JP3581585B2 - Electrodeposition equipment - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrodeposition apparatus for depositing an oxide, particularly zinc oxide, on a substrate by an electrodeposition method (eg, electrolytic plating, electrolytic deposition), and particularly to a case where a highly conductive electrodeposition bath is used. The present invention relates to an electrodeposition apparatus capable of stably depositing an oxide.
[0002]
[Prior art]
Conventionally, there have been several methods for depositing a functional film, such as a resistance heating evaporation method, a CVD method, a sputtering method, a spray pyrolysis method, and an electrodeposition method.
[0003]
Among them, the electrodeposition method (electroplating, which is synonymous with “plating”, which is included in the “wet process”) for electrochemically depositing a material dissolved in an aqueous solution on a substrate has the following advantages, It can also be applied to substrates.
[0004]
In addition, a long substrate refers to an extremely thin rectangular thin plate that can be wound up in the longitudinal direction and held in the form of a roll, and has various names such as roll substrate, web, hoop material, coil, tape, and reel material. However, hereafter, it is unified with a long substrate.
[0005]
By using such a long substrate, film formation can be performed continuously, which is extremely industrially advantageous, for example, the operating rate and running cost of the apparatus can be reduced.
[0006]
The first advantage in the case of using the electrodeposition method is that, unlike a vacuum apparatus used in a sputtering method or the like, film deposition is extremely simple. That is, in the electrodeposition method, an expensive vacuum pump is not required, and the power supply for using the plasma and the design around the electrodes are not disturbed, so that the film deposition becomes extremely simple.
[0007]
The second advantage of using the electrodeposition method is that running cost is generally low. That is, in the sputtering method, man-hours and equipment are required for manufacturing the target, which is expensive, and the utilization efficiency of the target is about 20% or less, and the running cost is high. Further, when the throughput of the apparatus must be increased or when the film thickness is large, the work of replacing the target occupies a considerable weight, and the work efficiency is poor.
[0008]
Further, in terms of running cost, the electrodeposition method is more advantageous than the CVD method and the vacuum evaporation method other than the sputtering method.
[0009]
The third advantage of using the electrodeposition method is that it is advantageous in terms of conductive properties and optical properties. That is, a film formed on a long substrate is often polycrystalline fine particles, and the electrodeposition method has conductive and optical characteristics comparable to those formed by a vacuum method. As shown, it is advantageous compared with the sol-gel method, the coating method using an organic substance, and the spray pyrolysis method.
[0010]
The fourth advantage of using the electrodeposition method is that even when an oxide is formed, in addition to the above-mentioned advantages, the waste liquid can be easily treated, so that the effect on the environment is reduced. And the cost for preventing environmental pollution is not high.
[0011]
There are various electrodeposition apparatuses capable of forming a film on a long substrate. For example, an electrodeposition tank and an electrodeposition tank provided on an entrance side and an exit side of the long substrate of the electrodeposition tank, respectively. There is known an apparatus in which a long substrate is supported and transported by an exit roller and continuously passed through an electrodeposition tank to form a film on the surface of the long substrate. Further, in such an electrodeposition apparatus, in order to stir the electrodeposition bath and to make the electrodeposition film uniform, a jet stream is generated by feeding stirring air into the electrodeposition bath.
[0012]
[Problems to be solved by the invention]
However, film formation using the above-mentioned conventional electrodeposition apparatus has the following problems.
[0013]
That is, when a film is formed using the above-described conventional electrodeposition apparatus, the long substrate vibrates up and down under the influence of the jet or the stirring air, so that the long substrate is moved into the electrodeposition tank or the electrodeposition electrode. There is a possibility that the long substrate may be adversely affected, for example, meandering without passing through the center of the tank exit roller or the like, and coming into contact with a structure or a wall installed in the electrodeposition tank.
[0014]
In addition, when the long substrate meanders and comes into contact with the electrodeposition tank wall or a structure installed in the electrodeposition tank, there is a possibility that the widthwise end of the long substrate may be bent.
[0015]
By the way, when a long substrate is transferred to a CVD process in order to form a solar cell using this long substrate, if such a bend is even part, abnormal discharge occurs or the long substrate Process obstacles, such as the inability to pass through a gate with a narrow clearance, cause the entire long substrate to be defective.
[0016]
Further, if there is a bias in the tension, the stirring air flows toward the weak side of the long substrate with a weak tension, and the long substrate is conveyed in a state inclined in the electrodeposition tank due to the influence. As a result, the distance to the anode varies in the width direction of the long substrate, and thus there is a possibility that unevenness in film thickness occurs in the width direction of the long substrate. Therefore, for example, when a semiconductor layer mainly composed of amorphous silicon or a transparent conductive layer of ITO is formed by a CVD process in order to form a solar cell, variations in characteristics occur.
[0017]
Such a phenomenon is more remarkable as the jet flow is stronger, and is more remarkable as the flow rate of the stirring air is increased to increase the stirring effect. In this case, the advantage that the electrodeposition method can reduce the running cost cannot be sufficiently exhibited.
[0018]
An electrodeposition apparatus according to the present invention has been proposed in view of the above circumstances, and provides an electrodeposition apparatus capable of preventing a long substrate from meandering and performing uniform film formation at a high deposition rate. The purpose is to do.
[0019]
[Means for Solving the Problems]
In order to achieve the above-described object, an electrodeposition apparatus according to the present invention includes an electrodeposition tank in which an electrodeposition bath is held and a long substrate can pass, and a long substrate passing through the electrodeposition tank. In the electrodeposition apparatus for depositing oxide on the surface of the electrode, an electrodeposition tank entrance roller for supporting the elongated substrate and an electrodeposition tank exit are provided on the entry side and the exit side of the elongated substrate of the electrodeposition tank, respectively. A roller is provided, between the electrodeposition tank entrance roller and the electrodeposition tank exit roller,By supporting the long substrate to hold itSuppress the vertical movement of the long substrateRuleA control member is provided.
[0020]
Further, it is preferable that the regulating member is provided on the upper or lower part of the long substrate.
[0021]
Further, it is preferable that the regulating member has a roller shape.
[0022]
Further, it is preferable that the regulating member has a floating potential.
[0023]
Further, it is preferable that the regulating member is formed of a dielectric or that the surface is coated with a dielectric.
[0024]
Further, when the regulating member is formed of a dielectric or its surface is coated with a dielectric, it is preferable that the dielectric be a fluororesin.Further, it is preferable that the regulating member supports the substrate without contacting the film formation surface.
[0025]
BEST MODE FOR CARRYING OUT THE INVENTION
[Main structure of electrodeposition equipment]
Hereinafter, an embodiment of the electrodeposition apparatus according to the present invention will be described.
[0026]
First, the main structure of the electrodeposition apparatus according to the present invention will be described.
[0027]
The electrodeposition apparatus according to the present invention includes, as main devices, an electrodeposition tank holding an electrodeposition bath for electrochemically depositing zinc oxide, and each electrodeposition bath (electrolyte solution) for the electrodeposition tank. It has two sets of a circulation tank heated to a predetermined temperature and fed, and an independent drainage tank electrodeposition tank capable of storing all the electrodeposition baths held in the electrodeposition tank and the circulation tank at one time.
[0028]
The electrodeposition tank used in the electrodeposition apparatus according to the present invention is made of corrosion-resistant stainless steel, heat-resistant vinyl chloride, FRP, or the like, and may have a double structure in which a heat insulating material is interposed to improve heat retention. Since the electrodeposition tank has both electrodes inside for electrodeposition of the anode and the long substrate, metal parts such as the tank wall are not exposed to prevent current stray from both electrodes. When a metal bath is used, it is preferable to provide an insulating lining inside and further to set the electrodeposition bath itself to a float potential.
[0029]
Further, it is also possible to use different electrodeposition baths for a plurality of electrodeposition tanks.
[0030]
The circulation tank used in the electrodeposition apparatus according to the present invention is made of stainless steel having excellent corrosion resistance and heat resistance, and has a built-in heater for heating the electrodeposition bath. In order to improve the heating efficiency, a double structure can be used similarly to the electrodeposition tank. Further, in order to improve the heating efficiency, it is preferable that the electrodeposition bath circulating in the circulation tank form a flow flowing around the heater. For this purpose, it is generally preferable to adopt a structure in which the electrodeposition bath is returned from the upper part of the circulation tank and the heated electrodeposition bath is sent to the electrodeposition tank from the lower part. Further, by providing a plurality of paths for sending the electrodeposition bath to the electrodeposition tank, the heating efficiency can be further improved.
[0031]
The drainage tank used in the electrodeposition apparatus according to the present invention has an internal capacity capable of holding at least all of the electrodeposition bath of the electrodeposition tank, so that the capacity of the electrodeposition bath including the electrodeposition tank and the circulation tank can be held. Is more preferable. The drainage tank does not necessarily need to be heat-resistant, but is preferably made of a heat-resistant material like an electrodeposition tank for the purpose of holding all the electrodeposition baths in an emergency.
[0032]
The air stirring means used in the electrodeposition apparatus according to the present invention is such that the electrodeposition bath moves the electrodeposition bath so that the surface of the long substrate can be exchanged in the electrodeposition bath, and further uses the long substrate. In this case, it is assumed that air is not formed on the surface of the long substrate. As a specific air stirring means, for example, the air stirring means can be formed such that bubbles come into contact with the long substrate film formation surface from the orifice formed in the tube by buoyancy. This stirring is important especially when the deposition rate is high, so that the electrodeposition bath is always fresh and touches the surface of the long substrate.
[0033]
Although not shown, a solar cell formed using the electrodeposition apparatus according to the present invention is provided on a substrate serving as a substrate, a backside reflective layer, a transparent conductive layer made of a zinc oxide film, a semiconductor layer, and a transparent electrode layer. And a current collecting electrode layer.
[0034]
[Specific configuration of electrodeposition apparatus]
Hereinafter, a specific configuration of an electrodeposition apparatus used when forming a transparent conductive layer made of a zinc oxide film or the like on a long substrate will be described in detail with reference to the drawings.
[0035]
FIG. 1 shows an embodiment of the regulating member of the electrodeposition apparatus according to the present invention. FIG. 1 (a) is a schematic plan view of the regulating member according to the first embodiment, and FIG. And a schematic plan view of a regulating member according to the second embodiment. FIG. 2 is a configuration diagram showing a specific configuration of an electrodeposition apparatus used when a transparent conductive layer is formed on a long substrate. 3 to 9 are enlarged views of each device constituting the electrodeposition apparatus shown in FIG. 2, FIG. 3 is an enlarged view of the unwinding apparatus, and FIG. 4 is a first electrodeposition tank and a first circulation unit. FIG. 5 is an enlarged view of the second electrodeposition tank and the second circulation tank, FIG. 6 is an enlarged view of the first drainage tank and the second drainage tank, and FIG. 7 is a pure water shower tank. , A first hot water tank, a second hot water tank, a drying unit, an enlarged view of a winding device, FIG. 8 is an enlarged view of a pure water heating tank, and FIG. 9 is an enlarged view near an exhaust duct.
[0036]
As shown in FIG. 2, the electrodeposition apparatus according to the embodiment of the present invention is roughly divided into an unwinding apparatus 2012 for feeding out a long substrate 2006 wound in a coil shape, and a first electrodeposition film. A first electrodeposition tank 2066 for depositing or processing, a second electrodeposition tank 2116 for depositing or processing a second electrodeposited film, and a first electrodeposition for circulating and supplying a heated electrodeposition bath to the first electrodeposition tank 2066. The circulation tank 2120, the second circulation tank 2222 for circulating and supplying the heated electrodeposition bath to the second electrodeposition tank 2116, and the second electrodeposition tank for once storing the bath when the electrodeposition bath of the first electrodeposition tank 2066 is drained. When draining the electrodepositing bath of one drainage tank 2172 and the second electrodeposition tank 2116, the powder in the electrodeposition bath in the second drainage tank 2274 and the first electrodeposition tank 2066 for temporarily storing the bath is removed. Filter circulation system for cleaning the electrodeposition bath (first electrodeposition tank filter A piping system connected to the circulation filter 2161 (shown in detail in FIG. 4), and a filter circulation system (second electrodeposition) for removing powder in the electrodeposition bath in the second electrodeposition tank 2116 and cleaning the electrodeposition bath. A piping system using a tank filter circulation filter 2263 (shown in detail in FIG. 5), a piping system for sending compressed air for bath stirring to the first electrodeposition tank 2066 and the second electrodeposition tank 2116 (from the compressed air inlet 2182). The starting piping system (shown in detail in FIGS. 4, 5, and 6), a pure water shower tank 2360 for cleaning the long substrate 2006 on which the electrodeposited film is deposited with a pure water shower, a first pure water rinse cleaning Hot water tank 2361 for performing the cleaning, a second hot water tank 2362 for performing the second pure water rinsing cleaning, and a pure water heating tank 2339 for supplying the hot water required for these hot water tanks 2361 and 236 to the hot water tank 2339 Is washed A drying unit 2363 for drying the long substrate 2006, a winding device 2296 for winding the long substrate 2006 on which the film deposition is completed again into a coil shape, and a heating step or a drying step of an electrodeposition bath or pure water. And an exhaust system (shown in detail in FIGS. 4, 5, and 7) composed of a steam exhaust system (electrodeposition washing exhaust duct 2020 or drying exhaust duct 2370).
[0037]
In addition, the long substrate 2006 is, from left to right in FIG. 2, an unwinding device 2012, a first electrodeposition tank 2066, a second electrodeposition tank 2116, a pure water shower tank 2360, a first hot water tank 2361, The hot water tank 2362, the drying unit 2363, and the winding device 2296 flow in this order, and a predetermined electrodeposited film is deposited.
[0038]
[Unwinder]
As shown in FIG. 3, the unwinding device 2012 is set with a coil-shaped long substrate 2006 wound on the unwinding device long substrate bobbin 2001, and the unwinding device unwinding adjustment roller 2003, unwinding device The long substrate 2006 is sent out through the direction change roller 2004 and the unwinding device discharge roller 2005 in this order.
[0039]
Especially when an undercoat layer is previously deposited on the coil-shaped long substrate 2006, an interleaf (interleaf) is supplied in a form in which the long substrate 2006 or an interleaf is inserted in order to protect the layer. come. Therefore, the unwinding device 2012 is provided with an unwinding device interleaf winding bobbin 2002. Therefore, when the interleaf is wound around the long substrate 2006, the interleaf 2007 is wound around the unwinding bobbin 2002 on the unwinding device together with the unwinding of the long substrate 2006. The transfer direction of the long substrate 2006 is indicated by an arrow 2010, the rotation direction of the unwinding device long substrate bobbin 2001 is indicated by an arrow 2009, and the winding direction of the unwinding device interleaf winding bobbin 2002 is This is indicated by arrow 2008.
[0040]
The long substrate 2006 discharged from the unwinding device long substrate bobbin 2001 and the interleaf wound up by the unwinding device interleaf take-up bobbin 2002 cause interference at the position at the start of the transfer and the position at the end of the transfer, respectively. Not to be. Further, the entire unwinding device 2012 has a structure covered with an unwinding device clean booth 2011 using a hepa filter and a down flow for dust prevention.
[0041]
[First electrodeposition tank]
As shown in FIG. 4, the first electrodeposition bath 2066 is provided with a temperature-controlled electrodeposition bath in a first electrodeposition bath holding bath 2065 capable of keeping the electrodeposition bath without corroding the electrodeposition bath. The first electrodeposition bath is held so as to have a bath surface 2025.
[0042]
The position of the first electrodeposition bath surface 2025 is realized by overflow by a partition plate (not shown) provided in the first electrodeposition bath holding tank 2065. The partition plate is installed so that the electrodeposition bath is dropped toward the back side in the entire first electrodeposition bath holding tank 2065, and the gutter structure collects and overflows the electrodeposition bath at the first electrodeposition tank overflow return port 2024. The deposition bath reaches the first circulation tank 2120 via the first electrodeposition tank overflow return path 2117, where it is heated and again heated to the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe. From 2064, it is refluxed to the first electrodeposition bath holding tank 2065 to form an inflow of the electrodeposition bath sufficient to promote overflow.
[0043]
The long substrate 2006 passes through an electrodeposition tank entrance turning roller 2013 (shown in FIG. 3), a first electrodeposition tank entry roller 2014, a first electrodeposition tank exit roller 2015, and an interelectrodeposition tank turning roller 2016. It passes through the inside of the electrodeposition tank 2066. A lower surface of the long substrate 2006 which is at least a film forming surface (hereinafter, referred to as a “front surface”) is provided between a first electrodeposition tank entrance roller 2014 and a first electrodeposition tank exit roller 2015. ) Are in the electrodeposition bath and face 28 anodes 2026-2053. In actual electrodeposition, a negative potential is applied to the long substrate 2006 and a positive potential is applied to the anodes 2026 to 2053, and an electrodeposition current accompanied by an electrochemical reaction flows between the two in the electrodeposition bath. By doing.
[0044]
Four anodes 2026 to 2053 in the first electrodeposition tank 2066 are mounted on seven anode mounting tables 2054 to 2060, respectively. Each of the anode mounting tables 2054 to 2060 has a structure in which the respective anodes 2026 to 2053 are placed via an insulating plate, and a unique electric potential is applied from an independent power supply. In addition, the anode mounting tables 2054 to 2060 also have a function of maintaining a distance between the long substrate 2006 and the anodes 2026 to 2053 in the electrodeposition bath. For this reason, it is preferable that the anode mounting tables 2054 to 2060 are designed and manufactured so that the height can be adjusted so as to maintain a predetermined interval.
[0045]
Immediately before the first electrodeposition tank exit roller 2015, a first electrodeposition tank back surface electrode 2061 is provided. The back electrode 2061 of the first electrodeposition tank electrochemically deposits a film deposited on the surface opposite to the film formation surface of the long substrate 2006 (hereinafter referred to as “back surface (uramen)”) in a bath. This is realized by setting the back electrode 2061 of the first electrodeposition tank to a negative potential with respect to the long substrate 2006. The fact that the back electrode 2061 of the first electrodeposition tank is actually effective is a film that electrochemically adheres to the back surface opposite to the film formation surface of the long substrate 2006 due to the electric field wraparound. It is confirmed that the film made of the same material as that formed on the film forming surface is visually and visually removed.
[0046]
The long substrate 2006 that has passed through the first electrodeposition tank exit roller 2015 and exited from the electrodeposition bath is subjected to the electrodeposition bath from the first electrodeposition tank outlet shower 2067, and the film formation surface dries to cause unevenness. It is prevented from occurring. In addition, the cover 2019 between electrodeposition tanks provided at a transition portion between the first electrodeposition tank 2066 and the second electrodeposition tank 2116 also traps vapor generated from the electrodeposition bath, and the film formation surface of the long substrate 2006 is dried. Is prevented from doing so. Further, the second electrodeposition bath inlet shower 2086 performs the same function.
[0047]
[First circulation tank]
As shown in FIG. 4, the first circulation tank 2120 is responsible for heating and keeping the temperature of the electrodeposition bath in the first electrodeposition tank 2066 and circulating the jet. As described above, the electrodeposition bath overflowed in the first electrodeposition tank 2066 is collected at the first electrodeposition tank overflow return port 2024, passes through the first electrodeposition tank overflow return path 2117, and overflows in the first electrodeposition tank overflow. Through the return path insulating flange 2118, it reaches the first circulation tank heating storage tank 2121. Eight first circulating tank heaters 2122 to 2129 are provided in the first circulating tank heating storage tank 2121, and are used for initial heating of the electrodeposition bath at room temperature or for the electrodeposition bath whose bath temperature is reduced by circulation. Reheat to maintain the electrodeposition bath at a predetermined temperature.
[0048]
Two circulation systems are connected to the first circulation tank heating storage tank 2121. That is, the first circulation tank electrodeposition bath upstream circulation source valve 2130, the first circulation tank electrodeposition bath upstream circulation pump 2132, the first circulation tank electrodeposition bath upstream circulation valve 2135, the first circulation tank electrodeposition bath upstream circulation flexible pipe 2136, a first electrodeposition tank upstream circulation recirculation system returning from the first electrodeposition tank upstream circulation jet pipe 2063 to the first electrodeposition bath holding tank 2065 through the first circulation tank electrodeposition bath upstream circulation flange insulation pipe 2137, First circulation tank electrodeposition bath downstream circulation source valve 2139, first circulation tank electrodeposition bath downstream circulation pump 2142, first circulation tank electrodeposition bath downstream circulation valve 2145, first circulation tank electrodeposition bath downstream circulation flexible pipe 2148, This is a first electrodeposition bath downstream circulation recirculation system that returns from the first electrodeposition bath downstream circulation jet pipe 2064 to the first electrodeposition bath holding bath 2065 through the first circulation bath electrodeposition bath downstream circulation flange insulation pipe 2149.
[0049]
The electrodeposition bath returning to the first electrodeposition tank 2066 from the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe 2064 is the electrodeposition bath in the first electrodeposition bath holding tank 2065. In order to make the exchange of the effect more effective, the first circulating jet pipe 2063 and the first circulating jet pipe 2064 provided below the first electrodeposition bath holding tank 2065 are connected to the respective jet pipes. It is recirculated as a jet through the pierced orifice.
[0050]
The amount of reflux in each circulation reflux system is controlled mainly by the opening / closing degree of the first circulation tank electrodeposition bath upstream circulation valve 2135 or the first circulation tank electrodeposition bath downstream circulation valve 2145. A bypass valve 2133 for the first circulation tank electrodeposition bath upstream circulation pump provided in a bypass system in which the outlet and the inlet of the circulation tank electrodeposition bath upstream circulation pump 2132 or the first circulation tank electrodeposition bath downstream circulation pump 2142 are short-circuited and connected. Alternatively, it is controlled by the first circulation tank electrodeposition bath downstream circulation pump bypass valve 2141.
[0051]
The bypass system also serves to prevent cavitation in the pump when the amount of reflux is reduced or when the bath temperature is extremely close to the boiling point. That is, the cavitation in which the bath liquid evaporates and the liquid cannot be sent due to boiling vaporization significantly shortens the life of the pump, and is prevented by the bypass system.
[0052]
When an orifice is formed in the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe 2064 to form a jet, the reflux amount is determined by the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank upstream circulation jet pipe 2063. It is substantially determined by the pressure of the bath liquid returned to the circulation jet pipe 2064 downstream of the electrodeposition tank. In order to know this, a first circulation tank electrodeposition bath upstream circulation pressure gauge 2134 and a first circulation tank electrodeposition bath downstream circulation pressure gauge 2143 are provided, and the balance of the reflux amount is determined by these pressure gauges 2134 and 2143. You can know by.
[0053]
The amount of the reflux bath discharged from the orifice exactly conforms to Bernoulli's theorem. However, when the orifice formed in the jet pipes 2963 and 2064 has a diameter of several millimeters or less, the upstream circulation jet pipe 2063 to the first electrodeposition tank and the second The jet flow rate can be substantially constant over the entire circulation jet pipe 2064 downstream of the electrodeposition tank. Further, when the reflux amount is sufficiently large, the exchange of the electrodeposition bath is performed extremely smoothly. Therefore, even if the first electrodeposition tank 2066 is considerably long, it is necessary to make the concentration of the electrodeposition bath and the temperature uniform. It can be achieved effectively. The first electrodeposition tank overflow return path 2117 has a thickness that allows a sufficient reflux amount to flow.
[0054]
The first circulation tank electrodeposition bath upstream circulation flexible pipe 2136 and the first circulation tank electrodeposition bath downstream circulation flexible pipe 2148 provided in each circulation reflux system absorb the distortion of the piping system. On the other hand, it is effective when using a flange-insulated pipe or the like which tends to have insufficient mechanical strength.
[0055]
The first circulating tank electrodeposition bath upstream circulating flange insulating pipe 2137 and the first circulating tank electrodepositing bath downstream circulating flange insulating pipe 2149 provided in each circulating reflux system are provided in the middle of the first electrodeposition tank overflow return path 2117. The first circulation tank 2120 and the first electrodeposition tank 2066 are electrically floated together with the provided first electrodeposition tank overflow return path insulating flange 2118. This is based on the knowledge of the present inventors that by preventing the formation of unnecessary current paths, it is possible to prevent stray currents and use most of the deposition current for electrochemical film formation reactions. is there.
[0056]
In one circulation recirculation system, a bypass recirculation system including a first circulation tank electrodeposition bath bypass circulation flexible pipe 2146 and a first circulation tank electrodeposition bath bypass circulation valve 2147 that returns directly to the first circulation tank heating storage tank 2121 is provided. ing. This bypass recirculation system is used when it is desired to circulate the electrodeposition bath without refluxing the bath solution into the first electrodeposition tank 2066, for example, when raising the temperature from room temperature to a predetermined temperature.
[0057]
In addition, the one circulation circulation system from the first circulation tank 2066 passes through the first electrodeposition tank exit roller 2015 and the second substrate for applying the electrodeposition bath to the long substrate 2006 that has exited from the electrodeposition bath. A liquid feed system leading to one electrodeposition tank outlet shower 2067 is provided. This liquid feed system is connected to a first electrodeposition tank outlet shower 2067 via a first electrodeposition tank outlet shower valve 2150. The spray amount of the electrodeposition liquid from the first electrodeposition tank outlet shower 2067 is adjusted by adjusting the opening / closing degree of the first electrodeposition tank outlet shower valve 2150.
[0058]
The first circulation tank heating storage tank 2121 is provided with a lid (not shown), and has a structure for preventing loss of moisture as steam. When the bath temperature is high, the temperature of the lid also increases. Therefore, it is necessary to consider, for example, attaching a heat insulating material to the surface of the lid from the viewpoint of work safety.
[0059]
A filter circulation system is provided to remove powder in the first electrodeposition bath electrodeposition bath. The filter circulation system for the first electrodeposition tank 2066 includes a first electrodeposition tank filter circulation return flexible pipe 2151, a first electrodeposition tank filter circulation return flange insulating pipe 2152, a first electrodeposition tank filter circulation source valve 2154, Electrodeposition tank filter circulation suction filter 2156, first electrodeposition tank filter circulation pump 2157, first electrodeposition tank filter circulation pump bypass valve 2158, first electrodeposition tank filter circulation pressure switch 2159, first electrodeposition tank filter circulation pressure Gauge 2160, first electrodeposition tank filter circulation filter 2161, first electrodeposition tank filter circulation flexible pipe 2164, first electrodeposition tank filter circulation flange insulating pipe 2165, first electrodeposition tank filter circulation valve 2166, first electrodeposition Tank return circulating system electrodeposition bath upstream return valve 2167, which is from the first electrodeposition vessel filter circulation system electrodeposition bath midstream return valve 2168, a first electrodeposition vessel filter circulation system electrodeposition bath downstream return valve 2169,.
[0060]
The electrodeposition bath flows in this path in the directions of the first electrodeposition tank filter circulation directions 2155, 2162, and 2163. The powder to be removed may jump in from outside the machine, or may be formed on the electrode surface or in a bath depending on the electrodeposition reaction. The minimum size of the powder to be removed is determined by the filter size of the first electrodeposition tank filter circulation filter 2161.
[0061]
The first electrodeposition tank filter circulation return flexible pipe 2151 and the first electrodeposition tank filter circulation flexible pipe 2164 absorb the distortion of the pipe, minimize the liquid leakage from the pipe connection part, and provide insulation with poor mechanical strength. This is to protect the piping and increase the degree of freedom in arranging components of the circulation system such as the pump.
[0062]
The first electrodeposition tank filter circulation return flange insulation pipe 2152 and the first electrodeposition tank filter circulation flange insulation pipe 2165 are provided to prevent the first electrodeposition bath holding tank 2065 floated from the earth ground to fall to the earth ground. It is intended to float electrically.
[0063]
The first electrodeposition tank filter circulation suction filter 2156 is a wire mesh such as a so-called “tea strainer”, removes large debris, and follows the first electrodeposition tank filter circulation pump 2157 and the first electrodeposition tank filter circulation filter 2161. It is for protecting.
[0064]
The first electrodeposition tank filter circulation filter 2161 is the main part of this circulation system, and is for removing powder mixed or generated in the electrodeposition bath.
[0065]
The circulation flow rate of the electrodeposition bath of the present circulation system is finely adjusted mainly by the first electrodeposition tank filter circulation valve 2166, and the first electrodeposition tank is provided in parallel with the first electrodeposition tank filter circulation pump 2157. Fine adjustment is made by the filter tank circulation pump bypass valve 2158. A first electrodeposition tank filter circulation pressure gauge 2160 is provided to grasp the circulation flow rate by adjusting these valves. In addition, the first electrodeposition tank filter circulation pump bypass valve 2158 prevents fine adjustment of the flow rate as well as damage to the first electrodeposition tank filter circulation pump 2157 due to cavitation when the entire filter circulation flow rate is reduced. It is preventing.
[0066]
[First drainage tank]
As shown in FIGS. 4 and 6, the electrodeposition bath can be transferred from the first electrodeposition tank drain valve 2153 to the first liquid drainage tank 2172 via the first electrodeposition tank filter circulation return flange insulating pipe 2152. This transfer is performed for electrodeposition bath exchange, maintenance of the electrodeposition apparatus, and in an emergency. The electrodeposition bath as the drainage to be transferred is dropped to the first drainage drainage storage tank 2144 by gravity drop. For maintenance and emergency purposes, it is preferable that the first drainage tank drainage storage tank 2144 has a capacity enough to store the total bath capacity of the first electrodeposition tank 2066 and the first circulation tank 2120. A first drainage tank drainage storage tank 2144 is provided with a first drainage tank drainage storage tank top lid 2277, and a first drainage tank air vent is provided for effective gravity drop transfer of the electrodeposition bath. 2171 and a first drain tank air vent valve 2170 are provided.
[0067]
As shown in FIG. 6, after the temperature of the electrodeposition bath once dropped into the first drainage tank drainage storage tank 2144 is lowered, the electrodeposition bath is sent from the first drainage tank drainage valve 2173 to the wastewater treatment facility on the building side. Or is collected in a drum (not shown) via a first drainage tank drainage recovery valve 2174, a drainage recovery source valve 2175, a drainage recovery suction filter 2176, and a drainage recovery pump 2177, and is disposed of appropriately. Is Prior to collection and disposal, dilution with water, treatment with a chemical solution, and the like may be performed in the first drainage tank drainage storage tank 2144.
[0068]
[Agitated air introduction means]
As shown in FIG. 4, in order to stir the electrodeposition bath and to make the electrodeposition film uniform, a first electrodeposition tank stirring air introduction pipe 2062 installed at the bottom of the first electrodeposition bath holding tank 2065 was pierced. Air bubbles are ejected from the plurality of orifices.
[0069]
The air that becomes air bubbles takes in compressed air supplied to the factory from a compressed air inlet 2182 (shown in FIG. 6), passes through a compressed air pressure switch 2183 for stirring the electrodeposition bath, and introduces compressed air from the first electrodeposition tank. In the direction shown by the direction 2184, the first electrodeposition tank compressed air main valve 2185, the first electrodeposition tank compressed air flow meter 2186, the first electrodeposition tank compressed air regulator 2187, the first electrodeposition tank compressed air mist separator 2188, first electrodeposition tank compressed air introduction valve 2189, first electrodeposition tank compressed air flexible pipe 2190, first electrodeposition tank compressed air insulation pipe 2191, and first electrodeposition tank compressed air upstream control valve 2193 or second electrode The gas passes through the control valve 2192 on the downstream side of the compressed air of the electrodeposition tank and reaches the stirring electrode introduction pipe 2062 of the first electrodeposition tank.
[0070]
The long substrate 2006 transported to the second electrodeposition tank 2116 via the inter-electrodeposition tank return roller 2016 has a second electrodeposition film deposited or processed. The second electrodeposition film is the same as the first electrodeposition film, but the first electrodeposition film and the second electrodeposition film may form one film, or the same material However, it may be a two-layer laminate having different properties (for example, a layer of zinc oxide having a different particle size), or a two-layer laminate having the same properties and different materials. In some cases, for example, the transparent conductive film may be a laminate of indium oxide and zinc oxide, or may be a completely different laminate of two layers.
[0071]
Further, a low oxide is deposited in the first electrodeposition tank 2066, and oxidation progress processing is performed in the second electrodeposition tank 2116, or a low oxide is deposited in the first electrodeposition tank 2066, and the second electrodeposition tank 2116 is deposited. And a combination such as performing an etching process.
[0072]
Therefore, electrodeposition or treatment conditions such as an electrodeposition bath or treatment bath, bath temperature, bath circulation amount, current density, and stirring amount are selected according to each purpose. For example, when it is necessary to change the electrodeposition or processing time between the first electrodeposition tank 2066 and the second electrodeposition tank 2116, the passage time of the long substrate 2006 is changed to the first electrodeposition tank 2066 and the second electrodeposition tank 2116. What is necessary is just to change with the tank 2116. For that purpose, the length is adjusted by changing the length of the tank between the first electrodeposition tank 2066 and the second electrodeposition tank 2116 or by folding back the long substrate 2006.
[0073]
[Second electrodeposition tank]
As shown in FIG. 5, the second electrodeposition bath 2116 is provided with a temperature-controlled electrodeposition bath in a second electrodeposition bath holding tank 2115 which can keep the electrodeposition bath without corroding the electrodeposition bath. The second electrodeposition bath is held so as to have a bath surface 2025.
[0074]
The position of the second electrodeposition bath surface 2025 is realized by overflow by a partition plate (not shown) provided in the second electrodeposition bath holding tank 2115. The partition plate is installed so that the electrodeposition bath is dropped toward the back side in the entire second electrodeposition bath holding tank 2115, and the gutter structure collects and overflows the electrodeposition bath at the second electrodeposition tank overflow return port 2075. The deposition bath reaches the second circulation tank 2222 via the second electrodeposition tank overflow return path 2219, where it is heated and again heated in the second electrodeposition tank upstream circulation jet pipe 2113 and the second electrodeposition tank downstream circulation jet pipe. From 2114, it is refluxed to the second electrodeposition bath holding tank 2115 to form an inflow of the electrodeposition bath sufficient to promote overflow.
[0075]
The long substrate 2006 passes through the inter-deposition tank return roller 2016 (shown in FIG. 4), the second electrodeposition tank entry roller 2069, the second electrodeposition tank exit roller 2070, and the pure water shower tank return entry roller 2279. It passes through the inside of the two electrodeposition tank 2116.
[0076]
Between the second electrode 4020 and the second electrode 2070, the surface of the long substrate 2006 is in the electrodeposition bath, and the 28 second electrode 2076- 2103. The actual deposition is performed by applying a negative potential to the long substrate 2006 and a positive potential to the anode, and flowing an electrodeposition current involving an electrochemical reaction between the two in the electrodeposition bath. .
[0077]
Four anodes 2076 to 2103 in the second electrodeposition tank 2116 are mounted on the seven second electrodeposition tank anode mounting tables 2104 to 2110, respectively. Each of the anode mounting tables 2104 to 2110 has a structure in which the respective anodes 2076 to 2103 are placed via an insulating plate, and an independent potential is applied to the anode mounting tables 2104 to 2110. Further, the anode mounting tables 2104 to 2110 also have a function of maintaining a distance between the long substrate 2006 and the anodes 2076 to 2103 in the electrodeposition bath. For this reason, it is preferable that the anode mounting tables 2104 to 2110 are designed and manufactured so that the height can be adjusted so as to maintain a predetermined interval.
[0078]
The second electrode on the back surface of the electrodeposition tank 2111 provided immediately before the second electrode 2070 is used for electrochemically removing the film deposited on the back surface of the long substrate 2006 in the electrodeposition bath. This is realized by setting the back electrode 2111 of the second electrodeposition tank to a negative potential with respect to the long substrate 2006. The fact that the back electrode 2111 in the second electrodeposition tank is actually effective is a film that electrochemically adheres to the back surface of the long substrate 2006 on the opposite side to the film formation surface due to the electric field wraparound. It is confirmed that the film made of the same material as that formed on the film forming surface is visually and visually removed.
[0079]
The long substrate 2006 that passed through the second electrodeposition tank exit roller 2070 and exited from the electrodeposition bath was subjected to the electrodeposition bath from the second electrodeposition tank outlet shower 2297, and the film formation surface was dried to cause unevenness. It is prevented from occurring. In addition, a pure water shower tank return entry roller cover 2318 provided at a transition portion between the second electrodeposition tank 2116 and the pure water shower tank 2360 also traps vapor generated from the electrodeposition bath and forms a film on the long substrate 2006. The surface is prevented from drying out. Furthermore, the pure water shower tank entrance surface pure water shower 2299 and the pure water shower tank entrance rear pure water shower 2300 (shown in FIG. 7) not only wash and drop the electrodeposition bath but also perform the same function.
[0080]
[Second circulation tank]
As shown in FIG. 5, the second circulation tank 2222 is responsible for heating and keeping the temperature of the electrodeposition bath in the second electrodeposition tank 2116 and circulating the jet. As described above, the electrodeposition bath overflowed in the second electrodeposition tank 2116 is collected at the second electrodeposition tank overflow return port 2075, passes through the second electrodeposition tank overflow return path 2219, and overflows in the second electrodeposition tank 2116. Through the return path insulating flange 2220, it reaches the second circulation tank heating storage tank 2223. Eight second circulating tank heaters 2224 to 2231 are provided in the second circulating tank heating storage tank 2223, and are used when initially heating the electrodeposition bath at room temperature or when the bath temperature is reduced by circulation. Reheat to maintain the electrodeposition bath at a predetermined temperature.
[0081]
Two circulation systems are connected to the second circulation tank heating storage tank 2223. That is, the second circulation tank electrodeposition bath upstream circulation source valve 2232, the second circulation tank electrodeposition bath upstream circulation pump 2234, the second circulation tank electrodeposition bath upstream circulation valve 2237, the second circulation tank electrodeposition bath upstream circulation flexible pipe 2238, a second electrodeposition tank upstream circulation recirculation system returning to the second electrodeposition bath holding tank 2115 from the second electrodeposition tank upstream circulation jet pipe 2113 via the second circulation tank electrodeposition bath upstream circulation flange insulation pipe 2239, Second circulation tank electrodeposition bath downstream circulation source valve 2242, second circulation tank electrodeposition bath downstream circulation pump 2245, second circulation tank electrodeposition bath downstream circulation valve 2247, second circulation tank electrodeposition bath downstream circulation flexible pipe 2248, A second electrodeposition bath downstream circulation recirculation system which returns from the second electrodeposition bath downstream circulation jet pipe 2114 to the second electrodeposition bath holding bath 2115 via the second circulation bath electrodeposition bath downstream circulation flange insulation pipe 2249.
[0082]
The electrodepositing bath returning to the second electrodeposition tank 2116 from the second electrodeposition tank upstream circulation jet pipe 2113 and the second electrodeposition tank downstream circulation jet pipe 2114 is the electrodeposition bath in the second electrodeposition bath holding tank 2115. In order to make the exchange of the water effective, the upstream circulation jet pipe 2113 and the downstream circulation jet pipe 2114 provided below the second electrodeposition bath holding tank 2115 are connected to the respective jet pipes. It is recirculated as a jet through the pierced orifice.
[0083]
The amount of reflux in each circulation reflux system is controlled mainly by the degree of opening and closing of the second circulation tank electrodeposition bath upstream circulation valve 2237 or the second circulation tank electrodeposition bath downstream circulation valve 2247. A second circulation tank electrodeposition bath upstream circulation pump bypass valve 2235 provided in a bypass system in which the outlet and the inlet of the circulation tank electrodeposition bath upstream circulation pump 2234 or the second circulation tank electrodeposition bath downstream circulation pump 2245 are short-circuited and connected. Alternatively, it is controlled by the second circulation tank electrodeposition bath downstream circulation pump bypass valve 2244.
[0084]
The bypass system also serves to prevent cavitation in the pump when the amount of reflux is reduced or when the bath temperature is very close to the boiling point. As described in the description of the first electrodeposition tank 2066, the cavitation in which the bath liquid evaporates and the liquid cannot be sent due to the boiling of the bath liquid is remarkably shortened in the service life of the pump. .
[0085]
When orifices are formed in the upstream circulation jet pipe 2113 of the second electrodeposition tank and the downstream circulation jet pipe 2114 of the second electrodeposition tank to form a jet, the amount of recirculation is determined by the upstream circulation jet pipe 2113 of the second electrodeposition tank and the second electrode. It is almost determined by the pressure of the bath liquid returned to the circulation jet pipe 2114 downstream of the precipitation tank. In order to know this, a second circulation tank electrodeposition bath upstream circulation pressure gauge 2236 and a second circulation tank electrodeposition bath downstream circulation pressure gauge 2246 are provided, and the balance of the amount of reflux is controlled by these pressure gauges 2236, 2246. You can know.
[0086]
The amount of the reflux bath discharged from the orifice exactly conforms to Bernoulli's theorem. The jet flow rate can be kept substantially constant over the entirety of the downstream circulation jet pipe 2114. Further, when the reflux amount is sufficiently large, the exchange of the electrodeposition bath is performed extremely smoothly. Therefore, even if the second electrodeposition tank 2116 is considerably long, it is necessary to make the concentration of the electrodeposition bath uniform and the temperature uniform. It can be achieved effectively. The overflow return path 2219 of the second electrodeposition tank has a thickness that allows a sufficient reflux amount to flow.
[0087]
The second circulation tank electrodeposition bath upstream circulation flexible pipe 2238 and the second circulation tank electrodeposition bath downstream circulation flexible pipe 2248 provided in each circulation reflux system absorb the distortion of the piping system. On the other hand, it is effective when using a flange-insulated pipe or the like which tends to have insufficient mechanical strength.
[0088]
The second circulation tank electrodeposition bath upstream circulation flange insulation pipe 2239 and the second circulation tank electrodeposition bath downstream circulation flange insulation pipe 2249 provided in each circulation reflux system are provided in the middle of the second electrodeposition tank overflow return path 2219. The second circulation tank 2222 and the second electrodeposition tank 2116 are electrically floated together with the provided second electrodeposition tank overflow return path insulating flange 2220. This is based on the knowledge of the present inventors that by preventing the formation of unnecessary current paths, it is possible to prevent stray currents and use most of the deposition current for electrochemical film formation reactions. is there.
[0089]
In one circulation recirculation system, a bypass recirculation system including a second circulation tank electrodeposition bath bypass circulation flexible pipe 2250 and a second circulation tank electrodeposition bath bypass circulation valve 2251 directly returning to the second circulation tank heating storage tank 2223 is provided. ing. This bypass recirculation system is used when it is desired to circulate the electrodeposition bath without refluxing the bath solution into the second electrodeposition tank 2116, for example, when raising the temperature from room temperature to a predetermined temperature.
[0090]
In addition, the two circulation circulation systems from the second circulation tank 2166 lead to a second electrodeposition tank entrance shower 2068 for applying an electrodeposition bath to the long substrate 2006 immediately before reaching the second electrodeposition tank entry roller 2069. The liquid feeding system and the two liquid feeding systems that pass through the second electrodeposition tank exit roller 2070 and reach the second electrodeposition tank outlet shower 2297 for applying the electrodeposition bath to the long substrate 2006 that has exited from the electrodeposition bath. Is provided. The former liquid feeding system is connected to the second electrodeposition tank inlet shower 2068 via the second electrodeposition tank inlet shower valve 2241, and the latter liquid feeding system is connected to the second electrodeposition tank outlet shower valve 2252. To the second electrodeposition bath outlet shower 2297.
[0091]
The amount of the electrodeposition liquid sprayed from the second electrodeposition tank inlet shower 2068 can be adjusted by adjusting the opening / closing degree of the second electrodeposition tank inlet shower valve 2241 and the amount of the electrodeposition liquid sprayed from the second electrodeposition tank outlet shower 2297. The spray amount is adjusted by adjusting the opening / closing degree of the second electrodeposition tank outlet shower valve 2252.
[0092]
The second circulation tank heating storage tank 2223 is provided with a lid (not shown), and has a structure for preventing loss of moisture as steam. When the bath temperature is high, the temperature of the lid also increases. Therefore, it is necessary to consider, for example, attaching a heat insulating material to the surface of the lid from the viewpoint of work safety.
[0093]
A filter circulation system is provided to remove powder in the electrodeposition bath of the second electrodeposition tank. The filter circulation system for the second electrodeposition tank 2116 includes a second electrodeposition tank filter circulation return flexible pipe 2253, a second electrodeposition tank filter circulation return flange insulating pipe 2254, a second electrodeposition tank filter circulation source valve 2256, Electrodeposition tank filter circulation suction filter 2258, second electrodeposition tank filter circulation pump 2260, second electrodeposition tank filter circulation pump bypass valve 2259, second electrodeposition tank filter circulation pressure switch 2261, second electrodeposition tank filter circulation pressure Gauge 2262, second electrodeposition tank filter circulation filter 2263, second electrodeposition tank filter circulation flexible pipe 2266, second electrodeposition tank filter circulation flange insulating pipe 2267, second electrodeposition tank filter circulation valve 2268, second electrodeposition Tank return circulating system electrodeposition bath upstream return valve 2269, the second electrodeposition vessel filter circulation system electrodeposition bath midstream return valve 2270, which is from the second electrodeposition vessel filter circulation system electrodeposition bath downstream return valve 2271.
[0094]
The electrodeposition bath flows in this route in the direction of circulation in the second electrodeposition tank filter 2257, 2264, and 2265. The powder to be removed may jump in from outside the machine, or may be formed on the electrode surface or in a bath depending on the electrodeposition reaction. The minimum size of the powder to be removed is determined by the filter size of the second electrodeposition tank filter circulation filter 2263.
[0095]
The second electrodeposition tank filter circulation return flexible pipe 2253 and the second electrodeposition tank filter circulation flexible pipe 2266 absorb the distortion of the pipe, minimize the liquid leakage from the pipe connection part, and provide insulation with poor mechanical strength. This is to protect the piping and increase the degree of freedom in arranging components of the circulation system such as the pump.
[0096]
The second electrodeposition tank filter circulation return flange insulation pipe 2254 and the second electrodeposition tank filter circulation flange insulation pipe 2267 are used to prevent the second electrodeposition bath holding tank 2115 floated from the earth ground to fall to the earth ground. It is intended to float electrically.
[0097]
The second electrodeposition tank filter circulation suction filter 2258 is a wire mesh such as a so-called “tea strainer”, removes large debris, and follows the second electrodeposition tank filter circulation pump 2260 and the second electrodeposition tank filter circulation filter 2263. It is for protecting.
[0098]
The second electrodeposition tank filter circulation filter 2263 is the main part of this circulation system, and is for removing powder mixed or generated in the electrodeposition bath.
[0099]
The circulation flow rate of the electrodeposition bath of the present circulation system is finely adjusted mainly by the second electrodeposition tank filter circulation valve 2268, and the second electrodeposition tank provided in parallel with the second electrodeposition tank filter circulation pump 2260 Fine adjustment is made by the filter tank circulation pump bypass valve 2259. A second electrodeposition tank filter circulating pressure gauge 2262 is provided to grasp the circulating flow rate by adjusting these valves. In addition, the second electrodeposition tank filter circulation pump bypass valve 2259 serves to prevent the second electrodeposition tank filter circulation pump 2260 from being damaged due to cavitation when the entire filter circulation flow rate is reduced in addition to fine adjustment of the flow rate. It is preventing.
[0100]
[Second drainage tank]
As shown in FIGS. 5 and 6, the electrodeposition bath can be transferred from the second electrodeposition tank drain valve 2255 to the second drainage tank 2274 via the second electrodeposition tank filter circulation return flange insulating pipe 2254. This transfer is performed for electrodeposition bath exchange, maintenance of the electrodeposition apparatus, and in an emergency. The electrodeposition bath as the drainage to be transferred is dropped into the second drainage drainage storage tank 2273 by gravity drop. For maintenance and emergency purposes, it is preferable that the second drain tank 2273 has a capacity sufficient to store the total bath capacity of the second electrodeposition tank 2116 and the second circulation tank 2222. A second drainage tank drainage storage tank 2273 is provided with a second drainage tank drainage storage tank top cover 2278, and a second drainage tank air vent for effective gravity drop transfer of the electrodeposition bath. 2276 and a second drain tank air vent valve 2275 are provided.
[0101]
As shown in FIG. 6, after the temperature of the electrodeposition bath once dropped into the second drainage tank drainage storage tank 2273 is lowered, the electrodeposition bath is sent from the second drainage tank drainage valve 2180 to the wastewater treatment facility on the building side. Or is collected in a drum (not shown) through a second drain tank drain collection valve 2181, a drain collection source valve 2175, a drain collection suction filter 2176 and a drain collection pump 2177, and is disposed of appropriately. Is Prior to the collection and disposal, dilution with water, treatment with a chemical solution, and the like may be performed in the second drainage tank 2273.
[0102]
[Agitated air introduction means]
As shown in FIG. 5, in order to stir the electrodeposition bath and to make the electrodeposition film uniform, a second electrodeposition bath stirring air introduction pipe 2112 installed at the bottom of the second electrodeposition bath holding tank 2115 was pierced. Air bubbles are ejected from a plurality of orifices.
[0103]
The air that becomes air bubbles takes in compressed air supplied to the factory from a compressed air inlet 2182 (shown in FIG. 6), passes through a compressed air pressure switch 2183 for stirring the electrodeposition bath, and introduces compressed air from the second electrodeposition tank. In the direction shown by the direction 2194, the second electrodeposition tank compressed air main valve 2195, the second electrodeposition tank compressed air flow meter 2196, the second electrodeposition tank compressed air regulator 2197, and the second electrodeposition tank compressed air mist separator in order. 2198, a second electrodeposition tank compressed air introduction valve 2199, a second electrodeposition tank compressed air flexible pipe 2220, a second electrodeposition tank compressed air insulation pipe 2201, and a second electrodeposition tank compressed air upstream control valve 2202 or It passes through the second electrodeposition tank compressed air downstream control valve 2272 and reaches the second electrodeposition tank stirring air introduction pipe 2112.
[0104]
[Preliminary introduction system]
As shown in FIGS. 4, 5, and 6, the first electrodeposition tank 2066 and the second electrodeposition tank 2116 are provided with a preliminary introduction system so that a preliminary liquid or gas can be introduced. The liquid or gas from the electrodeposition tank preliminary introduction port 2213 passes through the electrodeposition tank preliminary introduction valve 2214, the first electrodeposition tank preliminary introduction valve 2215, the first electrodeposition tank preliminary introduction insulating pipe 2216, and the first electrode It is sent to the precipitation tank 2066. Similarly, the liquid or gas from the electrodeposition tank preliminary introduction port 2213 passes through the electrodeposition tank preliminary introduction valve 2214, the second electrodeposition tank preliminary introduction valve 2217, and the second electrodeposition tank preliminary introduction insulating pipe 2218. It is sent to the second electrodeposition tank 2116.
[0105]
The most probable pre-introduction system is a holding agent or replenisher for keeping the performance of the electrodeposition bath constant for a long time, but in some cases, it is a gas that dissolves in the electrodeposition bath or a powder. It is an acid that removes the body.
[0106]
[Washing]
As shown in FIG. 7, cleaning is performed in three stages: a pure water shower tank 2360, a first hot water tank 2361, and a second hot water tank 2362. In this cleaning, heated pure water is supplied to the second hot water tank 2362, the drainage liquid is used in the first hot water tank 2361, and the drainage liquid is used in the pure water shower tank 2360. I have. As a result, the long substrate 2006 is gradually washed with high-purity water after the electrodeposition in the electrodeposition tank is completed.
[0107]
The second hot water tank 2362 uses pure water of the highest purity. This pure water is supplied to the second hot water tank outlet back surface pure water shower 2309 and the second hot water tank outlet front surface pure water shower 2310 immediately before the long substrate 2006 exits.
[0108]
As shown in FIG. 8, pure water to be supplied is temporarily stored in a pure water heating tank 2339 through a flushing pure water inlet 2337 and a flushing pure water supply source valve 2338, and is supplied to the pure water heating tank pure water heater 2340. Heated to a predetermined temperature at 2343, pure water heating tank pure water delivery valve 2344, pure water heating tank pure water delivery pump 2346, pure water heating tank pressure switch 2347, pure water heating tank cartridge type filter 2349, pure water heating tank One passes from the second hot water tank outlet backside shower valve 2351 to the second hot water tank outlet backside pure water shower 2309 (shown in FIG. 7) through the flow meter 2350, and the other from the second hot water tank outlet backside shower valve 2352 to the second hot water tank outlet backside shower valve 2352. It reaches the hot water tank outlet surface pure water shower 2310 (shown in FIG. 7). The reason why the pure water is heated is to improve the cleaning effect.
[0109]
As shown in FIG. 7, pure water supplied to the showers 2309 and 2310 and stored in the second hot water tank hot water holding tank 2317 forms a pure water rinsing bath. Here, the long substrate 2006 is washed with still water. Further, in order to prevent the temperature of the pure water from dropping, the second hot water tank 2361 is provided with a second hot water tank hot water keeping heater 2307.
[0110]
Pure water overflowing from the second hot water tank hot water holding tank 2317 flows into the first hot water tank 2361 via the hot water tank connecting pipe 2232 provided in the second hot water tank 2362. Supplied to As in the second hot water tank 2317, the first hot water tank hot water holding heater 2304 is provided in the first hot water tank hot water holding tank 2362 so as to hold the temperature of pure water. Further, an ultrasonic source 2306 is provided in the first hot water tank 2361, and positively removes dirt on the surface of the long substrate 2006 between the first hot water tank roller 2282 and the second hot water tank return entry roller 2283. It is designed to be removed.
[0111]
As shown in FIG. 8, pure water from the first hot water tank hot water holding tank 2316 is supplied to a pure water shower tank pure water shower supply source valve 2323, followed by a pure water shower tank pure water shower supply pump 2325, and a pure water shower. A pure water shower supply pressure switch 2326, a pure water shower tank pure water shower supply cartridge type filter 2328, a pure water shower tank pure water shower supply flow meter 2329, and a pure water shower valve 2330 from the pure water shower tank entrance surface pure water shower valve 2330. It is sent to the pure water shower 2299 (shown in FIG. 7) at the surface of the shower tub entrance, and is sent from the pure water shower tub inlet back pure water shower valve 2331 to the pure water shower tub inlet back pure water shower 2300 (shown in FIG. 7). .
[0112]
The pure water is sent from the pure water shower tank outlet back surface pure water shower valve 2332 to the pure water shower tank outlet back surface pure water shower 2302 (shown in FIG. 7), and the pure water shower tank outlet surface pure water shower valve is provided. From 2333, it is sent to the pure water shower tank outlet surface pure water shower 2303 (shown in FIG. 7).
[0113]
Then, as shown in FIG. 7, a cleaning shower flow is applied to the front and back surfaces of the long substrate 2006 at the entrance and exit of the pure water shower tank 2360, respectively.
[0114]
The water after the shower is received in the pure water shower tank receiving tank 2315, and merges with a part of the first hot water tank hot water holding tank 2316 and a part of the second hot water tank hot water holding tank 2317 as it is, and is discarded in the washing system drainage 2336. Normally, since the washed water contains ions and the like, a predetermined treatment is required.
[0115]
In the pure water shower tank 2360, the first hot water tank 2361, and the second hot water tank 2362 for cleaning, the long substrate 2006 is formed by a pure water shower tank return entry roller 2279, a pure water shower tank roller 2280, and a first hot water tank return. It is sent to the entry roller 2281, the first hot water tank roller 2282, the second hot water tank return entry roller 2283, the second hot water tank roller 2284, and the drying return roller 2285. A pure water shower tank back surface brush 2298 is provided immediately after the pure water shower tank return entry roller 2279, and can remove relatively large powder and a product having a weak adhesive force attached to the back surface of the long substrate 2006. It has become.
[0116]
The long substrate 2006 that has reached the drying unit 2363 is firstly drained at the drying unit entrance by a drying unit entrance back surface air knife 2311 and a drying unit entrance surface air knife 2312. As shown in FIG. 8, the introduction of air into the air knife is performed by a drying system compressed air inlet 2353, a drying system compressed air pressure switch 2354, a drying system compressed air filter regulator 2355, a drying system compressed air mist separator 2356, and a drying system compressed air. Via the supply valve 2357, the drying is performed in a path of the drying section inlet back surface air knife valve 2358 or the drying section inlet front surface air knife valve 2359.
[0117]
Since the air supplied to the drying unit 2363 is particularly disadvantageous if it contains water droplets, the role of the drying system compressed air mist separator 2356 is important. That is, water supplied to the drying unit 2363 is removed by the drying system compressed air mist separator 2356.
[0118]
As shown in FIG. 7, the long substrate 2006 is dried by the radiant heat of the IR lamps 2313 provided in parallel in the process of being conveyed from the drying turn-back roller 2285 to the take-up device entry roller 2286. If the radiant heat of the IR lamp 2313 is sufficient, there is no inconvenience even if the long substrate 2006 is put into a vacuum device such as a CVD device after forming the electrodeposited film. At the time of drying the long substrate 2006, since there is generation of fog due to draining and generation of water vapor due to IR lamp radiation, the drying section exhaust port 2314 connected to the exhaust duct is indispensable.
[0119]
As shown in FIG. 9, most of the steam collected in the drying system exhaust duct 2370 returns to water in the drying system condenser 2371, is discarded to the drying system condenser drain 2373, and a part of the drying system exhaust 2374. It is thrown away. When the steam contains a harmful gas, the exhaust gas should be subjected to a predetermined treatment.
[0120]
[Winding device]
As shown in FIG. 7, the winding device 2296 is provided with a winding device entering roller 2286, a winding device direction changing roller 2287, and a winding adjusting roller 2288, and in this order, the long substrate 2006 is elongated. It is wound on a substrate winding bobbin 2289 in a coil shape. The take-up device 2296 is provided with an inter-leaf feeding bobbin 2290. When protection of the deposited layer is necessary, the inter-leaf is fed out from the inter-leaf feeding bobbin 2290 and is wound around the long substrate 2006.
[0121]
The transport direction of the long substrate 2006 is indicated by an arrow 2292, the rotation direction of the long substrate winding bobbin 2289 is indicated by an arrow 2293, and the winding direction of the interleaf feeding bobbin 2290 is indicated by an arrow 2294. ing. In FIG. 7, the long substrate 2006 wound up on the long substrate winding bobbin 2289 and the interleaf unwound from the interleaf feeding bobbin 2290 do not cause interference at the position at the start of the transfer and the position at the end of the transfer, respectively. Has become. Further, the entire winding device 2296 is covered with a clean booth 2295 using a hepa filter and a down flow for dust prevention.
[0122]
The winding device direction change roller 2287 provided in the winding device 2296 has a function of correcting the meandering of the long substrate 2006. That is, based on a signal from a meandering detector (not shown) provided between the winding device direction changing roller 2287 and the winding adjustment roller 2288, the winding device direction changing roller 2287 is wound by hydraulic servo. By shaking about the axis set on the side of the take-in device entry roller 2286, meandering can be corrected.
[0123]
The control of the winding device direction change roller 2287 is approximately the movement of the roller to the near side or the back side in FIG. 7, and the direction of the movement is opposite to the long board meandering detection direction from the meandering detector. It is. The servo gain depends on the transport speed of the long substrate 2006, but generally does not need to be large. Even when a long substrate 2006 having a length of several hundred meters is wound up, its end faces are aligned with sub-millimeter accuracy.
[0124]
[Exhaust duct]
When an electrodeposition bath or hot water is used at a temperature higher than room temperature, steam is inevitably generated. Particularly at temperatures above 80 ° C., the generation of water vapor is considerable. The water vapor generated from the bath surface of the tank accumulates on the bath surface of the tank and blows out vigorously from the gap of the electrodeposition device, sees a large amount of discharge when opening and closing the lid, and becomes water droplets from the gap of the electrodeposition device. And the operating environment of the electrodeposition apparatus is deteriorated. For this reason, it is preferable to forcibly evacuate and exhaust through the electrodeposition washing system exhaust duct 2020.
[0125]
As shown in FIG. 4, the first electrodeposition tank 2066 has a first electrodeposition tank upstream exhaust port 2021, a first electrodeposition tank middle flow exhaust port 2022, and a first electrodeposition tank downstream exhaust port 2023. An exhaust duct 2020 is connected in communication.
[0126]
As shown in FIG. 5, the electrodeposition of the second electrodeposition tank 2116 upstream exhaust port 2071, the second electrodeposition tank middle flow exhaust port 2072, and the second electrodeposition tank downstream exhaust port 2073 are performed. A flushing exhaust duct 2020 is connected in communication.
[0127]
Further, as shown in FIG. 9, a pure water shower tank exhaust port 2301 of the pure water shower tank 2360, a first hot water tank exhaust port 2305 of the first hot water tank 2361, and a second hot water tank exhaust port 2308 of the second hot water tank 2362. Is connected to an electrodeposition water washing system exhaust duct 2020.
[0128]
As shown in FIG. 9, most of the water vapor collected in the electrodeposition water washing system exhaust duct 2020 passes through the insulating flange 2365 and returns to water in the electrodeposition water washing system exhaust duct condenser 2366. It is discarded to the condenser drainage drain 2368, and a part is discarded to the electrodeposition water washing system exhaust 2369. When the steam contains a harmful gas, the exhaust gas should be subjected to a predetermined treatment.
[0129]
Further, in the electrodeposition apparatus according to the present embodiment, since the exhaust duct 2020 is made of stainless steel, the first electrodeposition bath holding tank 2065 of the first electrodeposition tank 2066 and the second electrodeposition bath of the second electrodeposition tank 2116 are formed. In order to make the holding tank 2115 have a float potential from the earth ground, a core insulating flange 2365 for electrodeposition water washing system exhaust duct and a water-insulating flange 2364 for electrodeposition water washing system exhaust duct were provided and electrically separated.
[0130]
[substrate]
The substrate material used in the electrodeposition apparatus according to the present embodiment may be any material as long as it is electrically conductive on the film deposition surface and is not affected by the electrodeposition bath, for example, SUS, Al, Metals such as Cu and Fe are used. Also, a PET film or the like with a metal coating can be used. Among these, SUS is excellent as the long substrate 2006 for performing the element formation process in a later step.
[0131]
As SUS, any of non-magnetic SUS and magnetic SUS can be applied. A typical nonmagnetic SUS is SUS304, which has excellent polishing properties and can have a mirror surface of about 0.1 s. A typical magnetic SUS is a ferrite-based SUS 430, which is effectively used in conveyance using magnetic force.
[0132]
The substrate surface may be smooth or rough. The surface properties of SUS can be changed by changing the type of rolling roller in the rolling process. For example, SUS called BA is close to a mirror surface, and SUS called 2D has noticeable unevenness. In any of the surfaces, when observed under an SEM (electron microscope), pleasantness on the order of microns may be conspicuous. For a solar cell substrate, a micron unit structure has a greater effect on the characteristics of the solar cell in both good and bad directions than large undulating irregularities.
[0133]
Further, these substrates may have another conductive material formed thereon, and are selected according to the purpose of electrodeposition. In some cases, it is preferable to form a very thin layer of zinc oxide in advance by another method since the deposition rate in the electrodeposition method can be stably improved. Certainly, the electrodeposition method is advantageous in that the cost can be reduced, but the combined use of the two methods is advantageous if the cost can be reduced comprehensively even if a somewhat expensive method is additionally employed.
[0134]
[Interleaf]
As an interleaf for protecting the deposited film, a nonwoven fabric represented by Nomex, a resin film represented by PET, or the like can be used. As a resin film such as PET, it is also possible to use a thin film of a soft Cu or Al metal. Of course, the resin film melts or fuses at an excessively high temperature, so it is necessary to confirm in advance that the long substrate 2006 has cooled to a sufficient temperature. Since the interleaf is eventually discarded, it is preferable to avoid expensive materials as much as possible from the viewpoint of cost reduction technology.
[0135]
[tension]
The tension applied to the long substrate 2006 between the unwinding device long substrate bobbin 2001 and the long substrate winding bobbin 2289 is 0.05 to 50 kg per 1 cm width of the long substrate 2006. If the tension is too weak, the long substrate 2006 may inadvertently hang down, deviate from a predetermined transport path, rub off the ends of the substrate off the rollers, or significantly deteriorate the controllability of the meandering correction. On the other hand, if the tension is too strong, the long substrate 2006 itself may be stretched, or if the conveyance is uneven, only the end in the width direction may be stretched to form a so-called “wakame” shape, distorting the entire device. Sometimes
[0136]
The tension can be generated by a force for winding the long substrate winding bobbin 2289 and a slip of a clutch (a powder clutch or the like is used) attached to a shaft of the unwinding device long substrate bobbin 2001. In this case, the transport path hardly changes irrespective of the magnitude of the tension, and all the intermediate rollers can be driven rollers, so that the degree of freedom in designing the layout of the transport components including the rollers is extremely high. On the other hand, since tension is not generated during non-transportation, another locking means is required to prevent the long substrate 2006 from hanging down at rest.
[0137]
Tension can also be generated by using a kind of tension roller that can move its axis. In this case, the tension is easily controlled and monitored, but the position of the tension roller changes, so that a design for taking the stroke is required, and the parallelism of the roller is shifted, so that the meandering is likely to occur.
[0138]
Furthermore, tension can also be generated by positively moving the intermediate roller in the direction in which friction occurs with the long substrate 2006. In this method, there is an advantage that the transport path does not change and the tension works even when the apparatus is stationary. On the other hand, for a material in which the dynamic friction and the static friction are significantly different, the design is troublesome.
[0139]
Tension, of course, has its effect on rollers that are conveyed over a larger area than rollers that contact horizontally. In order to expect the effect, not only a winding roller but also a feeding roller and a meandering correction roller can be cited.
[0140]
[Transport speed]
The transport speed of the long substrate 2006 is determined solely based on a balance between the required film thickness of the electrodeposited film and the film deposition speed. Actually, there are a total of 56 anodes in the first electrodeposition tank 2066 and the second electrodeposition tank 2116, and the transport speed of the long substrate 2006 is determined by the sum of the respective film deposition rates.
[0141]
In the electrodeposition apparatus according to the present embodiment, the transport speed of the long substrate 2006 was designed in the range of 0.5 m / min to 5 m / min. Also, in the experiment, zinc oxide was applied to a long substrate 2006 of 500 m or more at a temperature rise of 85 ° C. under good conditions, even at the lowest design speed or the highest design speed. Has been demonstrated to be possible.
[0142]
[Regulator]
As shown in FIG. 1, the regulating member is provided between an electrodeposition tank entrance roller 1001 and an electrodeposition tank exit roller 1002 provided on the entry side and exit side of the long substrate 1000 in the electrodeposition tank. And has a function of suppressing the vertical movement of the long substrate 1000.
[0143]
In the first embodiment shown in FIG. 1A, two regulating members 1003, 1004 are provided, and in the second embodiment shown in FIG. 1B, five regulating members 1003, 1005 are provided. , 1006, 1007, and 1004.
[0144]
The distances between the electrode 1001 and the roller 1002 and the respective regulating members are, for example, as shown in FIGS. 1A and 1B, respectively. That is, in the first embodiment shown in FIG. 1A, the distance between the electrodeposition roller and the regulating member 1003 is 400 mm, the distance between the regulating members 1003 and 1004 is 4,500 mm, and the regulating member 1004 is The distance between the tank exit rollers 1002 is 400 mm. Further, in the second embodiment shown in FIG. 1 (b), the distance between the electrodeposition roller and the regulating member 1003 is 400 mm, the distance between the regulating members 1003 and 1005, and the distance between the regulating members 1007 and 1004 are respectively. 750 mm, the distance between the regulating members 1005 and 1006, and the distance between the regulating members 1006 and 1007 are each 1500 mm, and the distance between the regulating member 1004 and the electrodeposition roller 1002 is 400 mm. These distances can be appropriately changed according to the length of the electrodeposition tank and the like.
[0145]
In addition, the electrodeposition tank entrance roller 1001 and the electrodeposition tank exit roller 1002 shown in FIG. 1 correspond to the first electrodeposition tank entrance roller 2014 and the first electrodeposition tank exit roller 2015 in FIG. It corresponds to the second electrodeposition tank entry roller 2069 and the second electrodeposition tank exit roller 2070.
[0146]
The long substrate 1000 shown in FIG. 1 corresponds to the long substrate 2006 shown in FIG.
[0147]
The regulating member can be composed of, for example, a roller, a blade, a rod, or the like, and suppresses the vertical substrate 1000 from moving up and down during conveyance. Further, the regulating member should fulfill functions such as suppressing the inclination of the long substrate 1000 and preventing an unnecessary current stray path from being formed. In particular, from the viewpoint that damage to the surface of the long substrate 1000 is small, it is preferable that the regulating member is formed by a roller.
[0148]
The configuration of the roller applicable to the electrodeposition apparatus according to the present invention includes a roller in which a pipe rotates around an axis such as a tension pole, and a roller in which a cylinder is formed of resin and a metal rod is used as an axis. Alternatively, a roller having a sponge rotating cylindrical portion may be used. If the friction on the surface of the roller is sufficiently small, the roller itself does not need to rotate. Further, the roller itself may be rotated by its own drive, or may be driven to rotate. In short, as a function required for the regulating member, it is important to support the long substrate 1000 from above or below and to suppress the vertical movement of the long substrate 1000.
[0149]
In order to electrically float the regulating member, the regulating member may be formed of a dielectric such as nylon or polyethylene, or the metal surface may be coated with a dielectric. Further, insulation can be obtained by sandwiching a resin in the installation portion of the regulating member. The dielectric used for the regulating member is preferably a fluororesin which is advantageous in terms of heat resistance, chemical resistance and the like.
[0150]
As described above, the regulating member has a function of suppressing the vertical movement of the long substrate 1000 during conveyance. That is, when the regulating member is not provided, the distance between the anode and the long substrate 1000 may change irregularly due to the vertical movement of the long substrate 1000. Or meandering.
[0151]
Therefore, by using the regulating member to support the long substrate 1000 so as to be pressed from above or below, it is possible to suppress vertical movement of the long substrate 1000 due to a jet or agitated air during film formation.
[0152]
By the way, when it is not preferable that the regulating member is in contact with the film formation surface due to the properties of the film to be deposited, it is preferable to support the long substrate 1000 from above. On the other hand, from the viewpoint of facilitating the setting of the long substrate 1000, it is preferable to support the long substrate 1000 from below.
[0153]
Further, even if the stirring air flows to one side of the long substrate 1000 with a weak tension by installing the regulating member, the long substrate 1000 is inclined in the electrodeposition tank due to the influence. Can be prevented from being conveyed.
[0154]
[roller]
The roller used in the electrodeposition apparatus according to the present embodiment is different from the above-described roller of the regulating member, in addition to determining the transport path of the long substrate 2006, and applying a necessary potential to the long substrate 2006. And a function such as not forming an unnecessary current stray path.
[0155]
It is particularly important to determine the transport route, not only when the degree of parallelism is firm at the beginning, but also when the temperature of the electrodeposition bath rises to a high temperature (for example, 90 ° C.) and a large bathtub undergoes thermal expansion. , The displacement of the position should be kept to a minimum. In practice, submilli play is permissible, but it is preferable that the accuracy of the parallelism on the order of 100 minutes is ensured at the time of temperature rise. The deviation of the parallelism and the twisting cause the long substrate 2006 to be shifted particularly in the electrodeposition tank. In this case, the edge portion is rubbed very often, and so-called “wakame” is generated. I will.
[0156]
If there is a stiffness of the long substrate 2006, it is not necessary to consider the surface processing by using a parallel roller. However, in the case of a soft substrate such as Al foil, the drum is a drum type called a crown. It is preferable to inflate or to provide a drainage groove. Further, in such a case, it is effective to synchronously drive the rollers, because there is no tension required to make the rollers driven.
[0157]
In order to electrically float the roller, the roller may be formed of a resin such as nylon or polyethylene, or the shaft of the metal roller may be formed of a resin. Further, a resin member may be sandwiched between the bearing installation portions to provide insulation.
[0158]
Unless power is supplied directly to the long substrate 2006 by a brush or the like, or power is supplied via a bath, it is preferable to provide at least one roller for supplying a potential called a power supply roller. If a roller close to the electrodeposition part can be used as a feeding roller, the design of the electric path for the electrodeposition current is the simplest.
[0159]
If the feeding roller cannot be placed near the anode because the chemical substance in the electrodeposition bath reacts by touching the electrodeposition bath, alternative or combined use of other methods such as brush power supply or bath power supply should be considered. This is because the long substrate 2006 has a resistance of about 0.01 Ω per meter, and an extremely large heat loss occurs when an electrodeposition current of several tens of amperes is used.
[0160]
In the meandering correction, as a concept, it is preferable to establish a transport system that hardly shifts by giving the parallelism of the rollers, and to correct a slight shift immediately before winding. In this case, the correction amount may be detected, and the correction amount may be returned to the meandering correction roller by a feedforward or feedback system. Feed-forward systems are suitable for high-speed systems that are computationally cumbersome but exceed a few meters per second. On the other hand, the feedback system is not suitable for high-speed conveyance, but can have a simple configuration.
[0161]
In any case, it is preferable to have a meandering correction roller that moves the long substrate 2006 in the direction to be corrected. In the electrodeposition device according to this embodiment, the winding device direction change roller 2287 also serves as a meandering correction roller. In order to move the long substrate 2006 in the direction to be corrected, it is preferable that friction with the long substrate 2006 be large. On the other hand, in order to absorb the distortion of the long substrate 2006 caused by the correction movement, it is preferable that the long substrate 2006 slide on the meandering correction roller. The magnitude of the friction actually used is determined experimentally, including the tension. In some cases, it is effective to select a material that optimizes friction with the long substrate 2006 or to roughen the surface. In order to move the long substrate 2006 in the direction to be corrected, the entire roller may be configured to move in parallel, or may be configured to perform a swinging motion about an axis that is somewhat away from the axis (tangent). -Call it a roller). The translation roller is effective for large displacement. On the other hand, the tangent roller simplifies the device configuration.
[0162]
[Electrical configuration of bath, pipe, and other bath holding materials]
In order to reduce the stray current and contribute almost all of the flowing current to the electrodeposition and make it a current flowing between the long substrate 2006 and the anode, the electrodeposition tank, the piping connected to it, and the components in the bath holding tank, etc. It is preferable to perform insulation treatment. Basically, almost all the flowing current can contribute to the electrodeposition by minimizing the metal part in contact with the anode and the long substrate 2006 directly or through a bath.
[0163]
In addition, since the stray current can be reduced by setting the float potential, the electrodeposition apparatus according to the present embodiment has a structure in which the metal part constituting the electrodeposition tank and the substrate transport roller is floated from the ground. Insulated tubing, large diameter flanged insulated tubing, insulating flanges made for overflow return systems, insulating flanges provided in exhaust ducts, etc. are all for this purpose.
[0164]
[Insulating flange]
It is preferable to use a pipe with a flange made of an insulator such as vinyl chloride or heat-resistant vinyl chloride for the pipe section to be electrically disconnected. The first electrodeposition tank overflow return path insulating flange 2118 provided on the first electrodeposition tank overflow return path 2117 and the second electrode provided on the second electrodeposition tank overflow return path 2219 of the electrodeposition apparatus according to this embodiment. The deposition tank overflow return path insulation flange 2220, the electrodeposition water washing system exhaust duct provided in the electrodeposition water washing system exhaust duct 2020, the washing side insulation flange 2364, the electrodeposition water washing system exhaust duct main insulation flange 2365, and the like have square cross sections. It is provided on the conduit, and the bases are manufactured at the end of the conduit, and they are fastened with insulating bolts with insulating rubber therebetween. Insulating rubber can be used at a high temperature, for example, Viton (trade name). However, when compressed, some rubber suddenly shows conductivity, and its selection requires care.
[0165]
[Electrodeposition bath]
As the electrodeposition bath, basically, those confirmed with a small experimental device such as a beaker can be used. For depositing zinc oxide having a light confinement effect applied to a solar cell undercoat layer and having irregularities, for example, an aqueous solution containing at least nitrate ions and zinc ions can be preferably used. The concentration of nitrate ions and zinc ions is preferably 0.002 mol / l to 3.0 mol / l, more preferably 0.0 mol / l to 1.5 mol / l, and most preferably 0.05 mol / l to 0.7 mol / l. l. When an electrodeposition bath containing saccharose or dextrin is used to prevent abnormal growth, the concentration of saccharose is preferably 500 g / l to 1 g / l, more preferably 100 g / l to 3 g / l. The concentration of dextrin is preferably 10 g / l to 0.01 g / l, more preferably 1 g / l to 0.025 g / l, so that a zinc oxide thin film having a texture structure suitable for a light confinement effect can be efficiently formed. Can be formed.
[0166]
Further, by setting the temperature of the electrodeposition bath at 60 ° C. or higher, a uniform zinc oxide thin film with little abnormal growth can be efficiently formed.
[0167]
When the temperature of the electrodeposition bath is high and the generation of steam is remarkable, it is preferable to provide an exhaust duct to suck the steam. By providing the exhaust duct, it is possible to prevent steam and condensed water droplets from coming out of the gap of the electrodeposition apparatus.
[0168]
Further, when a lid is provided in the tank, steam is blown out when the lid is opened, which is dangerous. Therefore, also in this case, it is preferable to provide an exhaust duct.
[0169]
When the amount of liquid decreases due to the generation of steam from the electrodeposition bath and the suction of exhaust gas, pure water may be supplied periodically.
[0170]
[Heat insulation structure of tank and piping]
It is preferable that the tank and the piping for holding and supplying / draining the heated bath or the pure water have a heat insulating structure from the viewpoint of energy saving and prevention of danger. The heat insulating structure of the tank can be realized by a double wall structure sandwiching a heat insulating material such as glass wool, or by providing a heat insulating material on the outside. In general, the heat insulating structure of the pipe can be realized by covering with a heat insulating material.
[0171]
[Electrodeposition conditions]
In performing the electrodeposition, a negative potential is applied to the long substrate 2006 and a positive potential is applied to the anode to drive an electrochemical reaction. In order to control the film thickness, it is appropriate to perform electrodeposition by current control. The current is preferably defined by the current density, and is 0.3 to 100 mA / cm.²Set within the range.
[0172]
[anode]
As the anode, a zinc plate having a purity of 2N to 4N can be used as a soluble anode. If the surface of the long substrate 2006 is dirty, it may be lightly washed with diluted nitric acid. It is preferable that the power supply line to the anode be configured to be tightened with SUS bolts, since reliable electrical contact can be guaranteed for a long period of time. SUS or Pt can be used as the insoluble anode.
[0173]
In particular, when a soluble anode is used, it is preferable to wrap the soluble anode in an anode bag in order to prevent the generated zinc oxide powder from generating dust in the electrodeposition bath. As the material of the anode bag, cotton or amide resin fiber which is not attacked in the bath can be used, and it is preferable to form an appropriate mesh. The size of the mesh is determined by defining the maximum size of the powder that causes the electrodeposition bath to reliably touch the surface and generate dust. For example, the size of a general mesh is selected from 0.5 mm to several mm.
[0174]
[Electrodeposition power supply]
It is preferable that each power supply for performing the electrodeposition has a float output. As voltage control, when a predetermined potential is applied and a current may flow in the suction direction, a power supply of a suction type should be used.
[0175]
Each power supply applies a potential to a single or a plurality of combined anodes, and causes a current to flow. In order to prevent interference between the power sources, it is preferable that a current path connecting the anodes should not appear as much as possible. Therefore, it is effective to install an insulating plate such as Teflon or vinyl chloride in the bath.
[0176]
[pump]
The pump should basically be able to achieve a sufficient flow, but at the same time it should be arranged so as to prevent cavitation. In particular, at a temperature exceeding 90 ° C., the water evaporates at a stretch due to the negative pressure to be sucked, and the gas is likely to idle around the liquid sending fins inside the pump, which tends to cause a cavitation phenomenon. Once cavitation occurs, the pump runs idle, often leading to breakage of the pump, such as seizures and broken fins. In order to prevent breakage of the pump due to the occurrence of cavitation, it is preferable to arrange the pump at a position as low as possible so that the bath liquid is pushed in, that is, a structure in which a negative pressure is hardly generated.
[0177]
[valve]
The valve may be manual or automatic. In order to reduce malfunction, an automatic valve and a manual valve may be arranged in series.
[0178]
Some of the valves of the electrodeposition apparatus according to the present embodiment are adjusted based on predetermined conditions to control the flow rate. Representatives are a first circulation tank electrodeposition bath upstream circulation valve 2135, a first circulation tank electrodeposition bath downstream circulation valve 2145, a first electrodeposition tank filter circulation system electrodeposition bath upstream return valve 2167, a first electrodeposition tank filter. Circulating system electrodeposition bath middle return valve 2168, first electrodeposition tank filter circulating electrodeposition bath downstream return valve 2169, first electrodeposition tank filter circulation valve 2166, first electrodeposition tank compressed air introduction valve 2189, first electrode Control valve 2193 on the upstream side of the agitation tank stirring air, control valve 2192 on the downstream side of the agitation air in the first electrodeposition tank, or upstream circulation valve 2237 in the second circulation tank electrodeposition bath, second circulation valve 2247 in the second circulation tank electrodeposition bath, Electrodeposition tank filter circulation system upstream electrodeposition bath return valve 2269, second electrodeposition tank filter circulation system electrodeposition bath middle return valve 2270, second electrodeposition tank filter circulation system electrodeposition bath downstream return Lube 2271, second electrodeposition tank filter circulation valve 2268, second electrodeposition tank compressed air introduction valve 2199, second electrodeposition tank stirring air upstream control valve 2202, second electrodeposition tank stirring air downstream control valve 2272, etc. It is. Also, the valves leading to the shower and the air knife are adjusted based on predetermined conditions to control the flow rate.
[0179]
[filter]
The filters used in the bath liquid system are filters for removing particles of submicron to about 10 microns, typically cartridge-type filters, and wire mesh for removing dust of several millimeters or more. Suction filters consisting of
[0180]
The particle removal filter is required to positively remove powder generated inside from the bath liquid system. The size of dust remaining on the film formed on the long substrate 2006 that is finally rolled up is determined by the filter size. Therefore, the required filter size is determined based on the required properties of the membrane.
[0181]
Suction filters are used to prevent damage to pumps and valves.
[0182]
Filters used in air systems are mainly for removing oil mist and moisture mixed with compressed air.
[0183]
[Piping]
The thickness of the pipe is determined based on the required flow rate in the pipe, but it is preferable to set the nominal diameter to 40 A or more in a portion requiring a large flow rate. In the electrodeposition apparatus according to the present embodiment, in FIG. 2, a portion shown as a thick tube uses a nominal diameter of 40A, and a portion shown as a thin tube uses a nominal diameter of 25A.
[0184]
As the material of the tube, stainless steel is used under extremely favorable conditions, but when electric connection is not preferable, it is also possible to use only a part of a tube such as heat-resistant vinyl chloride. In addition, for the connection with the joint, an insert is sufficient for a thin pipe or the same material, but for the connection of a thick pipe of vinyl chloride and stainless steel, in order to prevent the occurrence of liquid leakage due to repeated thermal expansion and contraction, It is preferable to use a flange joint.
[0185]
[Circulation amount]
The circulation amount of the bath solution should be sufficient to make the temperature uniform and the concentration of the electrodeposition bath used. For example, it may be several tens l / min or more for an electrodeposition bath of several hundred liters. It is preferable that the circulating bath liquid moves on the anode surface or the long substrate 2006 surface to form a flow for constantly replenishing a new electrodeposition bath.
[0186]
[Agitated air volume]
The air stirring is an extremely effective means for stirring the bath liquid in the electrodeposition apparatus according to the present embodiment. For example, for several hundred liters of electrodeposition bath, several meters³The flow rate is preferably about / hr or more. In order to perform air stirring, it is preferable to discharge air as small bubbles in order to enhance the stirring effect. For this purpose, for example, a configuration may be employed in which agitated air is blown from the orifice into the electrodeposition bath.
[0187]
In addition, if an air pocket is formed under the long substrate 2006, the electrodeposition reaction does not proceed, so that the film formation does not proceed. For this reason, it is necessary for the blown air to float up without stagnating.
[0188]
[Back electrode]
Unnecessary electrodeposition films formed on the back surface of the long substrate 2006 are removed by the back electrode. A negative potential is applied to the back electrode with respect to the long substrate 2006. For this reason, especially in order to prevent interference with the power source for electrodeposition, the two need to have a floating output from each other. A current of 1 A to 30 A is used per back electrode installed in one electrodeposition tank.
[0189]
The material of the back electrode is preferably Ti or SUS having a high hydrogen overvoltage. Deposits such as zinc oxide that are peeled off from the back surface of the long substrate 2006 and accumulate in the back electrode portion may be mechanically peeled outside the apparatus for repeated use, or the back electrode may be disposable. It may be discarded for each electrode.
[0190]
【Example】
Specific Examples 1 to 3 of the electrodeposition apparatus using the above-described regulating member will be described with reference to FIG.
[0191]
In the following description, the electrodeposition tank turning-back roller 2013, the electrodeposition tank turning-over roller 2016, and the pure water shower tank turning-back entry roller 2279 are shown in FIGS. 3, 4, and 5, respectively.
[0192]
[Example 1]
In Example 1, as shown in FIG. 1A, an experiment was performed in which two regulating members 1003 and 1004 were installed between an electrodeposition tank entrance roller 1001 and an electrodeposition tank exit roller 1002.
[0193]
In the first embodiment, the rollers 1003 and 1004 are formed of SUS and have a floating potential. Further, the long substrate 1000 made of SUS430 is conveyed through an electrodeposition tank entrance roller 1001 and an electrodeposition tank exit roller 1002.
[0194]
The experiment of Example 1 was performed by incorporating rollers in the electrodeposition apparatus shown in FIG. 2 so as to correspond to the above-described configuration.
[0195]
The electrodeposition bath used was 0.2 mol / l zinc nitrate, which was kept at 80 ° C. Zinc nitrate causes zinc ions or complex ions to be present in the bath and, at the same time, nitrate ions to be present in the bath. Is to be analyzed. In addition, the electrodeposition bath further contained 0.1 g / l of dextrin in order to enhance the uniformity of the transparent conductive layer composed of a zinc oxide film. The conductivity of the electrodeposition bath was 65 mS / cm.
[0196]
Under the conditions described above, the long substrate 1000 was transported at a transport speed of 1270 mm / min, and a jet and stirring air were generated in the electrodeposition bath, and an experiment was performed with the tension applied to the long substrate 1000 being 100 kg.
[0197]
In the experiment of Example 1, the long substrate 1000 was able to be suppressed from vibrating up and down almost without being affected by the jet and the stirring air. In addition, the stirring air flows to one side of the long substrate 1000 to the side where the tension is weak, and due to the influence, the long substrate 1000 is not conveyed in a state of being inclined in the electrodeposition tank. The difference in height from the part to the upper part of the electrodeposition tank was settled at about 5 mm.
[0198]
As a result, when the long substrate 1000 was conveyed by 800 m, the center of the long substrate 1000 was displaced from the center of the electrode turning roller 2013 for the electrodeposition tank, the roller 2016 for the electrodeposition tank, and the roller 2279 for the pure water shower tank. Were within 2 mm, 2 mm and 3 mm, respectively.
[0199]
When the transport speed of the long substrate 1000 is set to 350 mm / s, a transparent conductive film made of a zinc oxide film having a thickness of 1 μm and having irregularities of about 1 μm is formed on the long substrate 1000. The layers could be formed continuously.
[0200]
In addition, the potential of all the rollers installed between the electrode 1001 and the roller 1002 was dropped to the ground for the study.
[0201]
In this case, the current distribution between the anode and the long substrate 1000 changes due to the stray current generated by the roller at the ground potential, and when the distance between the anode and the long substrate 1000 is set to 10 mm, a film formed is formed. Then, a large unevenness of the film thickness occurred, and when the solar cell was formed, a large variation in the characteristics appeared.
[0202]
On the other hand, as described above, when the floating potential roller, which is one embodiment of the regulating member according to the present invention, is installed, the current distribution between the anode and the long substrate 1000 is not affected. Also, no stray current was generated. As a result, the transparent conductive layer made of the zinc oxide film was uniform, for example, one interference ring was included in the film formation region. Further, when the transport speed of the long substrate 1000 is set to 350 mm / s, a transparent conductive film made of a zinc oxide film having a thickness of 1 μm and uniform and having irregularities of about 1 μm is formed on the long substrate 1000. The layers could be formed continuously.
[0203]
[Comparative Example 1]
In Comparative Example 1, all rollers installed between the electrode 1001 and the roller 1002 were removed.
[0204]
In Comparative Example 1, while the long substrate 1000 was being conveyed, the long substrate 1000 vibrated up and down under the influence of the jet and the stirring air, and the stirring air was biased to the side of the long substrate 1000 where the tension was weak. Flowed. Under the influence, the long substrate 1000 was conveyed while being inclined in the electrodeposition tank, and the difference in height from both ends of the long substrate 1000 to the upper part of the electrodeposition tank exceeded 20 mm.
[0205]
As a result, when the long substrate 100 was conveyed by 800 m, the center of the electrodeposition tank turning-over roller 2013, the electrodeposition tank turning-back roller 2016, the center of the pure water shower tank turning-back roller 2279, and the center of the long substrate 1000 were respectively set. The length was shifted by 10 mm, 12 mm, and 15 mm, and the long substrate 1000 was in contact with a structure, a wall, or the like in the electrodeposition tank, and the end in the width direction was bent. In addition, the distance between the anode and the long substrate 1000 is different in the width direction of the long substrate 1000 because the long substrate 1000 is inclined and conveyed, and the distance between the anode and the long substrate 1000 is set to 20 mm. As a result, a large thickness unevenness occurred in the film to be formed, and a large variation in characteristics occurred when the solar cell was formed.
[0206]
In addition, when the distance between the anode and the long substrate 1000 is set to be as large as 50 mm in order to reduce the difference in relative distance, the film forming rate is reduced by one digit or more, and the required specifications as an electrodeposition apparatus are completely satisfied. It did not.
[0207]
On the other hand, when the roller, which is one embodiment of the regulating member according to the present invention, is installed as in Example 1 described above, the deviation from the position where the long substrate 1000 is first set is within 3 mm. As a result, the amount of deviation could be significantly reduced. Further, the distance between the anode and the long substrate 1000 hardly changed in the width direction of the long substrate 1000. As a result, the transparent conductive layer made of the zinc oxide film was uniform, for example, one interference ring was included in the film formation region. Further, when the transport speed of the long substrate 1000 is set to 350 mm / s, a transparent conductive film made of a zinc oxide film having a thickness of 1 μm and uniform and having irregularities of about 1 μm is formed on the long substrate 1000. The layers could be formed continuously.
[0208]
[Example 2]
In the second embodiment, as shown in FIG. 1B, five regulating members 1003, 1005, 1006, 1007, and 1004 are provided between an electrodeposition roller 1001 and an electrodeposition roller 1002. Experiments.
[0209]
Other conditions are the same as in the experiment of the first embodiment described above.
[0210]
The experiment of Example 2 was performed by incorporating rollers into the electrodeposition apparatus shown in FIG. 2 so as to correspond to the above-described configuration.
[0211]
In the experiment of Example 2, the long substrate 1000 could be prevented from vibrating up and down almost without being affected by the jet and the stirring air. In addition, the stirring air flows to one side of the long substrate 1000 to the side where the tension is weak, and due to the influence, the long substrate 1000 is not conveyed in a state of being inclined in the electrodeposition tank. The difference in height from the part to the upper part of the electrodeposition tank was settled at about 2 mm.
[0212]
As a result, when the long substrate 1000 has been transported 1000 m, the center of the long substrate 1000 is deviated from the center of the electrode feeding tank return roller 2013, the electrode roller between the electrodeposition tanks 2016, and the pure water shower tank return roller 2279. Were within 1 mm, 1 mm, 0.5 mm, and 1 mm, respectively, from the first set position.
[0213]
Further, when the transport speed of the long substrate 1000 is set to 300 mm / s, a transparent conductive film made of a zinc oxide film having an extremely uniform thickness of 1 μm and having irregularities of about 1 μm is formed on the long substrate 1000. The layers could be formed continuously.
[0214]
[Example 3]
In Example 3, an experiment was performed using a roller made of SUS with Teflon coating, instead of the roller of Example 1 described above.
[0215]
Other conditions are the same as in the experiment of the first embodiment described above.
[0216]
The experiment of Example 3 was performed by incorporating rollers into the electrodeposition apparatus shown in FIG. 2 so as to correspond to the above-described configuration.
[0217]
In the experiment of Example 3, the long substrate 1000 was able to be suppressed from vibrating up and down with little influence from the jet and the stirring air. In addition, the stirring air flows to one side of the long substrate 1000 to the side where the tension is weak, and due to the influence, the long substrate 1000 is not conveyed in a state of being inclined in the electrodeposition tank. The difference in height from the part to the upper part of the electrodeposition tank was settled at about 5 mm.
[0218]
As a result, when the long substrate 1000 was transported 900 m, the center of the long substrate 1000 was displaced from the center of the electrode turning roller 2013 for the electrodeposition tank, the roller 2016 for the interelectrode tank and the roller 2279 for the pure water shower tank. Were within 2 mm from the initially set position, 2 mm, 2 mm, and 2 mm, respectively.
[0219]
Further, when the conveyance speed of the long substrate 1000 is set to 200 mm / s, the long substrate 1000 is formed of a zinc oxide film having a thickness of 1.2 μm, which is extremely uniform and has irregularities of about 1 μm. The transparent conductive layer could be formed continuously.
[0220]
In the third embodiment, since the SUS is coated with Teflon, the same effect as in the first or second embodiment described above can be obtained without setting the roller at the floating potential, and the configuration of the electrodeposition apparatus can be simplified. We were able to.
[0221]
【The invention's effect】
The electrodeposition apparatus according to the present invention includes a regulating member for suppressing the vertical movement of the long substrate.
[0222]
Therefore, as compared with a conventional electrodeposition apparatus in which a regulating member is not provided, it is possible to suppress the vertical movement of the long substrate and prevent unevenness in film thickness during film formation and meandering of the long substrate. . Therefore, the material cost is reduced, and the cost of manufacturing the solar cell can be significantly reduced.
[0223]
In addition, since the regulation member is formed in the shape of a roller, damage to the long substrate can be minimized. In this respect as well, the material cost is reduced, and the cost of manufacturing the solar cell is greatly reduced. It becomes possible.
[0224]
Further, by setting the regulating member to the floating potential, stray current is prevented, and the current distribution between the anode and the long substrate is not affected. In this regard, the material cost is reduced. It is possible to greatly reduce the cost of manufacturing a solar cell.
[0225]
Further, by forming the regulating member from a dielectric, the same effect as described above can be obtained without positively setting the regulating member to a floating potential, thereby reducing the apparatus cost. In this case, it is possible to greatly reduce the cost of manufacturing the solar cell.
[0226]
In addition, by coating the regulating member with a dielectric, the same effect as described above can be obtained without positively setting the regulating member to a floating potential, and the device cost is reduced. In addition, the cost of manufacturing the solar cell can be greatly reduced.
[0227]
Furthermore, by using a fluororesin as the dielectric material forming the regulating member or coating the regulating member with a fluororesin, the heat resistance and the chemical resistance are excellent, and the maintenance of the device is facilitated, thereby reducing the cost of the device. As a result, the cost of manufacturing the solar cell can be significantly reduced.
[Brief description of the drawings]
1A and 1B show a regulating member of an electrodeposition apparatus according to the present invention, wherein FIG. 1A is a schematic plan view of a regulating member according to a first embodiment, and FIG. FIG. 4 is a schematic plan view of a regulating member according to the embodiment.
FIG. 2 is a configuration diagram showing an embodiment of an electrodeposition apparatus according to the present invention.
FIG. 3 is an enlarged view of the unwinding device shown in FIG. 2;
FIG. 4 is an enlarged view of a first electrodeposition tank and a first circulation tank shown in FIG. 2;
FIG. 5 is an enlarged view of a second electrodeposition tank and a second circulation tank shown in FIG. 2;
FIG. 6 is an enlarged view of a first drainage tank and a second drainage tank shown in FIG. 2;
FIG. 7 is an enlarged view of the pure water shower tank, the first hot water tank, the second hot water tank, the drying unit, and the winding device shown in FIG.
FIG. 8 is an enlarged view of the pure water heating tank shown in FIG.
FIG. 9 is an enlarged view near the exhaust duct shown in FIG. 2;
[Explanation of symbols]
1000 long substrate
1001 Electrodeposition tank entry roller
1002 Electrodeposition tank exit roller
1003-1007 Regulatory member (roller)
2001 Unwinding device Long board bobbin
2002 Unreeling take-up bobbin
2003 Unwinding device feeding adjustment roller
2004 Unwinder direction change roller
2005 Unwinder discharge roller
2006 Long board
2007 Winding Interleaf
2008 Interleaf winding direction
2009 Unwinder Long direction bobbin rotation direction
2010 Unwinding direction of long substrate
2011 Unwinder clean booth
2012 Unwinding device
2013 Folded roller at electrodeposition tank entrance
2014 First electrodeposition tank entry roller
2015 First electrodeposition tank exit roller
2016 Roller between electrodeposition tanks
2017 Roller cover for electrodeposition tank entrance
2018 First Electrodeposition Bath Holder Cover
2019 Cover between electrodeposition tanks
2020 Electrodeposition washing system exhaust duct
2021 Exhaust port upstream of the first electrodeposition tank
2022 Exhaust outlet in the first electrodeposition tank
2023 Downstream exhaust port of the first electrodeposition tank
2024 First electrodeposition tank overflow return port
2025 First electrodeposition bath surface
2026-2053 First electrodeposition tank anode
2054-2060 First electrodeposition tank anode mounting table
2061 Back electrode of first electrodeposition tank
2062 First electrodeposition tank stirring air inlet pipe
2063 Circulating jet pipe upstream of the first electrodeposition tank
2064 Recirculation jet pipe downstream of the first electrodeposition tank
2065 First electrodeposition bath holding tank
2066 First electrodeposition tank
2067 First electrodeposition tank outlet shower
2068 Entrance shower of second electrodeposition tank
2069 Second electrodeposition tank entry roller
2070 Roller leaving second electrodeposition tank
2071 Exhaust port upstream of the second electrodeposition tank
2072 Middle electrode of second electrodeposition tank
2073 Downstream exhaust port of the second electrodeposition tank
2074 Second electrodeposition bath surface
2075 Second electrodeposition tank overflow return port
2076-2103 Anode of the second electrodeposition tank
2104 to 2110 Anode mounting table for second electrodeposition tank
2111 Back electrode of second electrodeposition tank
2112 Second electrodeposition tank stirring air inlet pipe
2113 Recirculation jet pipe upstream of the second electrodeposition tank
2114 Recirculation jet pipe downstream of the second electrodeposition tank
2115 Second electrodeposition bath holding tank
2116 Second electrodeposition tank
2117 Overflow return path of first electrodeposition tank
2118 First electrodeposition tank overflow return path insulation flange
2119 First electrodeposition tank overflow return direction
2120 First circulation tank
2121 Heating tank for first circulation tank
2122 to 2129 First circulation tank heater
2130 First circulation tank upstream electrodeposition bath upstream circulation valve
2131 Upstream circulation direction of electrodeposition bath in first circulation tank
2132 First circulation tank Electrodeposition bath upstream circulation pump
2133 First circulation tank electrodeposition bath upstream circulation pump bypass valve
2134 Recirculation pressure gauge upstream of electrodeposition bath in first circulation tank
2135 First circulation tank electrodeposition bath upstream circulation valve
2136 Flexible circulation pipe upstream of electrodeposition bath for first circulation tank
2137 First circulation tank electrodeposition bath upstream circulation flange insulation pipe
2138 Second electrodeposition bath holding tank cover
2139 Recirculation valve downstream of electrodeposition bath of first circulation tank
2140 Downstream circulation direction of electrodeposition bath in first circulation tank
2141 First circulation tank electrodeposition bath downstream circulation pump bypass valve
2142 Downstream circulation pump for electrodeposition bath of first circulation tank
2143 Circulation pressure gauge downstream of electrodeposition bath in first circulation tank
2144 First drainage tank Drainage storage tank
2145 Circulation tank Electrodeposition bath downstream circulation valve
2146 1st circulation tank electrodeposition bath bypass circulation flexible pipe
2147 First circulation tank electrodeposition bath bypass circulation valve
2148 Flexible pipe for downstream circulation electrodeposition bath
2149 Circulation tank electrodeposition bath downstream circulation flange insulation pipe
2150 First circulation tank outlet shower valve
2151 First electrodeposition tank filter circulation return flexible pipe
2152 First electrodeposition tank filter circulation return flange insulation pipe
2153 First electrodeposition tank drain valve
2154 First electrodeposition tank filter circulation source valve
2155 First electrodeposition tank filter circulation direction
2156 First electrodeposition tank filter Circulation suction filter
2157 First electrodeposition tank filter circulation pump
2158 First electrodeposition tank filter circulation pump bypass valve
2159 First electrodeposition tank filter circulation pressure switch
2160 First electrodeposition tank filter circulation pressure gauge
2161 First electrodeposition tank filter circulation filter
2162 First electrodeposition tank filter circulation direction
2163 First electrodeposition tank filter circulation direction
2164 First electrodeposition tank filter flexible pipe
2165 First electrodeposition tank filter circulation flange insulation pipe
2166 First electrodeposition tank filter circulation valve
2167 First electrodeposition tank filter circulation system electrodeposition bath upstream return valve
2168 First electrodeposition tank filter circulating system Electrodeposition bath return valve
2169 First electrodeposition tank filter circulation system electrodeposition bath downstream return valve
2170 First drain tank air release valve
2171 First drainage tank air vent
2172 First drainage tank
2173 First drain tank drain valve
2174 First drainage tank drainage collection valve
2175 Wastewater collection source valve
2176 Wastewater collection suction filter
2177 Wastewater collection pump
2178 Drain collection port
2179 Drainage tank common drain
2180 Second drain tank drain valve
2181 Second drainage tank drainage collection valve
2182 Compressed air inlet
2183 Compressed air pressure switch for electrodeposition bath stirring
2184 Direction of compressed air introduction in first electrodeposition tank
2185 First electrodeposition tank compressed air source valve
2186 First electrodeposition tank compressed air flow meter
2187 First electrodeposition tank compressed air regulator
2188 First electrodeposition tank compressed air mist separator
2189 First electrodeposition tank compressed air introduction valve
2190 First electrodeposition tank compressed air flexible pipe
2191 First electrodeposition tank compressed air insulation pipe
2192 Downstream control valve of the first electrodeposition tank stirring air
2193 First electrodeposition tank stirring air upstream control valve
2194 Direction of compressed air introduction in second electrodeposition tank
2195 Second electrodeposition tank compressed air source valve
2196 Second electrodeposition tank compressed air flow meter
2197 Second electrodeposition tank compressed air regulator
2198 Second electrodeposition tank compressed air mist separator
2199 Second electrodeposition tank compressed air introduction valve
2200 Compressed air flexible pipe for second electrodeposition tank
2201 second electrodeposition tank compressed air insulation pipe
2202 Control valve for upstream side of stirring air in second electrodeposition tank
2203 Electrodeposition tank pure water inlet
2204 Electrodeposition tank pure water introduction valve
2205 Flexible pipe for the first heated storage tank pure water introduction
2206 First heating storage tank pure water introduction valve
2207 First electrodeposition tank pure water introduction valve
2208 First electrodeposition tank pure water introduction insulation pipe
2209 Flexible heating pipe with second pure water storage tank
2210 Second heating storage tank pure water introduction valve
2211 Second electrodeposition tank pure water introduction valve
2212 Second electrodeposition tank pure water introduction insulation pipe
2213 Preliminary inlet for electrodeposition tank
2214 Electrodeposition tank preliminary introduction valve
2215 First electrodeposition tank preliminary introduction valve
2216 Preliminary insulation pipe for first electrodeposition tank
2217 Preliminary valve for second electrodeposition tank
2218 Preliminary insulation pipe for second electrodeposition tank
2219 Overflow return path for the second electrodeposition tank
2220 Second electrodeposition tank overflow return path insulation flange
2221 Overflow return direction of the second electrodeposition tank
2222 Second circulation tank
2223 Second circulation tank heating storage tank
2224-2231 Second circulation tank heater
2232 Second circulation tank electrodeposition bath upstream circulation source valve
2233 Upstream circulation direction of electrodeposition bath in second circulation tank
2234 Second circulation tank electrodeposition bath upstream circulation pump
2235 Second circulation tank electrodeposition bath upstream circulation pump bypass valve
2236 upstream circulation pressure gauge for electrodeposition bath in second circulation tank
2237 Second circulation tank Electrodeposition bath upstream circulation valve
2238 Flexible pipe for upstream circulation electrodeposition bath
2239 Second circulation tank electrodeposition bath upstream circulation flange insulation pipe
2240 Flexible shower pipe at inlet of second circulation tank
2241 Second circulation tank inlet shower valve
2242 Downstream circulation source valve of the second circulation tank electrodeposition bath
2243 Circulation direction downstream of electrodeposition bath in second circulation tank
2244 Circulation tank Electrodeposition bath downstream circulation pump bypass valve
2245 Circulation pump downstream of the second circulation tank electrodeposition bath
2246 Circulation pressure gauge downstream of electrodeposition bath in second circulation tank
2247 Downstream circulation valve in second circulation tank electrodeposition bath
2248 Flexible pipe downstream circulation electrodeposition bath
2249 Insulation piping for circulation flange downstream of electrodeposition bath in second circulation tank
2250 Flexible pipe with bypass circulation electrodeposition bath
2251 Second circulation tank electrodeposition bath bypass circulation valve
2252 Second electrodeposition tank outlet shower valve
2253 2nd electrodeposition tank filter circulation return flexible pipe
2254 Second electrodeposition tank filter circulation return flange insulation pipe
2255 Second electrodeposition tank drain valve
2256 Second electrodeposition tank filter circulation valve
2257 Direction of circulation in the second electrodeposition tank filter
2258 Second electrodeposition tank filter Circulation suction filter
2259 Second electrodeposition tank filter circulation pump bypass valve
2260 Second electrodeposition tank filter circulation pump
2261 Second electrodeposition tank filter circulation pressure switch
2262 Second electrodeposition tank filter circulation pressure gauge
2263 Second electrodeposition tank filter circulation filter
2264 Direction of circulation in the second electrodeposition tank filter
2265 Second electrodeposition tank filter circulation direction
2266 Second electrodeposition tank filter circulation flexible pipe
2267 Second electrodeposition tank filter circulation flange insulation pipe
2268 Second electrodeposition tank filter circulation valve
2269 Second electrodeposition tank filter circulation system electrodeposition bath upstream return valve
2270 Return valve in the electrodeposition bath of the second electrodeposition tank filter circulation system
2271 Second electrodeposition tank filter circulating system electrodeposition bath downstream return valve
2272 Downstream control valve for stirring air in second electrodeposition tank
2273 Second drain tank Drain tank
2274 Second drainage tank
2275 Second drain tank air release valve
2276 second drain tank air vent
2277 First drain tank Drain tank upper lid
2278 Second drainage tank drainage storage tank top lid
2279 Pure water shower tub folded entry roller
2280 Pure water shower tub roller
2281 First hot water tank folded entry roller
2282 First Hot Water Tank Roller
2283 Second hot water tank return entry roller
2284 Second hot water tank roller
2285 Dry folding roller
2286 Take-up device entry roller
2287 Take-up device direction change roller
2288 Rewind adjustment roller
2289 Long substrate winding bobbin
2290 Interleaf feeding bobbin
2292 Winding direction of long board
2293 Long substrate winding bobbin rotation direction
2294 Interleaf feeding bobbin rotation direction
2295 Take-up device clean booth
2296 Take-up device
2297 Second electrodeposition tank outlet shower
2298 Pure water shower tub back brush
2299 Pure water shower tub entrance surface pure water shower
2300 Pure water shower tub entrance back pure water shower
2301 Pure water shower tub exhaust
2302 Pure water shower tank back side pure water shower
2303 pure water shower tank outlet surface pure water shower
2304 First hot water tank hot water warming heater
2305 First hot water tank exhaust port
2306 First hot water tank ultrasonic source
2307 Second hot water tank hot water warming heater
2308 Second hot water tank exhaust port
2309 Pure water shower at the back of the outlet of the second hot water tank
2310 Pure water shower at the outlet of the second hot water tank
2311 Drying unit entrance back air knife
2312 Drying unit entrance surface air knife
2313 IR lamp
2314 Drying section exhaust port
2315 Pure water shower tub
2316 First hot water tank Hot water holding tank
2317 Second hot water tank Hot water holding tank
2318 Pure water shower tub folded entry roller cover
2319 First hot water tank folded entry roller cover
2320 Second hot water tank folded entry roller cover
2321 drying section cover
2322 Connecting pipe between hot water tanks
2323 pure water shower tank pure water shower supply valve
2324 pure water shower tank pure water shower supply pump bypass valve
2325 pure water shower tank pure water shower supply pump
2326 Pure water shower tank pure water shower supply pressure switch
2327 Pure water shower tank Pure water shower supply pressure gauge
2328 Pure water shower tank Pure water shower supply cartridge type filter
2329 pure water shower tank pure water shower supply flow meter
2330 Pure water shower tub entrance surface pure water shower valve
2331 Pure water shower tank back side pure water shower valve
2332 Pure water shower tub outlet back side pure water shower valve
2333 Pure water shower tub outlet surface pure water shower valve
2334 first hot water tank hot water holding tank drain valve
2335 Second hot water tank hot water holding tank drain valve
2336 Washing system drainage
2337 Rinse pure water outlet
2338 Washing pure water supply valve
2339 Pure water heating tank
2340-2343 Pure water heater Pure water heater
2344 Pure water heating tank pure water delivery valve
2345 Pure water heating tank pure water delivery pump bypass valve
2346 Pure water heating tank pure water delivery pump
2347 Pure water heating tank pressure switch
2348 Pure water heating tank pressure gauge
2349 Pure water heating tank cartridge type filter
2350 Pure water heating tank flow meter
2351 Shower valve on back side of outlet of second hot water tank
2352 Second hot water tank outlet surface shower valve
2353 Drying system compressed air inlet
2354 Drying system compressed air pressure switch
2355 Drying compressed air filter regulator
2356 Drying compressed air mist separator
2357 Drying compressed air supply valve
2358 Air knife valve on the back side of drying section entrance
2359 Drying unit inlet surface air knife valve
2360 Pure water shower tub
2361 First hot water tank
2362 Second hot water tank
2363 drying section
2364 Electrodeposition washing system exhaust duct Washing side insulation flange
2365 Core washing flange for electrodeposition water washing system exhaust duct
2366 Electrodeposition washing system exhaust duct condenser
2367 Electrodeposition rinsing system exhaust duct heat exchange grid
2368 Electrodeposition rinsing system exhaust duct condenser drain drain
2369 Electrodeposition washing system exhaust
2370 Drying system exhaust duct
2371 Drying condenser
2372 Drying heat exchange grid
2373 Drying condenser drainage drain
2374 Dry system exhaust

Claims (8)

An electrodeposition bath that holds an electrodeposition bath and allows an elongated substrate to pass therethrough, in an electrodeposition apparatus that deposits oxide on the surface of the elongated substrate passing through the electrodeposition tank,
On the entry side and exit side of the long substrate of the electrodeposition tank, an electrodeposition tank entrance roller and an electrodeposition tank exit roller for transporting the long substrate are provided, respectively.
During the electric tank approach roller and electric tank exit roller, and characterized in that a regulation member that to suppress the vertical movement of the long substrate by supporting such pressing said elongated substrate Electrodeposition equipment. 2. The electrodeposition apparatus according to claim 1, wherein said regulating member is provided at an upper portion or a lower portion of the long substrate. The electrodeposition device according to claim 1, wherein the regulating member has a roller shape. The electrodeposition apparatus according to claim 1, wherein the regulating member has a floating potential. The electrodeposition device according to any one of claims 1 to 4, wherein the regulating member is formed of a dielectric. The electrodeposition apparatus according to any one of claims 1 to 4, wherein a surface of the regulating member is coated with a dielectric. 7. The electrodeposition apparatus according to claim 5, wherein said dielectric is a fluororesin. The electrodeposition apparatus according to any one of claims 1 to 7, wherein the regulating member supports the substrate without contacting a film formation surface.

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