JP2008246428A - Recycling device of waste material, recycling method using the same, and metal, metal compound, and base material obtained by this method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an effective recycling device and recycling method, which recover a valuable resource containing rare metals such as indium from waste material containing a transparent conductive film, and enable a recycling as a material of the same manufactured article. <P>SOLUTION: The invention relates to the recycling device of the waste material, provided with a plasma generating device as a means plasma-treating the waste material containing the transparent conductive film, the recycling method of the waste material, including the process of plasma-treating the waste material containing the transparent conductive film using the recycling device, and metals, metal compounds, and base material obtained by the concerned method. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a waste material recycling apparatus including a transparent conductive film, a recycling method using the same, and a metal, a metal compound, and a substrate obtained by the method.

  In recent years, general waste and industrial waste have increased in general production and consumption activities in society, and global environmental issues such as illegal dumping and landfill tightness have attracted attention, and so far mass production, mass consumption, mass disposal type economy The shift from a system to a resource recycling economic system has become an important social issue.

  In response to this situation, the Home Appliance Recycling Law was enforced in April 2001, for example. Under the Home Appliance Recycling Law, it is obliged to recycle four home appliances such as air conditioners, TVs, refrigerators and washing machines. The re-commercialization rate of each product is 60% or more for air conditioners, 55% for TVs, and 50% for refrigerators. As mentioned above, the legal reference value of 50% or more of the washing machine is set.

  Recycling of these four home appliances has progressed significantly compared to the beginning of the law enforcement, with the utmost efforts of the people concerned. Currently, recycling of plastics is expanding as well as metals such as iron, copper, and aluminum used in four home appliances. In television, a recycling technique for cutting and recycling CRT (Cathode Ray Tube) glass to remove electron guns and phosphors, and then reusing the original CRT glass as a glass cullet has already been put into practical use.

  On the other hand, recently, flat panel displays (FPD: Flat Panel Display) such as liquid crystal displays, plasma displays, organic EL (Electro Luminescence) displays, inorganic EL displays, field emission displays (FED), and electronic paper have been around. For example, televisions, personal computers, monitors, videos, cameras, mobile phones, car navigation systems, portable information terminals, and small game machines have been widely used in various fields. The market size of FPD is increasing rapidly with the progress of the advanced information society in recent years due to its power saving, space saving and light weight. Along with this, the amount of disposal of these FPDs is expected to increase year by year, and in environmental activities such as recycling activities, there is an increasing demand for improving recyclability.

  However, these FPDs are relatively new products, and the amount of waste is relatively small at present, and appropriate recycling such as the CRT has not been put into practical use. The current situation is that the discarded FPD is crushed in a waste treatment facility and is landfilled or incinerated with shredder dust.

  In addition, flat TVs such as liquid crystal displays and plasma displays are being added as items to be applied under the Home Appliance Recycling Law in the near future. Against this background, development of recycling technology for FPD, which is a key component, has become an urgent task.

  A point to be considered in the development of FPD recycling technology is the regeneration of materials such as glass and indium. A glass or plastic substrate is used as the base material of the FPD display section. Since glass accounts for most of the product weight, it is desirable to recycle from the viewpoint of improving the recycling rate, and it is more desirable to perform high-level recycling, such as recycling again as a glass raw material for the same product. In addition, an indium compound such as ITO (Indium Tin Oxide) is processed as a transparent conductive film on the base material. Indium is a rare metal, and its price has soared due to the recent expansion of the FPD market, and recovery and recycling are being sought.

  In addition to the indium compound, the metal processed into the base material of the FPD display part includes, for example, molybdenum, tantalum, titanium, aluminum, and the like. It is difficult to recycle economically because it is less than the content in natural ore. On the other hand, indium is a rare metal that does not naturally contain ore mainly composed of indium, and is mainly contained in ores such as zinc in an amount of about 5 to 30 ppm. About 700 ppm is contained, and recovering and regenerating this is valuable in terms of effective use of resources, and is considered economically advantageous.

  Considering these, the regeneration of glass and indium materials in FPD is very significant, but there are many problems. For example, there are two major problems in recycling glass to the same material. The first is complete removal of impurities and the second is glass separation. In the former, it is necessary to completely remove components other than glass, such as an electrode material processed into glass, a color filter, an alignment film, and a liquid crystal material sealed between two glasses. In the latter case, glass with different composition needs to be sorted because its properties change, and glass of different grades must be sorted by the same manufacturer as well as glass of different manufacturers. On the other hand, various studies have been made on indium. However, the recovery of indium from waste FPD products is not economical, and it is necessary to recover the ITO residue adhering to the used target, device, and jig generated in the manufacturing process. It stays.

  Against this background, many R & D efforts have been made on waste materials containing transparent conductive films, including the removal of thin films on the substrate in the waste materials and the recovery technology of indium in ITO, including companies and research institutions. ing.

  For example, many techniques for separating and recovering indium in ITO using chemicals such as acid and alkali have been proposed (see, for example, Japanese Patent Application Laid-Open No. 2000-128531 (Patent Document 1)). However, such a method using a chemical solution requires a treatment facility for waste acid, waste alkali, and the like, and there are many environmental loads such as using a large amount of water for cleaning. In addition, strong acids and strong alkalis are often used, and it is necessary to consider the durability of the treatment facility in addition to work safety, which requires a large capital investment.

  In addition, a technique about a method of burning organic substances by heat treatment and recycling indium and glass is also disclosed (see, for example, Japanese Patent Laid-Open No. 2000-84531 (Patent Document 2)). However, in such a method, since a large amount of organic gas is generated by high-temperature treatment of the entire treated product, an exhaust gas treatment facility is required. Moreover, since the glass component is also melted, there is a problem that it is difficult to regenerate the glass material.

  On the other hand, a technique for a process of removing organic substances using a supercritical fluid and recovering indium by acid cleaning or a smelting process is also disclosed (for example, Japanese Patent Laid-Open No. 2001-235718 (Patent Document 3)). reference). However, in such a method, for example, a supercritical state is formed by a high-temperature and high-pressure process such as 500 ° C. and 35 MPa. Therefore, enormous energy and large-scale equipment are required, and an FPD that is expected to continue to increase in production is used. There is concern that the total environmental impact will increase when it is finished.

  As mentioned above, when recycling materials such as glass and indium from FPD waste materials collected from the market, enormous energy and large-scale equipment are not required, and recycling of FPD waste materials that do not use a wet process in the recovery of indium is possible. In spite of the strong demand for the development of a recycling method, such a recycling method is not yet publicly known.

  On the other hand, in the IC industry, cleaning technology that does not use water is adopted, but both technologies use a reduction cleaning device in the manufacturing process, and there is no viewpoint of application to recycling of FPD waste materials. In terms of application in this field, both functions and performance are not sufficient.

In addition to the FPD waste material described above, the waste material including the transparent conductive film includes, for example, a solar cell, a touch panel, an electromagnetic shielding film, a heater, an antifogging window, and an antistatic film waste material, which is more transparent than the waste material of these products. When recovering the conductive film, a solution to the same problem as described above is required.
JP 2000-128531 A JP 2000-84531 A JP 2001-235718 A

  The present invention has been made in order to solve the above-mentioned problems. The object of the present invention is to collect valuable materials containing rare metals such as indium from waste materials containing a transparent conductive film, and to re-use the material of the same product. It is to provide an efficient recycling apparatus and recycling method that can be recycled as More specifically, it is an object to provide an efficient FPD waste material recycling apparatus and method for recovering materials such as glass and indium from FPD waste materials and recycling them again as materials of the same product. More specifically, an efficient FPD waste material recycling apparatus and method that recovers materials such as glass and indium from FPD waste materials without using a wet process and can be recycled again as the same product material. Is to provide.

  Another object of the present invention is to provide glass, indium, and the like having high-quality properties that can be collected from FPD waste materials such as glass and indium and recycled again as the same product material.

  As a result of intensive studies in order to solve the above problems, the present inventors have plasma-treated waste material containing a transparent conductive film such as FPD waste material, so that the base material and / or the base material contained in the waste material is processed. The inventors have found that the indium component contained in the transparent conductive film formed can be recovered, and have completed the present invention. That is, the present invention is as follows.

  The waste material recycling apparatus of the present invention is characterized in that a plasma generator is provided as means for plasma processing waste material including a transparent conductive film.

  Here, the waste material preferably includes a base material and a transparent conductive film formed on the base material. The substrate is preferably made of glass and / or plastic.

  In the waste material recycling apparatus of the present invention, the plasma generator preferably includes an atmospheric pressure non-equilibrium plasma discharge mechanism, and the atmospheric pressure non-equilibrium plasma discharge mechanism preferably includes a dielectric barrier discharge mechanism. The dielectric barrier discharge mechanism is more preferably a parallel plate electrode in which two plate electrodes are arranged in parallel. In the waste material recycling apparatus of the present invention, it is preferable to install the waste material between two electrodes of the parallel plate electrode.

  In the waste material recycling apparatus of the present invention, it is preferable to provide a dielectric on at least one of the two electrodes of the parallel plate electrode, and it is more preferable to install the waste on the electrode provided with the dielectric. preferable. Furthermore, it is particularly preferable to dispose the waste material in the order of an electrode provided with the dielectric, a base material, and a transparent conductive film.

  The waste material recycling apparatus of the present invention preferably further includes a mechanism for observing a plasma current waveform. The waste material recycling apparatus of the present invention preferably further includes a mechanism for analyzing a current waveform of plasma. Furthermore, it is preferable that the waste material recycling apparatus of the present invention reads the change in the current waveform of the plasma and determines whether or not to end the plasma processing.

  The waste material recycling apparatus of the present invention further includes a mechanism for storing a plasma current waveform at the end of plasma processing, and performs plasma processing when the plasma current waveform being processed matches the stored plasma current waveform. It is preferable to determine whether or not to end. Furthermore, it is more preferable to convert the plasma current waveform and determine whether to end the plasma processing.

  The present invention also provides a waste material recycling method including a step of subjecting a waste material including a transparent conductive film to plasma treatment using the above-described waste material recycling apparatus of the present invention.

  In the waste material recycling method of the present invention, the waste material is preferably at least one selected from FPD, solar cell, touch panel, electromagnetic wave shielding film, heater, anti-fogging window, and antistatic film. The FPD is preferably at least one selected from a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, FED, and electronic paper.

  In the waste material recycling method of the present invention, the waste material preferably includes a base material and a transparent conductive film formed on the base material, and the base material is at least one selected from metals, metal compounds, and organic substances. It is more preferable to contain.

  In the waste material recycling method of the present invention, it is preferable to separate at least one selected from a metal, a metal compound and an organic substance from the base material by plasma treatment, and the metal or metal compound separated from the base material It is more preferable to collect and recycle at least one selected from organic substances.

  Here, the metal and / or metal compound is preferably indium and / or an indium compound.

  In the waste material recycling method of the present invention, it is preferable that the plasma-treated substrate is also recycled.

  The present invention also provides the above-described waste metal and / or metal compound of the present invention.

  The present invention further provides a substrate obtained from a flat panel display by the above-described waste material recycling method of the present invention.

  According to the present invention, it is possible to separate a rare metal contained in a waste material as a transparent conductive film without applying an environmental load. In addition, according to the present invention, in order to treat waste material containing a transparent conductive film by plasma, for example, at least any one selected from a metal, a metal compound, and an organic substance contained in a display substrate, and / or a display Unlike conventional cases where acids, alkalis and organic solvents are used to clean the substrate, there is no need to use substances that have an impact on the environment. Furthermore, according to the present invention, since no water is used, energy is not required for drying or the like, and material recycling for maintaining a sustainable environment can be realized by a technology friendly to the earth.

  The waste material recycling method of the present invention includes a transparent conductive film formed of an indium compound such as a solar cell, a touch panel, an electromagnetic wave shielding film, a heater, an antifogging window, and an antistatic film in addition to the FPD. It can be suitably applied to the recycling of waste materials.

  Moreover, this invention can also provide about at least any selected from the metal obtained by carrying out the plasma processing of the base material contained in a waste material, a metal compound, and a base material. At least one selected from the metal, the metal compound, and the base material collected by the method of the present invention can be recycled again as the material of the same product.

  Further, the waste material recycling apparatus of the present invention provides a substrate for separating at least one selected from a metal, a metal compound, and an organic substance from a base material contained in an FPD waste material and / or a base material contained in an FPD waste material. Since the plasma generator for cleaning is provided, it can be used particularly preferably in the above-described recycling method of the present invention.

  FIG. 1 is a diagram schematically showing a waste material recycling apparatus 1 of a preferred example of the present invention, and FIG. 2 conceptually shows a plasma generator 2 used in the waste material recycling apparatus 1 of the present invention. FIG. The recycling apparatus 1 of the present invention is characterized by including a plasma generator 2 as means for plasma processing waste material including a transparent conductive film. According to the waste material recycling apparatus 1 of the present invention, it is possible to separate a rare metal contained in the waste material as a transparent conductive film without applying an environmental load. Moreover, according to the waste material recycling apparatus 1 of the present invention, since the waste material including the transparent conductive film is processed by plasma, for example, at least one selected from metals, metal compounds, and organic substances contained in the base material of the display Unlike the case of using conventional acids, alkalis and organic solvents to separate and / or clean the substrate of the display, there is no need to use substances that give an impact to the environment. Furthermore, according to the waste material recycling apparatus 1 of the present invention, water is not used, so energy is not required for drying, etc., and material recycling for maintaining a sustainable environment is realized with earth-friendly technology. can do.

  Here, the plasma generation technology itself used in the waste material recycling apparatus of the present invention is applied as a technology related to decomposition and modification of substances that have been put into practical use in the fields of the IC industry and the electronic component industry. . However, the waste material recycling apparatus of the present invention is intended to apply the plasma technology to the field of recycling industrial waste, and specifically includes at least a base material and a transparent conductive film. By irradiating the waste material with plasma, at least one selected from a metal, a metal compound, and an organic compound containing a material for forming the transparent conductive film formed on the base material is separated and / or the base material is washed. Thus, these metals, metal compounds, and base materials are to be recycled. Such attention is an epoch-making thing that has not existed before.

  Here, FIG. 3 is a cross-sectional view schematically showing a liquid crystal panel 51 that is an FPD as an example of a waste material including a transparent conductive film that is to be recycled by the waste material recycling apparatus 1 of the present invention. The waste material to be recycled by the waste material recycling apparatus 1 of the present invention is not particularly limited as long as it contains a transparent conductive film, but preferably a base material and a transparent material formed on the base material. A conductive film. Examples of such waste materials include at least one selected from FPD, solar battery, touch panel, electromagnetic wave shielding film, heater, anti-fogging window, and antistatic film. Among these, the FPD includes at least one selected from a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an FED, and electronic paper. All of these are formed by forming ITO made of an indium compound such as ITO on a substrate made of glass and / or plastic, and have a common structure. Hereinafter, prior to the description of the waste material recycling apparatus 1 of the present invention, a liquid crystal panel will be described as an example of a waste material to be recycled in the present invention in the FPD.

  FIG. 3 schematically shows a general structure (side cross-sectional view) of a TFT (Thin Film Transistor) type liquid crystal panel 51. In the example shown in FIG. 3, an electrode material (including TFT) 54 and an ITO electrode 55 that is a transparent conductive film are formed on the TFT side substrate 52, and an alignment film 56 is formed thereon. On the other hand, a color filter 57, an ITO electrode 58, which is a transparent conductive film, and an alignment film 59 are sequentially formed on the color filter side substrate 53. Then, the liquid crystal 60 is injected between the processed base materials 52 and 53, and the periphery thereof is sealed with sealing materials 61 and 62. On the base materials 52 and 53, polarizing plates 63 and 64 are usually attached.

  In the present invention, for example, in the liquid crystal panel shown in FIG. 3, the base materials 52 and 53 are divided, and after collecting the liquid crystal 60, the base 52 and 53 on the surface on which the alignment films 56 and 59 are formed. The plasma generated by the plasma generator 2 of the recycling apparatus 1 of the invention is irradiated. Therefore, the substrates 52 and 53 that can be separated by plasma treatment include alignment films 56 and 59, ITO electrodes 55 and 58 that are transparent conductive films, electrode materials (including TFTs) 54, sealing materials 61 and 62, and A color filter 57 is formed. Specifically, these are formed of materials as shown in Table 1.

  As shown in Table 1, as materials that can be separated by plasma treatment using the waste material recycling apparatus 1 of the present invention, for example, organic substances such as polyimide, acrylic resin, epoxy resin, tantalum, It turns out that inorganic substances, such as titanium, molybdenum, aluminum, and ITO, are mentioned. In addition, the material shown in Table 1 is an example, and the material isolate | separated using the recycling apparatus 1 of this invention is not limited to these.

  According to the waste material recycling apparatus 1 of the present invention, the alignment film 56 made of at least one of a metal, a metal compound, and an organic material as shown in Table 1 is formed from the base materials 52 and 53 by plasma treatment. , ITO electrode 55, electrode material (including TFT) 54, sealing materials 61 and 62, alignment film 59, ITO electrode 58 and color filter 57 can be separated, and the substrate is cleaned by plasma treatment. can do. The base material cleaned by the plasma treatment in this manner can be reused for the same product or the like because the above-mentioned materials are removed very well. Moreover, by using the recycling apparatus 1 of the present invention, the metal, metal compound, and organic substance separated from the base material can also be recovered and reused. In addition, since at least any one of the metal, the metal compound, and the organic material described above has a different chemical structure from the base material on which these are formed, radicals generated by plasma generated by the plasma generator 2 are used. It can be removed.

  In the waste material recycling apparatus 1 of the present invention, the plasma generator 2 for plasma processing the waste material including the transparent conductive film as described above is not particularly limited, but a vacuum device or the like is unnecessary. Therefore, it is preferable to provide an atmospheric pressure non-equilibrium plasma discharge mechanism because the apparatus cost is not required and the reaction process can be constructed with much less energy consumption than the equilibrium plasma discharge mechanism. The atmospheric pressure non-equilibrium plasma discharge mechanism preferably includes a dielectric barrier discharge mechanism so that uniform glow discharge can be easily generated. In addition, the dielectric barrier discharge mechanism is capable of processing a large area at a time, and considering high processing efficiency, it is preferably a parallel plate electrode in which two plate electrodes are arranged in parallel. It is more preferable to install the waste material between two electrodes of these parallel plate electrodes. Further, from the viewpoint of improving plasma irradiation efficiency, it is particularly preferable to provide a structure in which a dielectric is provided on at least one of the two electrodes of the parallel plate electrode.

  In the plasma generator 2 of the example shown in FIGS. 1 and 2, the two electrodes A and B, which are parallel plate electrodes, are spaced apart from each other, and the dielectric 5 is in close contact with the B electrode 4 therebetween. The power source 6 is electrically connected to the A electrode 3 and the B electrode 4. A waste material 7 including a transparent conductive film 9 is installed between the A electrode 3 and the B electrode 4 of such a plasma generator 2. As the waste material 7, a material having a base material 8 and a transparent conductive film 9 formed on the base material 8 is preferably used. In the example of FIG. 3 described above, the waste material 7 including the base material 8 and the transparent conductive film 9 is the TFT side base material 52 on which the electrode material 54, the ITO electrode 55 and the alignment film 56 are formed, or the color filter 57, The color filter side substrate 53 on which the ITO electrode 58 and the alignment film 59 are formed corresponds.

  In the waste material recycling apparatus 1 of the present invention, the waste material 7 only needs to be installed between the A electrode 3 and the B electrode 4. The method can be adopted without any particular limitation. For example, the waste material 7 may be transported so as to pass between the A electrode 3 and the B electrode 4 using a belt conveyor or the like (not shown). In order to intensively irradiate the waste material 7 with plasma, the waste material 7 is preferably placed on the electrode (the B electrode 4 in the example shown in FIGS. 1 and 2) provided with the dielectric 5. In this case, the transparent conductive film 9 can be intensively irradiated with plasma to improve the plasma processing efficiency and shorten the plasma processing time. Therefore, as in the example shown in FIGS. 5 is preferably disposed in the order of the electrode 8 (B electrode 4 in the example shown in FIGS. 1 and 2), the base material 8, and the transparent conductive film 9.

  The material for forming the A electrode 3 and the B electrode 4 used in the plasma generator 2 in the present invention is not particularly limited, and any appropriate material that has been widely used in the art can be used. From the viewpoints of properties and corrosion resistance, it is preferable to use stainless steel (specifically, SUS304 or the like). The dielectric 5 is not particularly limited, and any appropriate material that has been widely used in the art can be used. However, if durability is considered, it is preferable to use glass, In order to generate a uniform glow discharge having a high dielectric constant, it is preferable to use alumina. These may be properly used depending on the discharge characteristics to be obtained.

  In addition, the power source 6 used in the plasma generator 2 in the present invention may be any of direct current, alternating current, and pulse as long as it can activate air, water vapor, and other gases. It is preferable to use a pulse power supply that can be turned off. By using a pulse power supply, the electric field strength can be increased rapidly, the plasma density can be increased, and the current, voltage, and the like can be turned off before heat is generated by plasma discharge. When a pulse power source is used as the power source 6, the frequency is not particularly limited, but for example, a range of 1 to 100 kHz is exemplified.

  Further, in the plasma generator 2 in the example shown in FIGS. 1 and 2, a gas supply path 10 for supplying a source gas is formed between the A electrode 3 and the dielectric 5. Examples of the source gas supplied into the plasma generator 2 through the gas supply path 10 include oxygen gas, nitrogen gas, air, water vapor, helium gas, argon, carbon dioxide, hydrogen gas, methane gas, ammonia gas, and fluorine. Although gas etc. are mentioned, it is not limited to this, You may use the mixture of these gas. The method for supplying the source gas is not particularly limited, and a conventionally known method can be appropriately used.

  Here, there are various effective radicals that can be included in the plasma used in the present invention. However, toxic and expensive radicals should be avoided, and air itself may be used as the source gas. In this way, when air is used as one of the source gases, it may be supplied using a blower. Note that a small amount of oxygen gas or water vapor may be added to the air in order to increase the oxygen radical concentration in the region where the plasma treatment is performed. Among these, the method of adding water vapor to air is simpler and more preferable than the method of adding oxygen gas to air.

  In addition, when air added with oxygen gas or water vapor is used as a source gas as described above, the plasma generator 2 observes the region irradiated with plasma rather than controlling the added oxygen gas or water vapor at the supply stage. Thus, it is preferable to realize the control so that the frequency of the power source 6 is changed according to the observed result to adjust the concentration of oxygen radicals in the region. That is, it is economical and safe to use air itself as a raw material gas, but it is not preferable that a change in humidity appears as a change in the concentration of oxygen radicals in the region irradiated with plasma. It is preferable to control the frequency of the power source 6 and the amount of oxygen gas or water vapor added.

  In addition, in the plasma generator 2 of the example shown in FIG. 1, the gas supply path 10 has an A electrode frame that covers from the A electrode 4 side except for the supply gas inlet 11 with the waste material 7 installed as described above. 13 and the B electrode frame 14 covering from the B electrode 4 side. The gas supply path 10 also communicates with the supply gas outlet 12 and is configured so that the gas in the gas supply path 10 after the plasma processing can be discharged from the supply gas outlet 12.

  In the plasma processing using the plasma generator 2 according to the present invention, the waste material 7 is installed as described above, and the gas supply path 10 is sealed by the A electrode frame 13 and the B electrode frame 14 from the supply gas inlet 11. While supplying the source gas, a voltage higher than a certain value is applied to the A electrode 3 and the B electrode 4 from the power source 6. As a result, a discharge is generated between the A electrode 3 and the B electrode 4, and this discharge generates plasma containing various ions and radicals resulting from the components of the atmospheric gas (the raw material gas supplied to the gas supply path 10). The waste material 7 including at least the base material 8 and the transparent conductive film 9 described above is irradiated. The transparent conductive film 9 is separated from the substrate 8 and the substrate 9 is washed. Specifically, as described above, the waste material 7 including the base material 8 and the transparent conductive film 9 is the TFT in which the electrode material 54, the ITO electrode 55, and the alignment film 56 are formed in the example shown in FIG. The side substrate 52, or the color filter side substrate 53 on which the color filter 57, the ITO electrode 58 and the alignment film 59 are formed, corresponds to plasma irradiation using the waste material recycling apparatus 1 of the present invention. By doing so, the metal, metal compound, and organic substance formed on the base materials 52 and 53 can be separated, and the surfaces of the base materials 52 and 53 can be cleaned. That is, gas components entering from the gas supply path 10 by discharge collide with electrons accelerated at high speed, and are ionized, dissociated, and excited, and various ions and radicals resulting from the gas components are generated. These radicals act on the metal, metal compound, organic matter and the like processed on the base material of the liquid crystal panel, which is an FPD waste material, and separate these processed materials from the base material.

  The time for irradiating the waste material 7 with plasma using the recycling apparatus 1 of the present invention is particularly limited as long as the above-described materials including the material for forming the transparent conductive film 9 formed on the base material 8 are separated. For example, it is 1 second to 1 hour. Moreover, in order to wash | clean the base-material surface more highly, you may make it irradiate plasma to the base material 8 after isolate | separating the material mentioned above containing the formation material of the transparent conductive film 9, for example. It should be noted that the voltage and frequency applied by the power source 6 may be changed during the plasma processing as long as the effects of the present invention are not impaired. The distance between the electrode on the side where the waste material 7 is not installed and the waste material 7 is not particularly limited, and for example, a linear distance within a range of 1 mm to 1 m can be appropriately selected.

  Here, whether or not the transparent conductive film 9 has been removed from the waste material 7 that is a plasma object can be determined by analyzing the surface of the substrate using, for example, an energy dispersive X-ray apparatus. When an energy dispersive X-ray apparatus is used, time is required for analysis and the apparatus becomes large, which is not a good solution from the viewpoint of practical use. For this reason, the present inventors at the time when plasma irradiation is started on the substrate 8 on which the transparent conductive film 9 is formed and when the transparent conductive film 9 is removed by plasma irradiation. It was found that the plasma current waveform is different, and that it is possible to determine whether or not to end the plasma processing by using the difference in the current waveform.

  In view of the above, the waste material recycling apparatus of the present invention preferably further includes a mechanism for observing the plasma current waveform, and further preferably includes a mechanism for analyzing the plasma current waveform. As a mechanism for observing the current waveform of the plasma, an appropriate mechanism that has been widely used in the art can be used without any particular limitation, and is not particularly limited. However, from the viewpoint of resolution and ease of data processing. It is preferable to use a digital oscilloscope. In addition, the mechanism for analyzing the current waveform of the plasma is not particularly limited as long as the waveform change before and after the plasma treatment can be compared, and an appropriate mechanism that has been widely used conventionally is used without any particular limitation. Can do. Examples of methods for comparing waveform changes before and after plasma processing include a method using image recognition and image conversion processing, and a method of converting a current waveform into its wave height, amplitude, standard deviation, and the like and comparing the current waveform. be able to.

  In addition to the plasma generator 2 described above, FIG. 1 shows an oscilloscope 16 as a mechanism for observing the plasma current waveform, a current waveform analyzer 17 as a mechanism for analyzing the plasma current waveform, and a control for controlling these. The waste material recycling apparatus 1 provided with the apparatus 18 is shown typically. In the example shown in FIG. 1, an oscilloscope 16 is electrically connected to the A electrode 3 and the B electrode 4 in order to observe the current flowing between the A electrode 3 and the B electrode 4 which are parallel plate electrodes and the applied voltage. The current waveform analyzer 17 and the controller 18 are further electrically connected to the oscilloscope 16. By providing a mechanism for observing the plasma current waveform and a mechanism for analyzing the plasma current waveform in this way, it is possible to read the above-described change in the plasma current waveform and determine whether or not to end the plasma processing. The recycling apparatus 1 can be realized. In this case, the recycling apparatus of the present invention preferably further includes a mechanism for storing the plasma current waveform at the end of the plasma processing. In the example shown in FIG. It also has a mechanism for storing the plasma current waveform at the end.

  Here, FIG. 4 is a flowchart showing an example of a method for controlling the waste material recycling apparatus 1 of the present invention of the example shown in FIG. The waste material recycling apparatus 1 of the example of the present invention shown in FIG. 1 can be controlled to determine whether or not to end the plasma processing in a series of flows as shown in FIG. 4, for example. it can.

  First, the plasma current waveform (waveform X) at the time when the transparent conductive film 9 is removed from the substrate 8 is stored in the current waveform analyzer 17 (step 501). At this time, a plasma current waveform may be obtained from a base material on which a transparent conductive film is not formed. The plasma current waveform (waveform X) may be subjected to fast Fourier transform so that it can be easily observed.

  Next, observation of the plasma current waveform is started with the oscilloscope 16 (step 502), and plasma processing is started on the substrate 8 on which the transparent conductive film 9 is formed (step 503). During the plasma processing, the plasma current waveform is observed with the oscilloscope 16, and the observed plasma current waveform is transmitted to the current waveform analyzer 17. The plasma current waveform observed in this way may be subjected to fast Fourier transform so that it can be easily observed.

  Next, the current waveform analyzer 17 compares the plasma current waveform received from the oscilloscope 16 with the waveform X stored in advance (step 504). When the plasma current waveform received from the oscilloscope 16 substantially coincides with the waveform X (step 505), it is determined that the transparent conductive film 9 has been removed from the substrate 8, and the current waveform analyzer 17 transfers the control to the controller 18. A signal is sent (step 506). The control device 18 receives the processing end signal and proceeds to the next step (step 507). In this way, it is possible to realize suitable plasma processing control using the waste material recycling apparatus 1 of the present invention.

  The examples shown in FIGS. 1 and 2 are merely preferable examples, and the waste material recycling apparatus of the present invention includes a plasma generator as a means for plasma processing waste materials including a transparent conductive film. The present invention is not particularly limited, and may be realized with any configuration.

  FIG. 5 is a flowchart showing a preferred example of the method for recycling waste materials according to the present invention. The present invention also provides a waste material recycling method including a step of subjecting a waste material including a transparent conductive film to plasma treatment using the above-described waste material recycling apparatus of the present invention. In the waste material recycling method of the present invention, as described above, the waste material including the base material and the transparent conductive film formed on the base material is the target of the resource recycling. Examples of such waste materials include at least one selected from FPD, solar cell, touch panel, electromagnetic wave shielding film, heater, anti-fogging window, and antistatic film as described above. Among these, the FPD includes at least one selected from a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an FED, and electronic paper. FIG. 1 shows a case where a waste material of a liquid crystal television including a liquid crystal panel (FIG. 3) which is an FPD waste material is recycled as an example of a waste material including such a transparent conductive film.

  In the waste material recycling method of the example of the present invention shown in FIG. 1, first, FPD waste material (for example, liquid crystal television waste material including a liquid crystal panel) discarded from a home or a manufacturing factory is collected (step 101). Next, the collected liquid crystal TV waste is disassembled (for example, manually disassembled) by a conventionally known appropriate method, metal parts such as shield cases and steel plates, plastic parts such as printed boards, cases and stand covers, It is disassembled into a fluorescent tube or the like (step 102), and the liquid crystal panel 51 as shown in FIG. 3 is taken out (step 103).

  Next, the polarizing plates 63 and 64 attached to the liquid crystal panel 51 are removed (step 104). The removing method of the polarizing plates 63 and 64 can be removed by a conventionally known appropriate method. For example, a method in which one end portion (for example, a corner) of the polarizing plates 63 and 64 is partially peeled using a tool such as a cutter and then the peeling portion is pulled with an appropriate force to peel the entire polarizing plates 63 and 64. And a method of peeling the polarizing plates 63 and 64 using a commercially available polarizing plate peeling apparatus.

  Subsequently, the liquid crystal panel 51 is sorted (step 105). This is performed for the purpose of recycling the display base material used for each same type. Therefore, depending on the use of the base material to be regenerated, the separation step may be unnecessary. As a method for separating the substrate in this step, for example, in the case of a substrate formed of glass, a separation method using fluorescent X-rays can be suitably employed. Specifically, the glass is irradiated with soft X-rays, and fluorescent X-rays emitted from the glass are separated using, for example, a fluorescent X-ray analyzer. In addition, there is a method of tracking the type of glass used for the base material from the manufacturer of the LCD TV, the model number, etc., but the separation method uses any means as long as the glass can be separated into the same type It doesn't matter. In the case of a base material formed of plastic, the above tracking method is effective. Further, the base material may be made of glass and plastic containing resin or organic matter.

  Next, in order to expose the indium compound formed on the base materials 52 and 53 to the surface, the two base materials 52 and 53 of the sorted liquid crystal panel 51 are divided (step 106). The method of dividing the base materials 52 and 53 is not particularly limited, and examples thereof include a method of cutting four sides inside the sealing area with a cutter. Moreover, a liquid crystal panel may be crushed and a means is not specifically limited.

  Subsequently, the encapsulated liquid crystal and the liquid crystal adhering to the divided glass surface are recovered (step 107). The recovery method is not particularly limited, but the recovery of the encapsulated liquid crystal includes, for example, washing with an organic solvent such as acetone. In addition, as a method of collecting the liquid crystal attached to the divided glass surface, for example, there is a method of scraping off the liquid crystal attached to the glass surface using a plate-like object such as a spatula. The liquid crystal collected in this way has no process such as heating so far, so that the quality at the time of product use is maintained, and it is suitable for reuse. The liquid crystal may be subjected to removal or purification of impurities as necessary, and the components may be readjusted according to the purpose of reuse.

  In the subsequent process, the waste material including the transparent conductive film is subjected to plasma treatment using the above-described waste material recycling apparatus of the present invention (step 108). Specifically, in this process, the electrode material 54 divided or crushed in step 106, the TFT side substrate 52 on which the ITO electrode 55 and the alignment film 56 are formed, or the color filter 57, the ITO electrode 58 and the alignment film. A metal (specifically indium) as shown in Table 1 including a material for forming a transparent conductive film formed on the base material by irradiating plasma to the color filter side base material 53 having 59 formed thereon, metal The compound (specifically, indium compound) and the organic substance are separated, and the base materials 52 and 53 are washed.

  As described above, the waste material recycling apparatus of the present invention used in step 108 is not particularly limited as long as it includes a plasma generator as a means for performing plasma treatment on a substrate including a transparent conductive film. Although not intended, as in the example shown in FIG. 1, in addition to the plasma generator 2, the oscilloscope 16 is a mechanism for observing the plasma current waveform, and the current waveform analyzer 17 is a mechanism for analyzing the plasma current waveform. In addition, the waste material recycling apparatus 1 including the control device 18 for controlling them can be particularly preferably used. Furthermore, the waste material recycling apparatus 1 is controlled along the series of flows shown in FIG. 4 to read changes in the plasma current waveform, and whether or not to end the plasma processing. It is particularly preferable to implement so as to determine.

  In the subsequent process, indium and / or indium compounds separated from the base materials 52 and 53 by the plasma treatment are recovered (step 109). The recovered indium and / or indium compound is removed and purified as necessary, and recycled as a material again (step 110). The recovered indium and / or indium compound can be sufficiently recycled as a material for the transparent conductive film, but the application is not limited to this, and for example, it can be recycled into a solder material or a semiconductor material.

  Here, for other metals such as tantalum and titanium and / or other metal compounds separated together with indium and / or indium compounds, for example, a method of using a chemical solution such as acid or alkali as necessary. And indium and / or indium compounds can be separated and recovered using a method such as electrolysis. In addition, the organic matter separated together with indium and / or indium compounds can be separated from indium and / or indium compounds by, for example, extraction by washing with an organic solvent.

  In the example shown in FIG. 1, the substrate cleaned by the plasma treatment is also collected (step 111) and recycled as a material again (step 112). In the case of a substrate made of glass, as a method of recycling, the recovered glass substrate is put into the liquid crystal panel display manufacturing process, culleted with a crushing device, etc. The method of recycling, the method of recycling as a quartz stone substitute material and a tile material, etc. are mentioned.

  In the waste material recycling method of the present invention as described above, since the treatment is performed by plasma, at least any one selected from a metal, a metal compound, and an organic substance formed on the substrate of the display, and / or Unlike conventional cases where acids, alkalis or organic solvents are used to clean the substrate of the display, there is no need to use substances that give a burden to the environment. Furthermore, according to the plasma cleaning according to the present invention, water is not used, and thus energy is not required for drying or the like, and material recycling for maintaining a sustainable environment can be realized by a technology that is friendly to the earth. Moreover, the metal and / or metal compound and / or base material which were collect | recovered by the method of this invention can be reused as various materials.

  The waste material recycling method in which the transparent conductive film of the present invention is processed does not have to include all the steps shown in FIG. 1, and plasma processing is performed using the waste material recycling apparatus of the present invention. Any process including at least a step is included in the scope of the present invention. Further, steps not shown in FIG. 1 may be added to the waste material recycling method of the present invention as necessary.

  The present invention also provides a metal and / or metal compound obtained by the above-described waste material recycling method of the present invention, and further obtained from FPD by the above-described waste material recycling method of the present invention. A substrate is also provided. The metal, metal compound, and base material obtained by the waste material recycling method of the present invention can be recycled again as various materials such as materials of the same product.

  As described above, the metal and / or metal compound obtained by the recycling method of the present invention can be reused as a material after removing impurities and refining as necessary. Moreover, the indium content in the separated product by the plasma treatment is much higher than the indium content (about 150 to 700 ppm) in the liquid crystal panel, and is about several tens of percent or more. Therefore, in this state, it can be sold to a smelting company that handles indium, for example, and purified as an indium material. Further, if necessary, higher purity indium may be recovered from the separated material by using a method using a chemical solution such as acid or alkali or a method such as electrolysis. The recovered indium and / or indium compound can be regenerated as a material for the transparent conductive film by removing impurities and purifying as necessary. However, as described above, the application is not limited to this. For example, a solder material It can also be recycled into semiconductor materials.

  Moreover, the base material after plasma irradiation is in a state where at least one selected from a metal, a metal compound, and an organic material including the material for forming the transparent conductive film as described above is removed, and can be used again as a base material. For example, in the case of a substrate formed of glass, there is a method in which a glass substrate after plasma irradiation is cut, processed, and washed into the glass size that is input in the FPD manufacturing process and then input again into the FPD manufacturing process. In addition, there is a method in which a glass substrate after plasma irradiation is culleted by a crushing device or the like and regenerated for the same purpose by a glass manufacturer.

  In the waste material recycling method of the present invention described above, at least one specific recovery method selected from the metal, metal compound and substrate separated by plasma treatment is not particularly limited. Here, FIG. 6 is a diagram schematically showing a waste material recycling apparatus 31 of another preferred example of the present invention. The waste material recycling apparatus 31 of the example shown in FIG. 6 is further provided with a mechanism for recovering the metal, metal compound, and base material separated by the plasma processing, and the waste material recycling apparatus 31 of the example shown in FIG. The parts that are the same as those of the recycling apparatus 1 and that have the same configuration are denoted by the same reference numerals, and description thereof is omitted.

  In the example shown in FIG. 6, as a mechanism for recovering at least one selected from a metal, a metal compound, and an organic substance containing a material for forming the transparent conductive film 9 separated from the base material 8 by the plasma treatment (separate 35). The suction mechanism 33 and the dust collection mechanism 34 are provided in communication with the supply gas outlet 32. Since the separated matter 35 is originally a thin film, it is light and is sucked by the suction mechanism 33, so that it passes through the supply gas outlet 32 and moves to the suction mechanism 33 side. Here, when the indium component or the like is in a state other than solid such as liquid or gas due to plasma radical action, heat action, etc. (for example, vaporization temperature of indium oxide is 850 ° C., melting point of metal indium is 155 ° C., boiling point is 2000 ° C. However, since the atmosphere (atmosphere) temperature is normal temperature, the indium component immediately returns to the solid state. In this case, as shown in FIG. 6, a cooling mechanism 36 is provided between the supply gas outlet 32 and the dust collecting mechanism 34 to forcibly cool the indium component in a state other than the solid and return it to the solid state. You may comprise as follows. In this way, the solid separated matter 35 moved to the suction mechanism 33 side can be collected by the dust collection mechanism 34.

  In the example shown in FIG. 6, the suction mechanism 33, the dust collection mechanism 34, and the cooling mechanism 36 are not particularly limited, and can be realized by using conventionally known appropriate means. For example, the suction mechanism 33 can use a suction pump, and the dust collection mechanism 34 can use a bag filter.

  In the event that the indium component or the like is in a state other than a solid such as a liquid or a gas due to the radical action or thermal action of the plasma and adheres to the inner wall of the apparatus, for example, the gas supply path 10 A deposition sheet may be provided on the inner wall, and the deposited indium component may be collected periodically from the deposition sheet (not shown). Moreover, the recovery method of the indium component mentioned above may be physical methods, such as cutting and grinding | polishing, for example, and may use the chemical | medical solution. The material of the adhesion-preventing sheet is not particularly limited as long as it is suitable for these recovery methods and can be set in the apparatus, and examples thereof include metals and resins.

  Hereinafter, although an example of an experiment is given and the present invention is explained in detail, the present invention is not limited to these.

<Experimental example 1>
Three types of plasma generators having a parallel plate electrode structure with dielectric barrier discharge were prepared, and plasma treatment experiments were conducted. As shown in FIG. 2, the first plasma generator is a plasma generator 2 having an A electrode 3 (no dielectric) and a B electrode 4 provided with a dielectric 5, and a second plasma generator. As an apparatus, as shown in FIG. 7, a plasma generator 41 having an A electrode 3 provided with a dielectric 42 and a B electrode 4 provided with a dielectric 5 is shown in FIG. The plasma generator 46 provided with the A electrode 3 provided with the dielectric 42 and the B electrode 4 (without the dielectric) was used. The plasma generators 2, 41 and 46 use SUS electrodes for both the A electrode 3 and the B electrode 4 (electrode size: vertical 100 mm x horizontal 100 mm), and the dielectrics 5 and 42 are made of alumina. (Dielectric size: 150 mm long × 150 mm wide). In each of the plasma generators 2, 41 and 46, the linear distance between the A electrode 3 and the B electrode 4 was set to 2 mm.

  A region in which the transparent conductive film 9 irradiates plasma with a sample in which the transparent conductive film 9 is formed on the color filter side glass substrate 8 (length 50 mm × width 50 mm) of the liquid crystal panel. It installed in the B electrode 4 side so that it might become a side. Dry air was used as the source gas (total gas flow rate: 0.5 liter / min), and the output from the power supply was set so that the power was 300 W and the frequency was 10 kHz. In both cases, plasma irradiation was performed for 5 minutes under the same conditions. It was. Table 2 shows the plasma irradiation state in each of the three types of plasma generators 2, 41 and 46.

  From Table 2, when the plasma generator 2 shown in FIG. 2 provided with the dielectric 5 only on the B electrode 4 side was used, the plasma was discharged concentrated on the sample, and the discharge state was good. . On the other hand, when the plasma generator 41 shown in FIG. 7 in which the dielectrics 42 and 5 are provided on the A electrode 3 and the B electrode 4 respectively, the plasma discharge is concentrated on the sample, but the A electrode 3 Since the dielectric 42 was also provided on the side, the discharge itself became weak. Further, when the plasma generator 46 shown in FIG. 8 in which the dielectric 42 is provided only on the A electrode 3 side, the plasma discharge escapes directly to the B electrode 4 and the plasma discharge is concentrated outside the sample. In addition, almost no plasma discharge was observed inside the sample.

  Next, indium removal rates were calculated for each of three types of apparatuses. The plasma conditions were the same as those described above. In the calculation of the indium removal rate, the amount of indium in the transparent conductive film of the sample not subjected to plasma treatment and the amount of indium remaining in the sample subjected to plasma treatment with three types of apparatuses were each quantified and calculated. Indium was completely dissolved in 35% hydrochloric acid at 80 ° C. for 90 minutes, and quantified using an ICP emission analyzer (JY238ULTRACE manufactured by Horiba, Ltd.). FIG. 9 is a graph showing a comparison of indium removal rates when three types of plasma generators are used, and the vertical axis represents the indium removal rate (%). As a result, the indium removal rate is 81% in the case of the plasma generator 2 shown in FIG. 2, 51% in the case of the plasma generator 41 shown in FIG. 7, and in the case of the plasma generator 46 shown in FIG. Became 12%. This suggests that the structure shown in FIG. 3 has the highest plasma processing efficiency and the processing time is expected to be shortened in a plasma generator having a parallel plate electrode structure with dielectric barrier discharge.

<Experimental example 2>
Next, using the plasma generator 2 shown in FIG. 2, the plasma conditions and the samples used were the same as those used in Experimental Example 1, and current voltage waveform data immediately after plasma irradiation and 5 minutes after plasma irradiation were collected. Current voltage waveform data was collected with an oscilloscope (TDS2024 manufactured by Tektronix, Japan), P6015A type was used as the high voltage probe, and P6022 was used as the current probe. FIG. 10 shows current waveform data immediately after plasma irradiation, and FIG. 11 shows current waveform data after 5 minutes of plasma irradiation. 10 and 11, the vertical axis represents current (A) and the horizontal axis represents time (μsec).

  As a result, it can be seen that the current waveforms immediately after plasma irradiation and after 5 minutes are greatly different in the region of 1.5 to 2 μsec. The current wave height immediately after plasma irradiation in this region was about 0.4 A, whereas the current wave height after 5 minutes of plasma irradiation was as small as about 0.1 A. From this, for example, a method using fast Fourier transform (FFT), image recognition and image conversion processing, etc., or if the current waveform is converted into its wave height, amplitude, standard deviation, etc., and the change in the current waveform is read, It is possible to determine the end of the plasma processing.

<Experimental example 3>
FIG. 12 shows the change over time of the standard deviation of the current waveform when the plasma generator 2 shown in FIG. 2 is used and the plasma conditions and samples used are the same as in Experimental Example 1 and plasma irradiation is performed for 2 minutes. In FIG. 12, the vertical axis represents standard deviation (A) and the horizontal axis represents plasma irradiation time (sec). As a result, the standard deviation of the current waveform immediately after the plasma irradiation was about 0.16 A, but gradually decreased with the lapse of the irradiation time and converged to about 0.05 A standard deviation after 1 minute. As described above, it is effective to use the standard deviation data as means for reading the change in the current waveform.

  It should be considered that the embodiments and experimental examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

It is a figure which shows typically the waste-material recycling apparatus 1 of a preferable example of this invention. It is a figure which shows notionally the plasma generator 2 used for the waste-material recycling apparatus 1 of this invention. It is sectional drawing which shows typically the liquid crystal panel 51 which is FPD as an example of the waste material containing the transparent conductive film which the waste material recycling apparatus 1 of this invention makes the object of recycling. It is a flowchart which shows an example of the method of controlling the waste-material recycling apparatus 1 of the example of this invention shown in FIG. It is a flowchart which shows a preferable example of the recycling method of the waste material of this invention. It is a figure which shows typically the waste-material recycling apparatus 31 of the other preferable example of this invention. It is a figure which shows notionally the plasma generator 41 of an example provided with the A electrode 3 in which the dielectric material 42 was provided, and the B electrode 4 in which the dielectric material 5 was provided. It is a figure which shows notionally the plasma generator 46 provided with the A electrode 3 provided with the dielectric material 42, and the B electrode 4 (no dielectric material). It is a graph which compares and shows the indium removal rate at the time of using each of three types of plasma generators, and a vertical axis | shaft is an indium removal rate (%). It is a graph which shows the current waveform data immediately after plasma irradiation obtained in Experimental Example 2, the vertical axis is current (A), and the horizontal axis is time (μsec). It is a graph which shows the electric current waveform data 5 minutes after plasma irradiation obtained in Experimental example 2, a vertical axis | shaft is an electric current (A) and a horizontal axis is time (microsecond). FIG. 2 is a graph showing the change over time of the standard deviation of the current waveform when plasma irradiation is performed for 2 minutes in the same manner as in Experimental Example 1 using the plasma generator 2 shown in FIG. The axis represents standard deviation (A), and the horizontal axis represents plasma irradiation time (sec).

Explanation of symbols

  1,31 Waste material recycling device, 2,41,46 Plasma generator, 3 A electrode, 4 B electrode, 5,42 Dielectric, 6 Power source, 7 Waste material, 8 Base material, 9 Transparent conductive film, 10 Gas Supply path, 11 Supply gas inlet, 12, 32 Supply gas outlet, 13 A electrode frame, 14 B electrode frame, 16 Oscilloscope, 17 Current waveform analysis device, 18 Control device, 33 Suction mechanism, 34 Dust collection mechanism, 35 Separated material, 36 cooling mechanism, 51 liquid crystal panel, 52, 53 substrate, 54 electrode material, 55, 58 ITO electrode, 56, 59 alignment film, 57 color filter, 60 liquid crystal, 61, 62 sealing material, 63, 64 polarizing plate.

Claims (26)

  A waste material recycling apparatus comprising a plasma generator as means for plasma processing waste material containing a transparent conductive film.   The apparatus according to claim 1, wherein the waste material includes a base material and a transparent conductive film formed on the base material.   The apparatus according to claim 2, wherein the substrate is made of glass and / or plastic.   The apparatus according to claim 1, wherein the plasma generator includes an atmospheric pressure non-equilibrium plasma discharge mechanism.   The apparatus of claim 4, wherein the atmospheric pressure non-equilibrium plasma discharge mechanism comprises a dielectric barrier discharge mechanism.   6. The apparatus according to claim 5, wherein the dielectric barrier discharge mechanism is a parallel plate electrode in which two plate electrodes are arranged in parallel.   The apparatus according to claim 6, wherein the waste material is installed between two electrodes of the parallel plate electrode.   The apparatus according to claim 6 or 7, wherein a dielectric is provided on at least one of the two electrodes of the parallel plate electrode.   The apparatus according to claim 8, wherein the waste material is installed on an electrode provided with the dielectric.   The apparatus according to claim 8 or 9, wherein the waste material is installed in the order of an electrode provided with the dielectric, a base material, and a transparent conductive film.   The apparatus according to claim 1, further comprising a mechanism for observing a current waveform of the plasma.   The apparatus according to claim 1, further comprising a mechanism for analyzing a current waveform of plasma.   13. The apparatus according to claim 11, wherein a change in a current waveform of the plasma is read and it is determined whether to end the plasma processing.   It further comprises a mechanism for storing a plasma current waveform at the end of the plasma processing, and determines whether or not to end the plasma processing when the plasma current waveform being processed matches the stored plasma current waveform. The apparatus of claim 13.   15. The apparatus according to claim 13, wherein the plasma current waveform is subjected to a conversion process to determine whether or not the plasma process is to be terminated.   A method for recycling waste material, comprising the step of plasma-treating waste material including a transparent conductive film using the apparatus according to claim 1.   The method according to claim 16, wherein the waste material is at least one selected from a flat panel display, a solar cell, a touch panel, an electromagnetic wave shielding film, a heater, an antifogging window, and an antistatic film.   The method according to claim 17, wherein the flat panel display is at least one selected from a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, a field emission display, and electronic paper.   The method according to claim 16, wherein the waste material includes a base material and a transparent conductive film formed on the base material.   The method according to claim 19, wherein the substrate includes at least one selected from a metal, a metal compound, and an organic substance.   The method according to claim 20, wherein at least one selected from a metal, a metal compound, and an organic substance is separated from the base material by plasma treatment.   The method according to claim 21, wherein at least one selected from a metal, a metal compound, and an organic substance separated from a base material is collected and recycled.   The method according to any one of claims 20 to 22, wherein the metal and / or metal compound is indium and / or an indium compound.   The method according to any one of claims 19 to 23, wherein the plasma-treated substrate is recycled.   A metal and / or a metal compound obtained by the method for recycling waste materials according to any one of claims 16 to 24.   The base material obtained from the flat panel display by the recycling method of the waste material in any one of Claims 16-24.

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