JP2005216692A - Resin molding and its method of manufacture - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molding given a transparent conductive film, a resin molding provided with a solar battery using it and its method of manufacture. <P>SOLUTION: A transparent conductive sheet is placed inside a metal mold for injection molding, carrying out molding of the substrate consisting of synthetic resin by injection molding and the transparent conductive sheet is integrated to its surface. The transparent conductive film can be given even to a comparatively complicated shaped object and the sheet can also be inserted into places where it is needed. Furthermore, by having the sheet provided with the transparent conductive film inserted into the metal mold and molded integrally with the injection molding and providing a dye-sensitized solar cell on the molding by using the transparent conductive film on the resin molding surface, the solar cell can be provided directly on objects. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin molded product having a transparent conductive film and a resin molded product having a dye-sensitized solar cell using the transparent conductive film.

  A transparent conductive film that transmits light and has conductivity is formed on a light-transmitting substrate and used as an electrode for a solar cell, an electrode for a liquid crystal display, an electrode for a touch panel, an EL lamp, etc. Widely used.

  There are various kinds of transparent conductive films, such as indium tin oxide (ITO), tin oxide doped with fluorine (FTO), indium zinc oxide (IZO), zinc oxide doped with aluminum oxide or gallium oxide, and the like. It is done.

  These transparent conductive films are formed on the surface of glass or translucent resin by vacuum deposition, sputtering, sol-gel method, cluster beam deposition or the like, and vacuum deposition is particularly common.

In recent years, solar cells using the transparent conductive film have attracted attention. This solar cell is called a dye-sensitized solar cell. A metal oxide semiconductor such as titanium oxide is provided on a light-transmitting conductive thin film, and light is absorbed on the surface of the metal oxide semiconductor to form a semiconductor. An electrolyte material containing an electrolyte for attaching a dye capable of giving electrons to form a working electrode, providing a counter electrode made of a conductive film opposite to the working electrode, and transferring electrons between the electrodes Is filled.

When the dye-sensitized solar cell is irradiated with light, the dye attached to the surface of the metal oxide semiconductor is excited and electrons can be donated to the metal oxide semiconductor to the semiconductor. In addition, the metal oxide semiconductor can exchange these electrons, and the electrons are sent to the light emitter and the charging device through the circuit. The electrons sent to the illuminant and the like pass through the circuit, then return to the counter electrode side, reduce the electrolyte with the counter electrode, and return to the system.

  This dye-sensitized solar cell can be made of resin itself, its shape can be freely determined, and bending can be performed after the battery is formed. High degree of freedom for shape. Also, the weight can be reduced.

Also, the materials used are relatively inexpensive, and silicon-based solar cells also require enormous energy for the purification of silicon in the manufacturing process, but dye-sensitized solar cells do not have such a process and the manufacturing cost is also high. Since it is relatively small, it is excellent in terms of cost.

  In addition, dye-sensitized solar cells have a feature that the amount of power generation is less reduced even when the illumination is low, such as during cloudy weather or indoor use, compared to silicon-based solar cells. It has excellent features such as no worries.

Japanese Patent Laid-Open No. 1-220380

  However, since the transparent conductive film used for the above solar cell or EL electrode is generally formed by a method such as vapor deposition industrially, it has a limited shape or size such as a sheet, a film, or a flat plate. Can only be provided on goods.

  In addition, a method of forming a transparent conductive film on various articles by forming a transparent conductive film on a film and pasting it on other articles is also performed. A high bonding technique is also required to prevent problems such as denaturation and air bubbles and wrinkles.

  Therefore, the present invention has been made in view of the above-described problems, and the scope of application of articles to which a transparent conductive film is imparted is expanded by integrally forming a transparent conductive sheet on which a transparent conductive film is formed. The present invention is to provide a production method capable of producing a resin, a resin molded product formed thereby, a resin molded product provided with a solar cell using the same, and a method for producing the same.

  In order to achieve the above object, the present invention is configured as follows. That is, a transparent conductive sheet having a transparent conductive film formed on one side of a light-transmitting resin sheet is integrally formed on the surface of a base material made of synthetic resin.

  If a transparent conductive sheet having a transparent conductive film formed on one side of a light-transmitting resin sheet is formed integrally with the surface when forming the resin molded product, the molded product can be easily formed. A transparent conductive film can be provided on the surface. As a method for this, for example, the conductive film is placed on the outside where the transparent conductive film is to be provided in the injection mold, the mold is closed, the mold is closed, and the resin is poured into the mold. A sheet may be integrally formed on the surface.

  Thus, by inserting a sheet having a transparent conductive film into a mold and molding it integrally with an injection molded product, the transparent conductive film can be formed on the surface of the article very easily. According to this method, a transparent conductive film can be applied even to a relatively complicated shape, and if a sheet is inserted only in a necessary portion, only a part of the surface of the article is transparent. A conductive film can also be formed.

  Also, compared to pasting a sheet having a transparent conductive film to a molded article, according to the method of the present invention, there is no air bubbles, the sheet can be integrated without wrinkles, and the adhesion and appearance are also good. Can be integrated. In addition, the work process can be shortened, and no skill is required as in the case of bonding sheets.

  Further, a metal oxide semiconductor is provided on the transparent conductive film, and a dye is attached to the surface of the metal oxide semiconductor to serve as a working electrode of a dye-sensitized solar cell. The working electrode is a counter electrode made of a conductive thin film. Are provided opposite to each other and an electrolyte material is filled between the opposing electrodes to form a dye-sensitized solar cell.

  A sheet having a transparent conductive film can be integrally formed on the surface of a base material made of a synthetic resin, and a dye-sensitized solar cell can be provided on the molded article using the transparent conductive film. By doing in this way, a solar cell can be directly provided in an article. Conventionally, when a solar cell is provided on an article, a solar cell module must be prepared separately and attached to the article. In the present invention, a solar cell can be directly formed on an article. Is possible.

  In a dye-sensitized solar cell, first, a metal oxide semiconductor is provided on a transparent conductive film on the surface of a resin molded article by a method such as painting, spraying, vapor deposition, or pressure bonding, and the dye is applied to the surface of the metal oxide semiconductor by impregnation. The working electrode is completed by adsorption. A counter electrode made of the other conductive thin film is stacked on top of that, and an electrolyte material containing an electrolyte is filled between the electrodes.

  In addition, a transparent conductive sheet having a transparent conductive film formed on one side of a light-transmitting resin sheet is placed in an injection mold, and a base material made of synthetic resin is molded by injection molding on the surface. A transparent conductive sheet is integrated.

  In addition, a transparent conductive sheet having a transparent conductive film formed on one side of a light-transmitting resin sheet is placed in an injection mold, and a base material made of synthetic resin is molded by injection molding on the surface. Operation of a dye-sensitized solar cell by integrating a transparent conductive sheet, providing a metal oxide semiconductor on the transparent conductive film on the integrated transparent conductive sheet, and attaching a dye to the surface of the metal oxide semiconductor A dye-sensitized solar cell is formed on the surface of an injection-molded product by forming an electrode, providing a counter electrode made of a conductive thin film so as to face the working electrode, and filling an electrolyte material between the facing electrodes Is formed.

  In addition, a transparent conductive film having a transparent conductive film formed on one side of a light-transmitting resin sheet and a metal oxide semiconductor provided on the transparent conductive film is placed in an injection mold and injected. A substrate made of synthetic resin is molded by molding, and a transparent conductive sheet is integrated on the surface, and a dye is attached to the surface of the metal oxide semiconductor on the transparent conductive sheet to function as a dye-sensitized solar cell. A dye-sensitized solar cell is formed on the surface of an injection-molded product by forming an electrode, providing a counter electrode made of a conductive thin film so as to face the working electrode, and filling an electrolyte material between the facing electrodes May be formed.

  By forming the sheet having the transparent conductive film integrally on the surface of the substrate made of synthetic resin, the transparent conductive film can be formed on the surface of the article very easily. As a method for this, a transparent conductive sheet is placed in an injection mold, a base material made of synthetic resin is molded by injection molding, and the transparent conductive sheet is integrated on the surface thereof. According to this method, a transparent conductive film can be applied even to a relatively complicated shape, and if a sheet is inserted only in a necessary portion, only a part of the surface of the article is transparent. A conductive film can also be formed. In addition, adhesion and appearance can be integrated well, and the work process can be shortened.

  Also, a sheet having a transparent conductive film is inserted into a mold and molded integrally with an injection molded product, and a dye-sensitized solar cell is provided on the molded product using the transparent conductive film on the surface of the resin molded product. Thus, the solar cell can be directly provided on the article.

  Embodiments according to the present invention will be specifically described below with reference to the drawings. FIG. 1 is a cross section showing an example of a resin molded product of the present invention, in which a sheet having a transparent conductive film is integrally molded with an injection molded product 2.

  FIG. 1a is a schematic view of a cross section of a resin molded product having a transparent conductive film on the surface, and a transparent conductive sheet 1 having a transparent conductive film 11 on the surface is formed integrally with a base material 2 made of synthetic resin. As a result, a transparent conductive film is provided on the surface of the resin molded product. FIG. 1b is a schematic cross-sectional view of a resin molded product 3 in which a transparent conductive sheet 1 having a transparent conductive film 11 on its surface is integrally formed on a curved surface of a base material made of synthetic resin. FIG.

  These resin molded products may be formed by injection molding using, for example, a mold shown in FIG. That is, after placing the transparent conductive sheet 1 having the transparent conductive film 11 on the surface in the injection mold 4 and clamping the mold, the resin is poured into the mold and cooled, By opening and removing the mold, the sheet 1 and the base material 2 made of resin are integrated as shown in FIG. When the sheet is placed on the mold, the sheet may be fixed by evacuation.

  The material of the sheet having the transparent conductive film on the surface is particularly limited as long as it can withstand the heat at the time of molding the base material made of resin and can be integrally molded, and can provide the transparent conductive film on the surface. For example, a polyester resin film such as PET resin or PEN resin, a polyolefin resin film such as polyethylene or polypropylene, a polycarbonate resin, a polyvinyl chloride resin, an acrylic resin, a polyamide resin, or a polyimide resin can be used. . The thickness of the sheet having the transparent conductive film is not particularly limited, but a sheet having a thickness of about 25 μm to 1000 μm is preferably used. When integrally forming a base material made of resin and a transparent conductive sheet, the adhesion between the sheet and the base material is obtained by fusing by heat during molding, but in order to further improve the adhesion, Surface treatment may be performed on the adhesive surface. Examples of the surface treatment for improving the adhesion include surface treatment such as UV treatment, corona discharge treatment, plasma discharge treatment, flame treatment, and sanding. Moreover, an adhesive resin layer may be provided between the sheet and the substrate made of resin to improve the adhesion. At this time, for example, ethylene vinyl acetate copolymer (EVA), polyvinyl butyral, modified polyethylene, modified polypropylene, and the like can be used as the adhesive resin.

  Moreover, as a transparent conductive film, there exist an ITO film | membrane, a FTO film | membrane, a zinc oxide film | membrane, etc., for example, What is necessary is just to select according to the use. The ITO film is transparent and conductive. This is a thin film composed of indium oxide and a small amount of tin oxide, and Sn4 + substituted at the In3 + position generates carrier electrons and exhibits conductivity. FTO is tin oxide doped with fluorine. Further, the zinc oxide film is obtained by adding aluminum oxide or gallium oxide to zinc oxide, and a transparent film can be formed although the resistance is slightly high. Examples of the method for forming the film on a sheet include vacuum deposition, sputtering, sol-gel method, and deposition by a cluster beam.

  The resin used for the base material made of synthetic resin may be selected in consideration of its use and durability. For example, polyolefin resin such as polypropylene resin and polyethylene resin, acrylic resin, polyester such as PET resin and PEN resin, etc. Resin, ABS resin, polystyrene resin, ethylene vinyl acetate resin, polycarbonate resin, polymethylmethacrylic resin, methacrylic resin, polyamide, polyimide resin, and the like can be used.

  Next, using the transparent conductive film of the resin molded product having a transparent conductive film on the surface formed as described above, a cross section of the resin molded product in which the dye-sensitized solar cell is formed on the surface of the injection molded product FIG. 3 shows a schematic diagram showing the above.

  The metal oxide semiconductor 51 is provided on the transparent conductive film 11 of a molded product in which the transparent conductive sheet 1 having the transparent conductive film 11 on the surface is molded integrally with the base material 2 made of synthetic resin. The surface of the metal oxide semiconductor 51 is attached with a dye that can be excited when irradiated with light and donate electrons to the metal oxide semiconductor. In this way, metal oxide fine particles having a dye attached thereto are provided on the transparent conductive film to form the working electrode 5 of the dye-sensitized solar cell. Further, a counter electrode 6 is provided on the working electrode 5 so as to face each other, and an electrolyte material 7 is filled between the working electrode 5 and the counter electrode 6. The counter electrode 6 is made of a conductive material 61 that has conductivity and has a catalytic function as a cathode that helps reduce the electrolyte at least on the surface and is not affected by the electrolyte. In this way, a dye-sensitized solar cell is formed on the surface of the injection molded product.

  Examples of metal oxide semiconductors include titanium oxide, zinc oxide, tin oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, indium oxide, yttrium oxide, lanthanum oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, and oxide. Molybdenum, iron oxide, nickel oxide, silver oxide, etc., strontium titanate, calcium titanate, etc., and mixtures thereof can be used, and titanium oxide is used in consideration of chemical stability, cost, and electromotive force of power generation. Is preferred.

  At this time, the titanium oxide is preferably anatase type titanium oxide having high activity. The titanium oxide on the conductive thin film is preferably laminated with fine particles. By doing so, the surface area becomes large, the area irradiated with light is wide, and the exchange of electrons with the electrolyte is also suitable. To be done. At this time, the titanium oxide is preferably fine particles of about several tens nm to several hundreds nm. Further, two or more kinds of particles having different particle diameters may be mixed, and incident light can be suitably scattered to absorb light efficiently. Further, even when a tubular nanotube type titanium oxide having a diameter of several nanometers to several tens of nanometers is used instead of fine particles, the efficiency can be increased because the surface area is large.

  The method of forming the metal oxide semiconductor of titanium oxide on the conductive thin film is not particularly limited. For example, fine titanium oxide powder may be dispersed in an appropriate solvent and applied to the thin film and baked. The fine titanium oxide powder may be fused by a high pressure press. In addition, a coating solution made of titanium alkoxide as a raw material is created and applied and baked by the sol-gel method, or a sol-gel solution made of titanium alkoxide as a raw material is atomized and heated, May be atomized and sprayed onto the electrode to be fixed. Alternatively, a spray pyrolysis method (SPD method) may be used in which an object on which a metal oxide semiconductor is formed is heated in advance, and a solution containing a titanium oxide raw material is sprayed to deposit titanium oxide on a heating substrate. .

  After the metal oxide semiconductor layer is formed as described above, a dye is adsorbed on the surface of the metal oxide semiconductor. Various dyes have been proposed for dye-sensitized solar cells and can be used. For example, ruthenium complex system, cobalt complex system in metal complex system, cyanine system, merocyanine system, phthalocyanine system, coumarin system, riboflavin system, xanthene system, triphenylmethane system, etc. are well known, These can be used. In particular, ruthenium complexes are preferable for metal complex systems, and merocyanine systems are preferable for organic systems.

  Electrolytic material quality has also been proposed for various dye-sensitized solar cells, and these can be used. As a general one, lithium iodide, iodine, and DMPImI which is an imidazolium salt of a room temperature molten salt are used as an electrolyte, and these are dissolved in a solvent of methoxyacetonitrile, and 4-tert-butylpyridine for voltage adjustment as an additive. Is used as an electrolyte material. In addition, ethylene carbonate or the like may be blended as a solvent, and MPrImI or MBuImI may be used as a room temperature molten salt. Further, MEImBF4- may be added as a diluent.

  Moreover, when a polymerizing agent is added to the above electrolyte material to cause gelation, accidents such as leakage of the electrolyte material from the solar cell can be prevented in advance. Moreover, CuI which is a solid electrolyte material can also be used as an electrolyte material.

  The counter electrode only needs to have a catalytic function as a cathode that assists in the reduction of the electrolyte and at least the surface of a conductive substance that is not affected by the electrolyte. For example, a metal sheet such as platinum can be used as it is as the counter electrode. Alternatively, a material obtained by attaching platinum, carbon, carbon nanotube, or the like on a conductive film such as an ITO or FTO film may be used.

FIG. 4 shows a schematic diagram of a product using a resin molded product having the dye-sensitized solar cell of the present invention. In FIG. 4, the resin molded product 3 having a solar cell is used as a part of the product, and as shown in the figure, the dye-sensitized solar cell 8 is provided so as to be the back side b of the resin molded product. . Therefore,
Sunlight a passes through the base material 2 made of synthetic resin and is irradiated onto the metal oxide semiconductor surface dye. In this case, the resin forming the resin molded product 2 is preferably translucent. Unlike the figure, the solar cell 8 may be provided on the outer surface of the product, but it is preferably provided on the back side of the molded product in consideration of the weather resistance of the solar cell.

  When the dye is irradiated with sunlight, the dye absorbs its light energy and donates electrons to the metal oxide semiconductor. At this time, since the dye extracts electrons from the electrolyte, the electrolyte is oxidized. The electrons donated from the dye are transferred to the semiconductor and sent to an external circuit. The electrons sent out from the working electrode 5 and passed through the external circuit return to the counter electrode 6, and on the substance 61 having a catalytic function as a cathode, the electrolyte is reduced and the electrons return to the system. In this way, a series of electric circuits is completed.

  In addition, when a dye-sensitized solar cell is provided on a resin molded body, a metal oxide semiconductor or a raw material composition of a metal oxide semiconductor is previously provided on a sheet having a transparent conductive film, and the sheet is inserted into a mold. And you may make it shape | mold integrally by injection molding. At this time, when providing the raw material composition of the metal oxide semiconductor on the sheet, the metal oxide semiconductor can be formed from the raw material by the heat at the time of injection molding, and the integration of the sheet and the metal oxide The formation of the semiconductor can be performed simultaneously.

It is a schematic diagram which shows the cross section of one Embodiment of this invention product. It is a figure which shows the cross section of the metal mold | die for forming this invention goods. It is a schematic diagram which shows the cross section of one Embodiment of this invention product. It is the schematic diagram by which sunlight was irradiated to this invention product.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent conductive sheet 11 Transparent conductive film 2 Base material which consists of synthetic resins 3 Resin molded product 4 Mold 5 Working electrode 51 Metal oxide semiconductor 6 Counter electrode 61 Conductive substance 62 Conductive film 7 Electrolyte material 8 Dye-sensitized solar cell Part 9 Products using resin molded products

Claims (5)

A resin molded product, wherein a transparent conductive sheet having a transparent conductive film formed on one side of a light transmissive resin sheet is integrally formed on a surface of a base material made of a synthetic resin. A metal oxide semiconductor is provided on a transparent conductive film, and a dye is attached to the surface of the metal oxide semiconductor to serve as a working electrode of a dye-sensitized solar cell. A counter electrode made of a conductive thin film is relative to the working electrode. The resin molded article according to claim 1, wherein a dye-sensitized solar cell is formed by filling an electrolyte material between electrodes facing each other and facing each other. A transparent conductive sheet having a transparent conductive film formed on one side of a light-transmitting resin sheet is placed in an injection mold, a base material made of synthetic resin is molded by injection molding, and a transparent conductive film is formed on the surface. A method for producing a resin molded product, comprising integrating an adhesive sheet. A transparent conductive sheet having a transparent conductive film formed on one side of a light-transmitting resin sheet is placed in an injection mold, a base material made of synthetic resin is molded by injection molding, and a transparent conductive film is formed on the surface. A conductive sheet, a metal oxide semiconductor is provided on the transparent conductive film on the integrated transparent conductive sheet, and a dye is attached to the surface of the metal oxide semiconductor to form a working electrode of the dye-sensitized solar cell. And forming a dye-sensitized solar cell on the surface of the injection-molded product by providing a counter electrode made of a conductive thin film so as to face the working electrode and filling an electrolyte material between the facing electrodes A method for producing a resin molded product, characterized by comprising: A transparent conductive sheet in which a transparent conductive film is formed on one side of a light transmissive resin sheet and a metal oxide semiconductor is provided on the transparent conductive film is placed in an injection mold, and injection molding is performed. A base material made of synthetic resin is molded and a transparent conductive sheet is integrated on the surface, and a dye is attached to the surface of the metal oxide semiconductor on the transparent conductive sheet to form a working electrode of a dye-sensitized solar cell. And forming a dye-sensitized solar cell on the surface of the injection-molded product by providing a counter electrode made of a conductive thin film so as to face the working electrode and filling an electrolyte material between the facing electrodes A method for producing a resin molded product, characterized by comprising:

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