol having a boiling point of 162 ° C. and dimethylpropylene diglycol having a boiling point of 176 ° C. are dissolved in n-butanol and have a higher viscosity than n-butanol, and the boiling point is higher than that of n-butanol. The temperature is lower than the temperature at which the copper complex is thermally decomposed. For this reason, a mixed solution in which a copper complex or an aluminum carboxylate compound is dispersed in n-butanol and these dispersions are mixed with these dialkyl glycol ethers constitutes a suspension. Furthermore, dialkyl glycol ethers other than the above-mentioned three types of dialkyl glycol ethers dissolve in n-butanol, have a higher viscosity than n-butanol, have a boiling point higher than that of n-butanol, and the copper complex is thermally decomposed. It is higher than the temperature but lower than the temperature at which the aluminum carboxylate compound thermally decomposes. For this reason, a mixed liquid in which an aluminum carboxylate compound is dispersed in n-butanol and any one of these dialkyl glycol ethers is mixed with this dispersion constitutes a suspension.
Ethylene glycol ethers and propylene glycol ethers are used as raw materials for paints, inks, dyes, photocopy liquids, cleaning agents, electrolytes, soluble oils, hydraulic fluids, brake fluids, refrigerants, antifreezes, etc. It is a general-purpose organic compound. Dialkyl glycol ether is a general-purpose organic compound used as a raw material for a reaction solvent, a separation / extraction agent, a polymerization solvent, a decomposition preventing and stabilizing agent, an electrolytic solution for batteries and capacitors, in addition to the above-mentioned applications.
As explained above, among the carboxylic acid esters, glycols, or glycol ethers, the organic compound having the three properties explained at the beginning is combined with the alcohol dispersion of the copper complex explained in the 33rd paragraph. The suspension constitutes a suspension together with the alcohol dispersion of the carboxylic acid aluminum compound described in paragraph 34, and becomes a regulator for adjusting the viscosity in these suspensions.

Example 1
In this example, a transparent conductive film made of a collection of transparent conductive fine particles bonded with copper fine particles is formed on the surface of a synthetic resin transparent film. A transparent film of acrylic resin (for example, product number HBS006, manufactured by Mitsubishi Rayon Co., Ltd.) is used as the transparent film, and fine particles obtained by doping antimony into tin oxide as the transparent conductive fine particles (hereinafter referred to as “ATO” for abbreviation of Antimony Tin Oxide). For example, a product of SIGMA-ALDRICH Co., Ltd., product number 549541) is used, and tetraammine copper nitrate [Cu (NH ₃ ) ₄ ] which is a nitrate of tetraammine copper ion [Cu (NH ₃ ) ₄ ] ²⁺ as a raw material for copper fine particles. (NO ₃ ) ₂ (for example, a product of Mitsuwa Chemicals) was used, and vinyl acetate (monomer) (for example, a product of Showa Denko KK) was used as the organic compound. The film thickness of the acrylic resin transparent film is 50 μm, the size of the ATO fine particles is smaller than 50 nm, and the specific surface area is 47 m ² / g. The transparent film is not limited to an acrylic resin, and a synthetic resin transparent film of the materials listed in the 16th paragraph can be used. The transparent conductive fine particles are not limited to ATO fine particles, and transparent conductive fine particles of the materials listed in the 14th paragraph can be used.
First, 51 g corresponding to 0.2 mol of tetraammine copper nitrate is dispersed in methanol at a ratio of 10% by weight. Vinyl acetate (monomer) is mixed in the dispersion at a ratio of 5% by weight. This mixed liquid is put into an ultrasonic bath (for example, an ultrasonic cleaner Model 8800-J manufactured by Emanson Japan). Furthermore, 45.2 g of ATO fine particles (corresponding to 0.3 mol of tin oxide) was mixed in the ultrasonic bath, the ultrasonic bath was operated for 10 minutes, and the mixture was stirred with an ultrasonic spherical wave to suspend the suspension. It was created.
Next, the suspension was screen-printed with a thickness of 5 μm on the surface of a 10 cm × 10 cm acrylic resin film (the printing machine is, for example, a product MTVC-320 manufactured by Microtech Co., Ltd.). Furthermore, the acrylic resin film was heat-treated in a hydrogen gas atmosphere. First, the temperature was raised to 75 ° C. to vaporize methanol and vinyl acetate. Next, it was left at 200 ° C. for 5 minutes to thermally decompose tetraammine copper nitrate.
About the sample manufactured on the said conditions, both the surface and several cut | disconnected cross sections were observed with the electron microscope. As the electron microscope, an extremely low acceleration voltage SEM owned by JFE Techno-Research Corporation was used. This apparatus can observe the surface with an extremely low acceleration voltage from 100 V, and can directly observe the surface of the sample without forming a conductive film.
First, a secondary electron beam between 900 to 1000 V of the reflected electron beam from various portions of the surface of the sample and a plurality of cross sections was taken out and image processing was performed. Two types of fine particles were observed on any part of the sample surface, and among these, larger granular fine particles had a size of 40-60 nm and protruded from the surface. As for the sample cross section, two kinds of fine particles were observed in any part. Among these, smaller spherical fine particles were fine particles smaller than 50 nm and were discretely surrounded by granular fine particles. The gathering of the two types of fine particles formed a thickness of 0.5 μm.
Next, image processing was performed by extracting energy between 900-1000 V of the reflected electron beam from various parts of the surface of the sample and a plurality of cross sections, and the difference in the material of the fine particles was observed depending on the density of the image. . The granular fine particles were not composed of light and shade, and were composed of the same atoms. On the other hand, shading was observed in the spherical fine particles.
Furthermore, image processing was performed on the energy and intensity of characteristic X-rays from various parts of the sample surface and a plurality of cross sections, and the types of elements constituting the fine particles were analyzed. Since the particulate fine particles are composed only of copper atoms, they are copper particulate fine particles. On the other hand, the spherical fine particles were composed of oxygen atoms, tin atoms, and very few antimony atoms, and the amount of oxygen atoms was twice that of tin atoms. For this reason, the spherical fine particles are ATO fine particles.
From the above observation results, it was found that the ATO fine particles are discretely surrounded by the copper fine particles, and the ATO fine particles are bound by the copper fine particles.
Furthermore, the total light transmittance of the sample was measured with a haze meter (for example, a spectroscopic haze meter model NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.). The used acrylic resin transparent film had a total light transmittance of 93% in the visible light wavelength region of 380 nm or more, but the prepared sample showed a total light transmittance of 91%.
Moreover, the surface resistance value of the sample surface was measured with the surface resistance meter (for example, surface resistance meter ST-4 of Simco Japan Co., Ltd.). Since the surface resistance value was less than 1 × 10 ³ Ω / □, the sample has a surface resistance close to that of a metal.
Furthermore, as a result of measuring the bonding strength of the prepared transparent conductive film to the transparent film based on the adhesive strength test method defined in JIS-Z0237, it withstood a load of 5500 g. For this reason, a transparent conductive film has sufficient handling property, and can be crimped | bonded to the surface of various base materials and components.
From the results described above, a transparent conductive film in which copper fine particles discretely deposited on the surface of the ATO fine particles are metal-bonded to bond the ATO fine particles is formed on the surface of the transparent film. This transparent conductive film had a total light transmittance close to that of glass and a conductivity close to that of metal.
The above results are schematically shown in FIG. 1 for the bonding state of two types of fine particles. 1 is a transparent conductive film, 2 is a copper fine particle, and 3 is an ATO fine particle. Moreover, the state in which the transparent conductive film was formed on the surface of the transparent film was schematically shown in FIG. 4 is a transparent conductive film, and 5 is a transparent film of acrylic resin.

Example 2
In this example, a transparent conductive film made of a collection of transparent conductive fine particles bonded with aluminum fine particles is formed on the surface of a synthetic resin transparent film. A transparent film of PET resin (for example, brand K in the product of Teijin DuPont Film Co., Ltd.) is used as the transparent film, the ATO fine particles in Example 1 are used as the transparent conductive fine particles, and aluminum octylate Al ( C ₇ H ₁₅ COO) ₃ (for example, a product of Hope Pharmaceutical Co., Ltd.) was used, and the vinyl acetate (monomer) in Example 1 was used as the organic compound. The film thickness of the PET resin film is 50 μm. The transparent film is not limited to the PET resin, and any synthetic resin that starts thermal decomposition at a temperature higher than 290 ° C. at which aluminum octylate is thermally decomposed can be used among the synthetic resins of the materials listed in the 16th paragraph. The transparent conductive fine particles are not limited to ATO fine particles, and transparent conductive fine particles of the materials listed in the 14th paragraph can be used.
First, 92 g corresponding to 0.2 mol of aluminum octylate is dispersed in methanol at a ratio of 10% by weight. Vinyl acetate (monomer) is mixed with this dispersion at a ratio of 5% by weight. This mixed solution is put into the ultrasonic bath used in Example 1. Furthermore, 45.2 g of ATO fine particles (corresponding to 0.3 mol of tin oxide) was mixed in the ultrasonic bath, the ultrasonic bath was operated for 10 minutes, and the mixture was stirred with an ultrasonic spherical wave to suspend the suspension. It was created.
Next, the suspension was screen-printed with a thickness of 5 μm on the surface of a 10 cm × 10 cm PET resin film in the same manner as in Example 1. Furthermore, the PET resin film was heat-treated in an air atmosphere. First, the temperature was raised to 75 ° C. to vaporize methanol and vinyl acetate. Next, it was left at 290 ° C. for 1 minute to thermally decompose aluminum octylate.
About the sample manufactured on the said conditions, similarly to Example 1, both the surface and several cut | disconnected cross sections were observed with the electron microscope.
First, the secondary electron beam between 900-1000 V of the reflected electron beam from various parts of the surface of the sample and a plurality of cross sections was taken out and image processing was performed. Two types of fine particles were observed on any part of the sample surface. Among these, larger granular fine particles had a size of 40-60 nm and protruded from the surface. In any part of the sample cross section, two kinds of fine particles were observed. Among these, smaller spherical fine particles were fine particles smaller than 50 nm and were discretely surrounded by granular fine particles. Note that the collection of the two types of fine particles formed a thickness of 0.5 μm.
Next, image processing was performed by extracting energy between 900-1000 V of the reflected electron beam from various parts of the surface of the sample and a plurality of cross sections, and the difference in the material of the fine particles was observed depending on the density of the image. . The granular fine particles were not composed of light and shade, and were composed of the same atoms. On the other hand, shading was observed in the spherical fine particles.
Furthermore, image processing was performed on the energy and intensity of characteristic X-rays from various parts of the sample surface and a plurality of cross sections, and the types of elements constituting the fine particles were analyzed. Since the particulate fine particles are composed of only aluminum atoms, they are aluminum particulate particulates. On the other hand, the spherical fine particles were composed of oxygen atoms, tin atoms, and very few antimony atoms, and the amount of oxygen atoms was twice that of tin atoms. For this reason, the spherical fine particles are ATO fine particles.
From the above observation results, it was found that the ATO fine particles are discretely surrounded by the aluminum fine particles, and the ATO fine particles are bound by the aluminum fine particles.
Further, the total light transmittance of the sample was measured with a haze meter in the same manner as in Example 1. The used acrylic resin transparent film had a total light transmittance of 93% in the visible light wavelength region of 380 nm or more, but the prepared sample showed a total light transmittance of 91%.
Further, the surface resistance value of the sample surface was measured by a surface resistance meter in the same manner as in Example 1. Since the surface resistance value was less than 1 × 10 ³ Ω / □, the sample has a surface resistance close to that of a metal.
Furthermore, as a result of measuring the bonding strength of the prepared transparent conductive film to the transparent film based on the adhesive strength test method defined in JIS-Z0237, the test piece withstands a load of 500 g. For this reason, a transparent conductive film has sufficient handling property, and can be crimped | bonded to the surface of various base materials and components.
From the above results, a transparent conductive film was formed on the surface of the transparent film in which the aluminum fine particles discretely deposited on the surface of the ATO fine particles were metal-bonded to bond the ATO fine particles. This transparent conductive film had a total light transmittance close to that of glass and a conductivity close to that of metal.

Although the two embodiments related to the manufacture of the transparent conductive film integrated with the transparent base material have been described, the manufacture of the transparent conductive film integrated with the transparent base material according to the present invention is described in these two embodiments. It is not limited to. That is, in the same manner as the copper complex described in Example 1, by using a metal complex in which a molecule or ion made of an inorganic substance having a low molecular weight serves as a ligand and is coordinated to a metal ion, a metal that replaces copper fine particles is used. A transparent conductive film is produced on the transparent film of synthetic resin by the fine particles. Further, by using a metal octylate compound in place of aluminum octylate, a transparent conductive film is produced on a transparent film of synthetic resin by using metal fine particles in place of aluminum fine particles. Furthermore, if the temperature at which the thermal decomposition of the synthetic resin begins is higher than the temperature at which the metal complex or the metal octylate compound thermally decomposes, various synthetic resin transparent films can be used as the transparent substrate.
Further, a method for producing a transparent conductive film integrated with a transparent substrate according to the present invention includes a step of producing a suspension, a step of applying or printing the suspension on the transparent substrate, and a transparent substrate. It consists of only three extremely simple processing steps consisting of a step of heat-treating. For this reason, the transparent conductive film united with the transparent substrate can be manufactured at a very low cost. Moreover, there is no restriction | limiting in the magnitude | size of the transparent base material which apply | coats or prints a suspension.
In the present invention, the transparent conductive film integrated with the transparent base material has a structure in which the transparent conductive fine particles are bonded by the metal fine particles deposited by the thermal decomposition of the metal compound, and the refractive index of the metal constituting the metal fine particles. 2.0 or less, the size of the deposited fine metal particles is one tenth of the wavelength of visible light, and the size of the transparent conductive fine particles is one tenth or less of the wavelength of visible light. A transparent conductive film having these three properties, which has high transmittance, high transparency to visible light, and higher conductivity than the material of transparent conductive fine particles, can be manufactured integrally with a transparent substrate. .

DESCRIPTION OF SYMBOLS 1 Transparent conductive film 2 Copper fine particle 3 ATO fine particle 4 Transparent conductive film 5 Acrylic resin transparent film

Claims (10)

Method of manufacturing a magnetic BenQ material and a transparent conductive film formed by integrating the first metal compound in which the metal refractive index of 2.0 or less to precipitate pyrolysis dispersed in alcohol to create an alcohol dispersion One step, a first property dissolved or mixed in alcohol, a solution dissolved in alcohol or a mixed solution mixed in alcohol, a second property having a higher viscosity than the alcohol, and the metal compound being heated The second step of preparing a mixed solution by mixing the organic compound having these three properties, which has a boiling point lower than the decomposition temperature , with the alcohol dispersion prepared in the first step. If, grain child magnitude a collection of the transparent conductive fine particles of less than one tenth of the wavelength of visible light, third creating a suspension by mixing the mixed solution prepared in the second step and a step, On the surface of the BenQ material, annealing the third and fourth step of applying or printing a suspension created in step, a transparent substrate suspension created in the fourth step has been applied or printed It said metal compound consists of a fifth step of thermally decomposing Te, the manufacturing method continuously carried out these five steps, a method of manufacturing the transparent conductive film integrated with the transparent substrate. A manufacturing method for manufacturing a substrate or a part to which the properties of the transparent conductive film according to claim 1 are imparted is a transparent conductive film integrated with a transparent substrate manufactured by the manufacturing method according to claim 1. and a compressive load was applied by placing on a substrate or part article, a method of the transparent conductive film is bonded to the substrate or the component, the nature of the transparent conductive film according to claim 1 is applied A manufacturing method for manufacturing a base material or component . 2. The method for producing a transparent conductive film according to claim 1, wherein the transparent conductive fine particles according to claim 1 are fine particles obtained by doping indium oxide with tin, fine particles obtained by doping tin oxide with antimony or phosphorus, and zinc oxide. 2. The transparent conductive fine particle according to claim 1, which is a transparent conductive fine particle composed of at least one fine particle among these four kinds of fine particles doped with aluminum or gallium, or fine particles obtained by doping niobium into titanium oxide . A manufacturing method for manufacturing a transparent conductive film . In the method for producing a transparent conductive film according to claim 1, the transparent substrate in the claims 1, temperature at which thermal decomposition begins the synthetic resin, a metal compound is thermally decomposed according to claim 1 The manufacturing method which manufactures the transparent conductive film of Claim 1 which is a transparent film consisting of a synthetic resin with a property higher than temperature. In the method for producing a transparent conductive film according to claim 1, the metal compound in 請 Motomeko 1 is a copper compound to precipitate copper in the pyrolysis, the organic compounds in claim 1, wherein the copper compound is boiling point than the thermal decomposition temperature of the organic compound having a low nature, a method of manufacturing the transparent conductive film according to claim 1. 6. The method for producing a transparent conductive film according to claim 5, wherein the copper compound according to claim 5 has a copper complex ion in which a ligand composed of an inorganic molecule or ion is coordinated to a copper ion. The manufacturing method which manufactures the transparent conductive film of Claim 5 which is a complex. In the method for producing a transparent conductive film according to claim 5, the organic compound in claim 5, carboxylic acid esters, or, Ru any organic compound der consisting glycol ethers, in claim 5 A manufacturing method for manufacturing the described transparent conductive film . In the method for producing a transparent conductive film according to claim 1, the metal compound in 請 Motomeko 1, be aluminum compound to deposit aluminum with the pyrolysis
, Organic compounds in claim 1, a manufacturing method of the Aruminimu compound having a boiling point than the thermal decomposition temperature of the organic compound having a low nature, to produce a transparent conductive film according to claim 1. In the method for producing a transparent conductive film according to claim 8, the aluminum compound in claim 8, a first feature of the oxygen ions is covalently attached to the aluminum ions constituting mosquitoes carboxyl group, consisting of saturated fatty acids The manufacturing method which manufactures the transparent conductive film of Claim 8 which is a carboxylate aluminum compound which consists of the 2nd characteristic comprised by carboxylic acid, and has these two characteristics. In the method for producing a transparent conductive film according to claim 8, the organic compounds in claim 8, carboxylic acid esters, glycol ethers, or, Ru any organic compound der consisting glycols, wherein Item 9. A method for producing the transparent conductive film according to Item 8 .

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