JP2001152390A - Zinc oxide electrodeposition method and apparatus - Google Patents

Abstract

(57) [PROBLEMS] To provide a stable and low-resistance zinc oxide thin film without adding a secondary additive to an aqueous solution for electrochemical deposition. SOLUTION: In an electrodeposition method in which zinc oxide is electrochemically deposited on a substrate from an aqueous solution, and the deposited film is washed with water and dried, at least 30% of water adsorbed on zinc oxide is removed during drying. It is characterized by.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an improved method for electrochemically depositing zinc oxide from an aqueous solution on a substrate, and more particularly to a method and apparatus for forming a zinc oxide thin film having improved conductivity. According to. The zinc oxide thin film according to the present invention can be effectively used, for example, for a reflective layer of a solar cell. Hereinafter, the method of electrochemical deposition from an aqueous solution may be referred to as electrodeposition, but has the same meaning as electroplating.

[0002]

2. Description of the Related Art In Japanese Patent Application Laid-Open No. 9-92864,
An example in which a zinc oxide thin film is deposited and deposited on a long substrate from an aqueous solution and applied to a solar cell has been reported. Here, a technique is disclosed in which a transparent conductive film (zinc oxide film) can be deposited from an acidic solution containing zinc nitrate and nitric acid by passing an electric current.

[0003] Japanese Patent Application Laid-Open No. 10-140373 discloses a technique of electrochemically forming a zinc oxide film having excellent uniformity by adding a carbohydrate to an aqueous solution.

[0004] The present applicant has filed Japanese Patent Application No. 10-3770.
No. 05, "A substrate with a zinc oxide layer, a method for forming a zinc oxide layer, a photovoltaic element and a method for manufacturing the same", a metal aluminum layer formed by sputtering on a roll substrate, and an aluminum oxide layer whose surface is subjected to oxygen plasma treatment. Further, a method has been proposed in which a zinc oxide layer is formed by electrodeposition on a zinc oxide layer formed by sputtering.

[0005] The method of electrically depositing zinc oxide from an aqueous solution can form a film extremely easily and inexpensively as compared with a vacuum process such as a sputtering method. Is big.

[0006]

However, when the present inventor studied an electrochemical deposition method from an aqueous solution, it was found that the electrical resistance value of the formed zinc oxide film was not constant.
The disadvantage was found. In particular, it often showed a resistance value higher by two digits or more without knowing the reason, and could not be applied to, for example, a solar cell.

Zinc oxide is oxygen deficient as described in “Physical Science Selection: Electrically Conductive Oxide” (Nobuo Tsuda, Moichiro Nasu, Jun Fujimori, Kiichi Shiratori, Shokabo, 1993 revised 4th edition). It is an n-type semiconductor of the type, and its resistance value fluctuation has been pointed out before.

For example, in J. O. Barnes et a
l. , J. et al. Electrochem. Soc. , 127
(1980), 1636-1640, "Relation.
nship Between Deposition
Conditions and Physical P
rights of Sputtered Zn
In O ", it is pointed out that the resistance value of a zinc oxide film formed by sputtering under different oxygen concentrations varies greatly due to the difference in carrier density due to oxygen defects.

A. P. Roth et al. ,
JAP, 52 (1981), 6885-6692, "P
rightsies of zinc oxide f
ilms prepared by the oxid
In “ation of diethyl zinc”, it is described that, for a zinc oxide thin film formed by a CVD method, the oxygen amount during film formation and the chemical oxygen adsorption at crystal grain boundaries greatly affect the resistance value.

S. Major et al. , Thin
Solid Films, 143 (1986), 19
-30, "Thickness-Dependent
Properties of Indium-Dope
In dZnO Films, regarding the zinc oxide thin film formed by the sol-gel method, the thinner the film, the greater the influence of the interface barrier due to oxygen chemisorption, but the effect can be avoided by doping indium. I have.

Also, Baosheng Sang et.
al. , JJP, 37 (1998), L1125-
L1128, "Highly Stable ZnO
Films by Atomic Layer Dep
In “position”, it is reported that by introducing boron at the atomic layer level into a zinc oxide film formed by the MOCVD method and performing doping, the resistance value can be reduced even in a thin film.

The meaning of these documents is that zinc oxide adsorbs oxygen to the grain boundaries irrespective of the production method, thereby forming an acceptor level (ie, a trap for electrons that are n-type carriers), There is no effect if sufficient carriers can be supplied to fill the level, but if not, an interface barrier is formed and the resistance is increased. Therefore, when it is difficult to increase the resistance, it is necessary to adopt a method of absorbing oxygen, securing a film thickness enough to supply sufficient carriers, or increasing the carrier density in advance by doping. It is.

[0013] The difficulty encountered by the present inventor, however, was that the discussion due to oxygen adsorption was not applicable. That is, while vacuum annealing is extremely effective for oxygen adsorption, the inventors of the present invention can lower the resistance by raising the temperature, whether in vacuum or in air. Further, it has been found that a temperature of 400 ° C. or more causes a slight increase in resistance, which is not preferable. Furthermore, as described above, "it shows a resistance value higher by two digits or more without knowing the reason", but this was measured by applying an electric field to a zinc oxide thin film having a thickness of 1000 ° to several microns in a direction perpendicular to the film. When the potential applied to both ends of the film was about 0.01 V, and the potential was about 0.5 V, it exhibited a substantially predetermined resistance value, indicating a remarkable non-ohmic property. . Furthermore, as described in Japanese Patent Application Laid-Open No.
In the electrochemical deposition from an aqueous solution based on the publication, the film formation occurs on the negative electrode side, so that the adsorption of oxygen is rather hindered. If not, the source is unknown if oxygen adsorption is the cause.

For this reason, moisture adsorption is suspected, but none of the zinc oxide thin films has been quantitatively treated with respect to moisture adsorption and its electrical resistance in the thickness direction. Also, for the same film thickness, the initial low resistance is usually higher in the case of the sputtering method and the case of the electrochemical deposition from the aqueous solution. It is not clear whether it is inevitable due to the process restriction of immersion.

In the industrialization of electrochemical deposition from an aqueous solution based on Japanese Patent Application Laid-Open No. H10-140373, such unclear points became a major obstacle. In fact, in the process of examining using a roll film forming apparatus to be described later, even if it is intended that the water is sufficiently blown off by the IR heater, when the solar cell is actually constructed, an abnormally large series resistance R _S is exhibited, and The resistance in the thickness direction of the zinc film sometimes unexpectedly increased.

An object of the present invention is to provide a method and an apparatus capable of stably supplying a low-resistance zinc oxide thin film by using electrochemical deposition from an aqueous solution.

[0017]

[Means for avoiding the problems taught by the prior art]
The drying according to No. 2864 is described as “using an IR heater heating drying in the atmosphere, hot air heating drying with hot oxygen, vacuum drying and the like” (25 pages on page 4). A hot air nozzle 157 and an infrared heater 158 were used to simultaneously perform water repellency in the hot air nozzle 157. The temperature of the hot air in the hot air nozzle 157 was 150 ° C. The temperature of the infrared heater 158 was 200 ° C. It was disclosed. "

A drying system in which electrochemical deposition from an aqueous solution based on Japanese Patent Application Laid-Open No. H10-140373 has been practically attempted for industrialization and inconvenience has occurred is draining with a room temperature air knife followed by an IR heater. Although the temperature of the IR heater itself was heated at several hundred degrees, the temperature of the hollow thermocouple on the substrate surface was about 180 ° C. Vacuum drying had no effect. Further, in addition to the IR heater, hot air was sent by an electric heat dryer, but this did not show any improvement effect.

Japanese Patent Application Laid-Open No. Hei 10-140373 discloses the details of additives and orientation, but the drying of a zinc oxide film after film formation is described in the above-mentioned Japanese Patent Application Laid-Open No. 9-9-9.
There is no description beyond 2864 publication.

In Japanese Patent Application No. Hei 10-377005, entitled "Substrate with Zinc Oxide Layer, Method for Forming Zinc Oxide Layer, Photovoltaic Element and Manufacturing Method Thereof,"
In the stage, "... conveyed to a hot air drying furnace 2051. Here, drying is performed with convection air at a temperature sufficient to dry water. For the convection air, hot air generated in the hot air generation furnace 2055 is used. Then, dust is removed through a filter 2054, and supplied by blowing out from a hot air introducing pipe 2052. The overflowing air is collected again from a hot air collecting pipe 2053, mixed with the outside air from an external air introducing pipe 2056, and mixed with a hot air generating furnace 2055. ... ".

However, as described above, even if hot air was sent by an electric heat dryer, the effect was hardly obtained.

However, when the pieces cut from the roll were heated to 150 to 300 ° C. in an oven or an electric furnace, it was found that the resistance value was greatly reduced, and the existence of a factor that could be adjusted in a later step became clear. It has been speculated that this may be inevitable due to the limitations in the process of immersion in an aqueous solution. Therefore, it is necessary to suppress the conditions in order to stably supply a low-resistance zinc oxide thin film by using electrochemical deposition from an aqueous solution. Unfortunately, the prior art does not answer this request.

[0023]

[Experiment for grasping the mechanism] [Experiment 1: Quantification of adsorbed moisture and comparison with sputtered film] A zinc oxide film was formed on a SUS430 roll substrate (2D
On the surface) by electrochemical deposition from aqueous solution
A roll with a zinc oxide film was formed, which was formed into a film having a thickness of μm, dried by an IR heater, and had no visible moisture or the like at all. A 2 x 4 cm piece cut from the roll,
Similarly, a 2 × 4 cm piece cut out from a zinc oxide roll having a thickness of 1 μm formed by a sputtering method and a Karl Fischer moisture meter (MKC-51 manufactured by Kyoto Electronics Co., Ltd.)
0), the water content was determined. The results were about 150 μg for electrochemical deposition and about 15 μg for sputtered.
μg. It was found that those electrochemically precipitated from the aqueous solution contained about 10 times more water.

[Experiment 2: Existence of water of crystallization] In order to determine whether water is contained in the form of water of crystallization or is merely absorbed, the thickly deposited electrochemically deposited zinc oxide is scraped off. Differential thermal analyzer (EXST manufactured by Seiko Denshi)
AR6000). The measurement was performed up to 450 ° C, but no water release was observed at a specific temperature.
Changes in weight were always observed at a constant rate. From this, it was found that water was contained in the form of adsorption.

[Experiment 3: Relationship between residual moisture and resistance under some drying conditions] Using a roll with a zinc oxide film prepared in Experiment 1 (the IR heater step was passed), a part of which was 5 cm square Into a portable electric furnace (AMF-10 manufactured by Asahi Rika Seisakusho Co., Ltd.), and the rest into a roll drier (in-house production equipment, referred to as RD in this case). Let dry. Thereafter, the test piece was roll-dried, the test piece was cut to the size of the test piece, and Cr and Au were vapor-deposited using a mask of 0.25 cm ² (5.6φ) using a vacuum vapor deposition machine. And the resistance value between the SUS substrate and the SUS substrate was measured. Further, the test pieces under the same conditions were measured for the water content with the above-mentioned Karl Fischer water content meter, and the correlation with the resistance value was observed. Table 1 shows a list of the experimental results.

[0026]

[Table 1]

In the measurement of the electric resistance, since the measuring system including the measuring needle itself has a circuit resistance of about 0.4Ω, it can be considered that the degree includes an error (no correction). The residual water content is shown in% by standardizing the actual amount of the measured water content without drying anything (the IR heater process is passed). The following was found from Table 1 of the results. The resistance value depends on the residual water content. If 30% of the water is released, the resistance value is sufficiently lowered. Although the amount of water separation increases with temperature and time, the effect of temperature is greater. Although the set temperature of the system is shifted by about 100 ° C., the tendency is the same.

[Experiment 4: Moisture Adsorption After Drying] The test piece dried in Experiment 3 was allowed to stand in a normal indoor environment for 3 days, but no increase in the contained water was observed.

[Conclusion of the Experiment] It has been found that not only oxygen but also moisture adsorption increases the resistance value. Moisture adsorption is a fatal part of the process using water and involves more water than sputter. However, these moistures are released by drying in the atmosphere and lower the resistance value. Usually 10%, especially 3
A water separation of 0% guarantees a practically favorable resistance value. Once released, water does not easily adsorb. Drying that promotes water separation and removal requires applying a sufficient temperature to the membrane,
Since the set temperature varies greatly depending on the system, it must be determined experimentally.

[0030]

Means for Solving the Problems Based on the above experiments and conclusions, the invention reached by the present inventors to solve the above problems is as follows.

That is, the present invention provides a zinc oxide electrodeposition method in which zinc oxide is electrochemically deposited on a substrate from an aqueous solution, and the deposited film is washed with water and dried. It is characterized in that at least 30% is released.

The present invention also provides a zinc oxide electrodeposition apparatus for electrochemically depositing zinc oxide from an aqueous solution on a substrate, washing the deposited film with water, and drying the deposited film. It is characterized by having means for releasing at least 30%.

The zinc oxide electrodeposition method and the electrodeposition apparatus of the present invention have a further feature that "at least 30% of the water adsorbed on the zinc oxide is removed by, for example, hot air generated by a hot air generating circulator". That, "The temperature of hot air is 2
00 ° C. or more ”,“ the substrate is a roll-shaped metal ”,“ the substrate transfer speed is 1000 mm / min or more ”,“ the aqueous solution contains zinc nitrate and has a concentration of 0.05M. / L or more "," a zinc oxide thin film is formed on the substrate by sputtering prior to deposition by electrodeposition "," the thickness of the zinc oxide thin film formed by sputtering is 2000 mm or less ", Is included.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described based on specific devices.

[General Structure and Operation of Electrodeposition Apparatus of the Present Invention] FIG. 2 shows a long substrate electrodeposition apparatus to which the present invention can be applied. FIGS. 3 to 9 show enlarged views of the division. 2 and FIGS. 3 to 9, the names and reference numerals of the respective units are the same. A procedure for forming or depositing an electrodeposited film on a long substrate using the present apparatus will be described with reference to the drawings.

The apparatus is roughly divided into an unwinding apparatus 2012 for feeding a long substrate wound in a coil shape, a first electrodeposition tank 2066 for depositing or processing a first electrodeposited film, and a second electrodeposition film. A second electrodeposition tank 2116 to be deposited or processed, a first circulation tank 2120 for circulating the electrodeposition bath heated to the first electrodeposition tank, and a second circulation tank for circulating the electrodeposition bath heated to the second electrodeposition tank. The two-circulation tank 2222, the first drainage tank 2172 that temporarily stores the electrodeposition bath when draining the electrodeposition bath of the first electrodeposition tank 2066, and the second that temporarily stores the bath when the electrodeposition bath of the second electrodeposition tank 2116 is drained. Drainage tank 2274, filter circulation system for removing powder in the electrodeposition bath in first electrodeposition tank 2066 and cleaning the bath (first electrodeposition tank filter circulation filter 2161 (see FIG. 4))
(Piping system connected to the second electrodeposition tank filter circulation filter 2263 (see FIG. 5)) to remove the powder in the electrodeposition bath in the second electrodeposition tank 2116 and to clean the bath. , The first electrodeposition tank 2066 and the second electrodeposition tank 21
A piping system for sending compressed air for bath stirring to 16 (a piping system starting from a compressed air inlet 2182 (see FIG. 6)),
A pure water shower tank 2360 for cleaning the long substrate on which the electrodeposited film is deposited with a shower of pure water, a first hot water tank 2361 for performing a first pure water rinse cleaning, and a second for performing a second pure water rinse cleaning. A hot water tank 2362, a pure water heating tank 2339 for supplying hot water required for these hot water tanks, a drying unit 2363 for drying the washed long substrate, and a long substrate on which film deposition has been completed are coiled again. Winding device 2296, an exhaust system for vapor generated in a heating stage or a drying stage of the electrodeposition bath or pure water (electrodeposition washing exhaust duct 2020 (see FIGS. 4 and 5) or drying exhaust duct 2370 (see FIG. 4). 7)).

The long substrate is moved from left to right in the drawing,
12, the first electrodeposition tank 2066, the second electrodeposition tank 2116, the pure water shower tank 2360, the first hot water tank 2361, the second hot water tank 2362, the drying unit 2363, and the winding device 2296, and are transported in this order. Is deposited.

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 feeding adjusting roller 2003, the unwinding device direction. The long substrate 20 passes through the conversion roller 2004 and the unwinding device discharge roller 2005 in this order.
06 is transmitted. In the case of a coil-shaped long substrate, especially when an undercoat layer is previously deposited, an interleaf (interleaf paper) is supplied in a form entrained to protect the substrate or the layer. Therefore, when the interleaf is wound, the interleaf 2007 is wound around the unwinding bobbin 2002 in the unwinding device together with the feeding of the long substrate.

The transport direction of the long substrate 2006 is indicated by an arrow 201.
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 indicated by an arrow 2008.

In the drawing, the long substrate discharged from the unwinding device long substrate bobbin 2001 and the interleaf wound on the unwinding device interleaf take-up bobbin 2002 are respectively located at the start of the transfer and at the end of the transfer. This indicates that no interference has occurred at the location.

The entire unwinding device is structured to be covered with an unwinding device clean booth 2011 using a hepa filter and a downflow for dust prevention.

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. Is held so as to become the first electrodeposition bath surface 2025. The position of the bath surface is realized by overflow by a partition plate provided in the first electrodeposition bath holding tank 2065. The partition plate (not shown) is installed so as to drop the electrodeposition bath toward the back side in the entire first electrodeposition bath holding tank 2065, and was collected at the first electrodeposition tank overflow return port 2024 in a gutter structure. The overflowing electrodeposition bath is the first electrodeposition tank overflow return path 211.
7 and is then heated to the first circulation tank 2120 and again from the first electrodeposition tank upstream circulation jet pipe 2063 and the first electrodeposition tank downstream circulation jet pipe 2064.
It is refluxed to 65 and forms an inflow of the electrodeposition bath sufficient to promote overflow.

The long substrate 2006 is passed through an electrodeposition tank entrance turning roller 2013 (see FIG. 3), a first electrodeposition tank entry roller 2014, a first electrodeposition tank exit roller 2015, and an electrodeposition tank turning roller 2016. It passes through the inside of the first electrodeposition tank 2066. Between a first electrodeposition tank entrance roller 2014 and a first electrodeposition tank exit roller 2015, at least a lower surface of a long substrate which is a film formation surface (often referred to as “surface” in the present specification).
) Are in the electrodeposition bath and have 28 anodes 2
026-2053. The actual electrodeposition is performed by applying a negative potential to the long substrate and a positive potential to the anode, and flowing an electrodeposition current involving an electrochemical reaction between the two in the electrodeposition bath.

In this apparatus, four anodes 2026 to 2053 in the first electrodeposition tank 2066 are mounted on seven anode mounting tables 2054 to 2060.
The anode mounting table has a structure in which each anode is placed via an insulating plate, and a unique electric potential is applied from an independent power supply. Also, the anode mounting table 20
Reference numerals 54 to 2060 denote a long substrate and an anode 202 in an electrodeposition bath.
It also has the function of maintaining the interval between 6 and 2053. Therefore, usually, 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.

The electrode 2061 on the back of the first electrodeposition tank provided immediately before the roller for exiting the first electrodeposition tank 2015, the surface opposite to the film formation surface of the long substrate in the bath (herein often referred to as the “back surface”).
This is for electrochemically removing the film deposited on the first electrode of the long electrode 2006, and this is realized by setting the back electrode 2061 of the first electrodeposition tank to a negative potential.
The fact that the back electrode 2061 of the first electrodeposition tank actually has an effect is that the electrode 2061 is formed on the film formation surface of the long substrate, which electrochemically adheres to the back surface opposite to the film formation surface of the long substrate due to the electric field. It is confirmed that the film of the same material as that to be removed is visually and visually removed.

The long substrate that passed through the first electrodeposition tank exit roller 2015 and exited from the electrodeposition bath was subjected to an electrodeposition bath from the first electrodeposition tank outlet shower 2067, and the film formation surface was dried. The occurrence of unevenness is prevented. Also, the first electrodeposition tank 2066
The inter-deposition tank cover 2019 provided at the transition between the electrodeposition tank and the second electrodeposition tank 2116 also traps vapor generated from the electrodeposition bath and prevents the film-forming surface of the long substrate from drying. Further, the second electrodeposition bath inlet shower 2068 also functions to prevent drying.

The first circulation tank 2120 includes the first electrodeposition tank 206.
6 is responsible for heating and keeping the temperature of the electrodeposition bath and circulation of the jet. As described above, the electrodepositing bath overflowed in the first electrodeposition tank 2066 is returned to the first electrodeposition tank overflow return port 2.
024, return path of the first electrodeposition tank overflow 2
117, through the first electrodeposition tank overflow return path insulating flange 2118, to the first circulation tank heated 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 when initially heating the electrodeposition bath at room temperature or when the bath temperature is lowered by circulation. Is reheated to function in maintaining the electrodeposition bath at a predetermined temperature.

The first circulation tank heating storage tank 2121 is connected to two circulation systems. 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 213
5. Flexible pipe 21 circulating upstream of electrodeposition bath of first circulation tank
36, first circulation tank electrodeposition bath upstream circulation flange insulation pipe 21
37, 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, a first circulation tank electrodeposition bath downstream circulation source valve 2139, One 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, first circulation tank electrodeposition bath downstream circulation flange insulation pipe 2149 After that, it is a first electrodeposition tank downstream circulation recirculation system which returns from the first electrodeposition tank downstream circulation jet pipe 2064 to the first electrodeposition bath holding tank 2065.

The first electrodeposition tank 206 is circulated from the upstream circulation jet pipe 2063 and the downstream circulation jet pipe 2064 of the first electrodeposition tank.
The electrodeposition bath returned to 6 is the first electrodeposition bath holding tank 2 so that the exchange of the electrodeposition bath in the first electrodeposition bath holding tank 2065 can be effectively performed.
065 circulating jet pipe 20 upstream of the first electrodeposition tank
From the 63 and the downstream circulation jet pipe 2064 of the first electrodeposition tank, it is recirculated as a jet through orifices formed in each jet pipe.

The amount of reflux in each circulation reflux system is mainly
The degree of opening and closing of the first circulation tank electrodeposition bath upstream circulation valve 2135 or the first circulation tank electrodeposition bath downstream circulation valve 2145 is controlled, and further fine adjustment is performed by the first circulation tank electrodeposition bath upstream circulation pump 2132 or the first circulation tank. A first circulation tank electrodeposition bath upstream circulation pump bypass valve 2133 or a first circulation tank electrodeposition bath downstream circulation pump bypass halve provided in a bypass system in which the outlet and the inlet of the tank electrodeposition bath downstream circulation pump 2142 are short-circuited and connected. It is controlled by 2141. The bypass system also serves to prevent cavitation in the pump when the reflux rate is reduced or when the bath temperature is very close to the boiling point. Cavitation, in which the bath liquid evaporates and the liquid cannot be delivered, significantly shortens the life of the pump.

When orifices are formed in the upstream circulation jet tube 2063 and the downstream circulation jet tube 2064 to form a jet, the amount of reflux is almost the same as the upstream circulation jet tube 2063. And the pressure of the solution returned to the circulating jet pipe 2064 downstream of the first 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,
The balance of the reflux amount can be known from these pressure gauges. The amount of the reflux bath discharged from the orifice exactly follows Bernoulli's theorem. However, when the orifice formed in the jet pipe has a diameter of several millimeters or less, the upstream circulation pipe 2063 of the first electrodeposition tank or the downstream circulation of the first electrodeposition tank. The jet flow can be substantially constant over the entire jet tube 2064.

Further, when the reflux amount is sufficiently large, the exchange of the bath is carried out extremely smoothly.
Even if 66 is considerably long, uniformity of bath concentration and temperature can be effectively achieved. It is natural that the first electrodeposition tank overflow return path 2117 should be thick enough to allow this sufficient amount of reflux.

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 are:
It absorbs distortion in the piping system, and is particularly effective when using flange-insulated piping or the like, which tends to have insufficient mechanical strength against distortion.

The first circulation tank electrodeposition bath upstream circulation flange insulation pipe 2137 and the first circulation tank electrodeposition bath downstream circulation flange insulation pipe 2149 provided in each circulation reflux system are connected to 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 first electrodeposition tank overflow return insulating flange 2118 provided on the way. This is to prevent the formation of unnecessary current paths, that is, to prevent stray current leads to stably and effectively promote an electrochemical film formation reaction using an electrodeposition current. It is based on knowledge.

In one circulation recirculation system, a bypass circulation composed of a first circulation tank electrodeposition bath bypass circulation flexible pipe 2146 and a first circulation tank electrodeposition bath bypass circulation valve 2147 returning directly to the first circulation tank heating storage tank 2121. A system is provided, which is used when it is desired to circulate the bath without refluxing the bath liquid in the first electrodeposition tank, for example, when raising the temperature from room temperature to a predetermined temperature.

The first circulation tank 2120 is provided with one circulation recirculation system through the first electrodeposition tank exit roller 2015 and the first electrodeposition where the long substrate coming out of the electrodeposition bath is applied to the electrodeposition bath. A liquid feed system leading to the bath outlet shower 2067 is provided, and is connected to the first bath outlet shower 2067 via the first bath outlet shower valve 2150. The amount of the electrodeposition liquid sprayed from the first electrodeposition tank outlet shower 2067 is
It is adjusted by adjusting the opening / closing degree of the first electrodeposition bath outlet shower valve 2150.

The first circulating tank heating storage tank 2121 is actually provided with a lid, and has a structure for preventing water from being lost as steam. When the bath temperature is high, the temperature of the lid also increases, so that consideration such as attaching a heat insulating material is necessary from the viewpoint of work safety.

A filter circulation system is provided for removing powder from the electrodeposition bath of the first electrodeposition tank. The filter circulation system for the first electrodeposition tank 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, a first electrodeposition filter Deposition 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 216
1. First electrodeposition tank filter circulation flexible pipe 21
64, first electrodeposition tank filter circulation flange insulation pipe 21
65, first electrodeposition tank filter circulation valve 2166, first electrodeposition tank filter circulation system electrodeposition bath upstream return valve 216
7, the first electrodeposition tank filter circulation system electrodeposition bath return valve 2168 and the first electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2169. In this path, the electrodeposition bath is circulated in the first electrodeposition tank filter circulation direction 2155,
It flows in the direction of 2163. The powder to be removed may jump 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.

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 piping,
The purpose of the present invention is to minimize leakage of liquid from a pipe connection portion, protect insulating pipes having poor mechanical strength, and increase the degree of freedom in arranging components of a circulation system such as a pump.

The first electrodeposition tank filter circulation return flange insulating pipe 2152 and the first electrodeposition tank filter circulation flange insulation pipe 2165 are used to prevent the first electrodeposition bath holding tank 2065, which has been floated from the earth ground, to fall to the earth ground. It is intended to float electrically to prevent it.

The first electrodeposition tank filter circulation suction filter 2156 is a wire mesh such as a “tea strainer”, which removes large debris, and is followed by the first electrodeposition tank filter circulation pump 2157 and the first electrodeposition tank filter circulation. This is for protecting the filter 2161.

First electrodeposition tank filter circulation filter 21
Numeral 61 is a main part of this circulation system, and is for removing powder mixed or generated in the electrodeposition bath.

The circulating flow rate of the electrodeposition bath of the present circulation system is mainly controlled by the first electrodeposition tank filter circulation valve 2166, and the first electrodeposition tank provided in parallel with the first electrodeposition tank filter circulation pump 2157. Fine adjustment is made by the tank filter circulation pump bypass valve 2158. A first electrodeposition tank filter circulating pressure gauge 2160 is provided to grasp the circulating flow rate due to the halve adjustment. The first electrodeposition tank filter circulation pump bypass valve 2158 prevents fine adjustment of the flow rate, and also prevents the first electrodeposition tank filter circulation pump 2157 from being damaged due to cavitation when the entire filter circulation flow rate is reduced. I have.

The electrodeposition bath can be transferred from the first electrodeposition tank drain valve 2153 to the first liquid drainage tank 2172 (see FIG. 6) via the first electrodeposition tank filter circulation return flange insulating pipe 2152. This transfer is performed for electrodeposition bath replacement, equipment maintenance, and even in an emergency. The electrodeposition bath as the drainage to be transferred is dropped by a gravity drop in the first drainage tank drainage storage tank 2144.
Is dropped. For maintenance and emergency purposes, it is preferable that the first drainage tank drainage storage tank 2144 has a capacity sufficient 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 upper lid 2277, and the first drainage tank is provided for effective gravity drop transfer of the electrodeposition bath. An air vent 2171 and a first drain tank air vent valve 2170 are provided.

After the temperature of the electrodeposition bath once dropped into the first drainage tank drainage storage tank 2144 is lowered, the first drainage tank drainage valve 2173 is used for wastewater treatment on the building side. Tank drainage collection valve 2174, drainage drainage source valve 217
5. The waste liquid is collected in a drum (not shown) via a drain recovery suction filter 2176 and a drain recovery pump 2177, and is disposed of properly. Prior to the collection and processing, dilution with water, treatment with a chemical solution, and the like can be performed in the first drainage tank 2144.

In order to stir the electrodeposition bath and to make the electrodeposition film uniform, a first electrodeposition tank stirring air introduction pipe 2062 (see FIG. 4) installed at the bottom of the first electrodeposition bath holding tank 2065 was used. Air bubbles are ejected from a plurality of orifices drilled. The air takes in compressed air supplied to the factory from a compressed air inlet 2182 (see FIG. 6) and passes through a compressed air pressure switch for electrodeposition bath agitation 2183 and is shown in a first electrodeposition tank compressed air introduction direction 2184. In the order, 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 21
88, 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.

The long substrate conveyed to the second electrodeposition tank 2116 (see FIG. 5) via the inter-electrodeposition tank return roller 2016 is deposited or treated with a second electrodeposition film. Depending on the use of this device, the second electrodeposited film is the same as the first electrodeposited film, and the first electrodeposited film and the second electrodeposited film may form one film. In addition, there may be a two-layer laminate of the same material but with different characteristics (for example, a laminate of layers having different particle sizes with zinc oxide), and two layers of the same material but different materials. (For example, a layer of indium oxide and zinc oxide as a transparent conductive film), or a completely different layer of two layers. The second electrodeposition tank 2116 deposits a substance and performs oxidation progress processing in the second electrodeposition tank 2116, or deposits a low oxide in the first electrodeposition tank 2066.
The combination such as performing an etching process at 16 becomes possible. Therefore, the conditions for electrodeposition or treatment, such as the electrodeposition bath or treatment bath, bath temperature, bath circulation amount, current density, and stirring amount, are selected according to the respective purposes. 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. For this 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 turning a long substrate.

As shown in FIG. 5, a second electrodeposition bath 2116 is provided with a temperature-controlled electrodeposition bath in a second electrodeposition bath holding bath 2115 which can keep the electrodeposition bath without corroding the electrodeposition bath. Is held to be the second electrodeposition bath surface 2074. The position of the bath surface is realized by overflow by a partition plate provided in the second electrodeposition bath holding tank 2115. The partition plate (not shown) is installed so as to drop the electrodeposition bath toward the back side in the entire second electrodeposition bath holding tank 2115, and was collected at the overflow return port 2075 of the second electrodeposition tank in a gutter structure. The overflowing electrodeposition bath is used for overflow return path 221 of the second electrodeposition tank.
9 to the second circulation tank 2222, where it is heated and again from the second electrodeposition tank upstream circulation jet pipe 2113 and the second electrodeposition tank downstream circulation jet pipe 2114 to the second electrodeposition bath holding tank 21.
It is refluxed to 15 and forms an inflow of the electrodeposition bath sufficient to promote overflow.

The long substrate 2006 passes through the electrodeposition tank return roller 2016, the second electrodeposition tank entry roller 2069, the second electrodeposition tank exit roller 2070, the pure water shower tank return entry roller 2279, and then passes through the second electrodeposition tank. It passes through the tank 2116. The surface of the elongate substrate between the second electrodeposition tank entry roller 2069 and the second electrodeposition tank exit roller 2070 is in the electrodeposition bath, and the 28 second electrodeposition tank anodes 2076
To 2103. The actual electrodeposition is performed by applying a negative potential to the long substrate and a positive potential to the anode, and flowing an electrodeposition current involving an electrochemical reaction between the two in the electrodeposition bath.

In this apparatus, four anodes 2076 to 2103 in the second electrodeposition tank 2116 are mounted on seven anode mounting tables 2104 to 2110, respectively.
The anode mounting table has a structure in which each anode is placed via an insulating plate, and a unique electric potential is applied from an independent power supply. In addition, the anode mounting table 21
Reference numerals 04 to 2110 denote a long substrate and an anode 207 in an electrodeposition bath.
It also has the function of maintaining the interval between 6 and 2103. Therefore, usually, 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.

The second electrode of the back electrode 2111 of the electrodeposition tank provided immediately before the exit roller 2070 of the second electrodeposition tank is for electrochemically removing the film deposited on the back surface of the long substrate in the bath. This is realized by setting the second electrode on the back of the electrodeposition tank 2111 to a negative potential with respect to the long substrate 2006 as in the first electrode on the electrodeposition tank 2061.

The long substrate 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. The occurrence of unevenness is prevented. The second electrodeposition tank 2116
And a pure water shower tank 2360 provided at the crossing point between the pure water shower tank 2360 also traps vapor generated from the electrodeposition bath and prevents the film-forming surface of the long substrate from drying. I have. Furthermore, the pure water shower tank entrance surface pure water shower 2299 and the pure water shower tank entrance rear pure water shower 2300 (see FIG. 7) not only wash and drop the electrodeposition bath, but also perform the same function.

The second circulation tank 2222 includes a second electrodeposition tank 211.
6 is responsible for heating and keeping the temperature of the electrodeposition bath and circulation of the jet. As described above, the electrodeposition bath overflowed in the second electrodeposition tank 2116 is returned to the second electrodeposition tank overflow return port 2.
075, and the second electrodeposition tank overflow return path 2
219, through the second electrodeposition tank overflow return path insulating flange 2220 to the second circulation tank heated 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 for initial heating of the electrodeposition bath at room temperature or for the electrodeposition bath in which the bath temperature is lowered by circulation. Is reheated to function in maintaining the electrodeposition bath at a predetermined temperature.

The second circulation tank heating storage tank 2223 is connected to two circulation systems. 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 223.
7. Second circulation tank electrodeposition bath upstream circulation flexible pipe 22
38, second circulation tank electrodeposition bath upstream circulation flange insulation pipe 22
39, a second electrodeposition tank upstream circulation recirculation system returning from the second electrodeposition tank upstream circulation jet pipe 2113 to the second electrodeposition bath holding tank 2115, a second circulation tank electrodeposition bath downstream circulation source valve 2242, The second circulation tank electrodeposition bath downstream circulation pump 2245, the second circulation tank electrodeposition bath downstream circulation valve 2247, the second circulation tank electrodeposition bath downstream circulation flexible pipe 2248, and the second circulation tank electrodeposition bath downstream circulation flange insulation pipe 2249. After that, the second electrodeposition tank downstream circulation recirculation system returns from the second electrodeposition tank downstream circulation jet pipe 2114 to the second electrodeposition bath holding tank 2115.

The second electrodeposition tank 211 is circulated from the second electrodeposition tank upstream circulation jet pipe 2113 and the second electrodeposition tank downstream circulation jet pipe 2114.
The electrodeposition bath returned to 6 is the second electrodeposition bath holding tank 2 so that the exchange of the electrodeposition bath in the second electrodeposition bath holding tank 2115 can be effectively performed.
115 The second circulation tank upstream circulation jet pipe 21 provided at the lower part
From the 13 and the second electrodeposition tank downstream circulating jet pipe 2114, it is recirculated as a jet through orifices formed in each jet pipe.

The amount of reflux in each circulation reflux system is mainly
The degree of opening / closing of the second circulation tank electrodeposition bath upstream circulation valve 2237 or the second circulation tank electrodeposition bath downstream circulation valve 2247 is controlled, and further fine adjustment is performed by the second circulation tank electrodeposition bath upstream circulation pump 2234 or the second circulation tank. A second circulation tank electrodeposition bath upstream circulation pump bypass valve 2235 or a second circulation tank electrodeposition bath downstream circulation pump bypass halve provided in a bypass system in which the outlet and inlet of the tank electrodeposition bath downstream circulation pump 2245 are connected by short-circuiting. 2244. The bypass system also serves to prevent cavitation in the pump when the reflux rate is reduced or when the bath temperature is very close to the boiling point. As described in the description of the first electrodeposition bath, cavitation in which the bath liquid is boiled and vaporized and the liquid cannot be sent out significantly shortens the life of the pump.

When an orifice is 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, the amount of reflux is almost the same as that of the upstream circulation jet pipe 2113 of the second electrodeposition tank. And the pressure of the solution returned to the circulation jet pipe 2114 downstream of the second electrodeposition 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,
The balance of the reflux amount can be known from these pressure gauges. The amount of the reflux bath discharged from the orifice exactly follows Bernoulli's theorem. However, when the orifice formed in the jet tube has a diameter of several millimeters or less, the upstream circulation tube 2113 of the second electrodeposition tank or the downstream circulation of the second electrodeposition tank. The jet flow rate can be substantially constant over the entire jet pipe 2114.

Further, when the reflux amount is sufficiently large, the exchange of the bath can be performed very smoothly.
Even if the length 16 is considerably long, it is possible to effectively uniform the concentration of the bath and the temperature. Of course, the second electrodeposition tank overflow return path 2219 should be thick enough to allow this sufficient reflux.

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 are
It absorbs distortion in the piping system, and is particularly effective when using flange-insulated piping or the like, which tends to have insufficient mechanical strength against distortion.

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 connected to 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 second electrodeposition tank overflow return insulating flange 2220 provided on the way. This is to prevent the formation of unnecessary current paths, that is, to prevent stray current leads to stably and effectively promote an electrochemical film formation reaction using an electrodeposition current. It is based on knowledge.

One of the circulation recirculation systems has a bypass recirculation system composed of a second circulation tank electrodeposition bath bypass circulation flexible pipe 2250 and a second circulation tank electrodeposition bath bypass circulation valve 2251 which returns directly to the second circulation tank heating storage tank 2223. A system is provided, which is used when it is desired to circulate the bath without refluxing the bath liquid in the second electrodeposition tank, for example, when raising the temperature from room temperature to a predetermined temperature.

The two circulation circulation systems from the second circulation tank 2222 are sent to a second electrodeposition tank inlet shower 2068 for applying an electrodeposition bath immediately before reaching the second electrodeposition tank entrance roller 2069. There are provided two liquid feeding systems, one for sending to a second electrodeposition tank outlet shower 2297 for applying an electrodeposition bath to a long substrate that has passed through the second electrodeposition tank exit roller 2070 and exited from the electrodeposition bath. The former to a second electrodeposition tank inlet shower 2068 via a second electrodeposition tank inlet shower valve 2241 and the latter to a second electrodeposition tank outlet shower 2297 via a second electrodeposition tank outlet shower valve 2252. And, it is connected. The spray amount of the electrodeposited liquid from the second electrodeposition tank inlet shower 2068 can be adjusted by adjusting the opening / closing degree of the second electrodeposition tank inlet bath shower valve 2241 and the amount of the electrodeposition liquid sprayed from the second electrodeposition tank outlet shower 2297. The liquid spray amount is adjusted by adjusting the degree of opening and closing of the second electrodeposition tank outlet shower valve 2252.

The second circulation tank heating storage tank 2223 is actually provided with a lid, and has a structure for preventing water from being lost as steam. When the bath temperature is high, the temperature of the lid also increases, so that consideration such as attaching a heat insulating material is necessary from the viewpoint of work safety.

A filter circulation system is provided for removing powder from the electrodeposition bath of the second electrodeposition tank. The filter circulation system for the second electrodeposition tank 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, and a second electrodeposition filter. Deposition 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 226
3. Flexible filter for circulation of the second electrodeposition tank filter 22
66, second electrodeposition tank filter circulation flange insulation pipe 22
67, second electrodeposition tank filter circulation valve 2268, second electrodeposition tank filter circulation system electrodeposition bath upstream return valve 226
9, a second electrodeposition tank filter circulation system electrodeposition bath return valve 2270 and a second electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2271. The electrodeposition bath passes through the second electrodeposition tank filter circulation directions 2257, 2264,
It flows in the direction of 2265. The powder to be removed may jump 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.

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 piping,
The purpose of the present invention is to minimize leakage of liquid from a pipe connection portion, protect insulating pipes having poor mechanical strength, and increase the degree of freedom in arranging components of a circulation system such as a pump.

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 which has been floated from the earth ground to fall to the earth ground. It is intended to float electrically to prevent it.

The second electrodeposition tank filter circulation suction filter 2258 is a wire mesh such as a “tea strainer”, which removes large debris, and is followed by the second electrodeposition tank filter circulation pump 2260 and the second electrodeposition tank filter circulation. This is for protecting the filter 2263.

The second electrodeposition tank filter circulation filter 22
Reference numeral 63 is a main part of the circulation system, and is for removing powder mixed or generated in the electrodeposition bath.

The circulation flow rate of the electrodeposition bath of the present circulation system is mainly controlled 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 tank filter circulation pump bypass valve 2259. A second electrodeposition tank filter circulating pressure gauge 2262 is provided to grasp the circulating flow rate due to these halve adjustments. The second electrodeposition tank filter circulation pump bypass valve 2259 prevents fine adjustment of the flow rate and also prevents the second electrodeposition tank filter circulation pump 2260 from being damaged due to cavitation when the entire filter circulation flow rate is reduced. I have.

The electrodeposition bath can be transferred from the second electrodeposition tank drain valve 2255 to the second drainage tank 2274 (see FIG. 6) via the second electrodeposition tank filter circulation return flange insulating pipe 2254. This transfer is performed for electrodeposition bath replacement, equipment maintenance, and even in an emergency. The electrodeposition bath as the drainage to be transferred is dropped by the second drainage drainage storage tank 2273 by gravity drop.
Is dropped. For maintenance and emergency purposes, it is preferable that the second drainage tank drainage storage tank 2273 has a capacity sufficient to store the total bath capacity of the second electrodeposition tank 2116 and the second circulation tank 2222.

The second drainage tank 2273 is provided with a second drainage tank drainage tank upper lid 2278. The second drainage tank is used to effectively transfer the electrodeposition bath by gravity. An air vent 2276 and a second drain tank air vent valve 2275 are provided.

After the temperature of the electrodeposition bath once dropped into the second drainage tank drainage storage tank 2273 is lowered, the second drainage tank drainage valve 2180 is used for wastewater treatment on the building side or the second drainage tank. Tank drain collection valve 2181, drain collection valve 217
5. The waste liquid is collected in a drum (not shown) via a drain recovery suction filter 2176 and a drain recovery pump 2177, and is disposed of properly. Prior to collection and processing, dilution with water and processing with a chemical solution can be performed in the second drainage tank drainage storage tank 2273.

In order to stir the electrodeposition bath and to make the electrodeposition film uniform, a second electrodeposition tank stirring air introduction pipe 2112 (see FIG. 5) installed at the bottom of the second electrodeposition bath holding tank 2115. Air bubbles are ejected from a plurality of orifices drilled. The air takes in compressed air supplied to the factory from a compressed air inlet 2182 (see FIG. 6), passes through a compressed air pressure switch 2183 for electrodeposition bath agitation, and is shown in a second compressed air compressed air introduction direction 2194. Direction, the second electrodeposition tank compressed air source valve 2195, the second electrodeposition tank compressed air flow meter 2196, the second electrodeposition tank compressed air regulator 2197, the second electrodeposition tank compressed air mist separator 21
98, second electrodeposition tank compressed air introduction valve 2199, second electrodeposition tank compressed air flexible pipe 2220, second electrodeposition tank compressed air insulation pipe 2201, and 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.

The first electrodeposition tank 2066 and the second electrodeposition tank 2116
FIG. 6 shows that a spare liquid or gas can be introduced.
As shown in the figure, a preliminary introduction system is installed. The liquid or gas from the electrodeposition tank pre-introduction port 2213 passes through the electrodeposition tank pre-introduction valve 2214, passes through the first electrodeposition tank pre-introduction valve 2215, passes through the first electrodeposition tank pre-introduction insulation pipe 2216, and the first electrode. The gas is introduced into the deposition tank 2066, and further into the second electrodeposition tank 2116 via the second electrodeposition tank preliminary introduction valve 2217 and the second electrodeposition tank preliminary introduction insulating pipe 2218. The most likely pre-introduction systems are retention agents and replenishers to keep the bath capacity constant for long periods of time, but in some cases it may be a gas that dissolves in the bath or an acid that removes powder. And so on.

Washing is performed in the pure water shower tub 2 shown in FIG.
360, the first hot water tank 2361, and the second hot water tank 2362
Done in steps. The heated pure water is supplied to the second hot water tank 2362, and the drained water is used in the first hot water tank 2361,
Further, the drainage is used in the pure water shower tank 2360. As a result, the long substrate is gradually washed with high-purity water after completion of the electrodeposition in the electrodeposition tank.

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 just before the long substrate exits. As shown in FIG. 8, the pure water to be supplied is supplied from the pure water inlet 2337 to the pure water heating tank 2 via a pure water supply valve 2338 for the pure water.
339 stored in a pure water heating tank pure water heater 234
It is heated to a predetermined temperature at 0 to 2343, and a pure water heating tank pure water delivery valve 2344, a pure water heating tank pure water delivery pump 234.
6, pure water heating tank pressure switch 2347, pure water heating tank cartridge type filter 2349, pure water heating tank flow meter 23
50, one is from the second hot water tank outlet backside shower valve 2351 to the second hot water tank outlet backside pure water shower 2309
(FIG. 7), the other is from the second hot water tank outlet surface shower valve 2352 to the second hot water tank outlet surface pure water shower 2310.
(FIG. 7). The heating is for improving the cleaning effect.

The pure water supplied to the shower and accumulated in the second hot water tank hot water holding tank 2317 forms a pure water rinsing bath, where the long substrate is washed with still water. The second hot water tank 2362 is provided with a second hot water tank hot water keeping heater 2307 so that the temperature of the pure water does not drop.

Pure water overflowing from the second hot water tank hot water holding tank 2317 is supplied from the second hot water tank 2362 to the first hot water tank 2361 through the hot water tank connecting pipe 2232. Similar to the second hot water tank 2362, the first hot water tank 2361 is provided with a first hot water tank hot water keeping heater 2304 to maintain the temperature of pure water. Furthermore, the first hot water tank 2361
Is provided with an ultrasonic source 2306, which positively removes dirt on the surface of the long substrate between the first hot water tank roller 2282 and the second hot water tank return entry roller 2283.

The 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.
8, a pure water shower tank pure water shower supply pump 2325, a pure water shower tank 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 Through a pure water shower supply flow meter 2329, from the pure water shower tank inlet surface pure water shower valve 2330 to the pure water shower tank inlet back pure water shower 2299 (FIG. 7), from the pure water shower tank inlet back pure water shower valve 2331. Pure water shower 2300 (Fig. 7)
The pure water shower valve 233 on the back of the outlet of the pure water shower tank
2 to pure water shower tank 2302
(FIG. 7), from the pure water shower tank outlet surface pure water shower valve 2333 to the pure water shower tank outlet surface pure water shower 2
303 (FIG. 7), and a washing shower flow is applied to the back surface of the long substrate and the front surface of the long substrate at the entrance and exit of the pure water shower tank 2360, respectively.

The water after showering is received in a 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 to the washing system drainage 2336. Discarded. Normally, since the washed water contains ions and the like, a predetermined treatment is required.

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 is a pure water shower tank turning-in roller 2279, a pure water shower tank roller 2280, a first hot water tank. Folding entry roller 2281, first hot water tank roller 2282, second hot water tank folding entry roller 2283, second hot water tank roller 2
284, the sheet is sent to the drying section turning roller 2285.

[0103] Roller 227 for pure water shower tub turning back
Immediately after 9, a pure water shower tub back brush 2298 is provided to remove relatively large powders and products with low adhesion that adhere to the back surface of the long substrate.

The long substrate 2006 which reached the drying unit 2363
First, the air knife 23 on the back side of the drying section entrance at the drying section entrance
11. Draining is performed by the air knife 2312 on the drying unit entrance surface. As shown in FIG. 8, the introduction of air into the air knife is performed by the drying system compressed air inlet 2353, the drying system compressed air pressure switch 2354, the drying system compressed air filter regulator 2355, the drying system compressed air mist separator 2356, and the drying system compressed air supply. Valve 2357,
After that, the air knife valve 2358 on the back side of the drying section or the air knife valve 2359 on the front side of the drying section is formed. Since the air supplied to the drying unit 2363 is particularly inconvenient if it contains water droplets, the role of the drying system compressed air mist separator 2356 is important.

Subsequently, in the process of being conveyed from the drying turn-back roller 2285 to the take-up device entry roller 2286, the IR lamps 2313 arranged side by side are dried by radiant heat.
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 the deposition film is formed. At the time of drying, there is generation of fog due to drainage and generation of water vapor due to IR lamp radiation, and the drying section exhaust port 2314 connected to the exhaust duct is essential.

Most of the steam collected in the drying system exhaust duct 2370 returns to water in the drying system condenser 2371 as shown in FIG.
And a part is discarded to the drying system exhaust 2374. If the steam contains a harmful gas, the exhaust gas should be subjected to a predetermined treatment.

The winding device 2296 (see FIG. 7) includes a winding device entrance roller 2286 and a winding device direction changing roller 2286.
The long substrate 2006 is wound into a long substrate winding bobbin 2289 in the form of a coil via a roll 287 and a winding adjustment roller 2288 in this order. If protection of the deposited layer is required,
The interleaf is delivered from the interleaf delivery bobbin 2290 and is involved in a long substrate. Long board 2
The transfer direction of 006 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. In FIG. 7, the long substrate wound up on the long substrate winding bobbin 2289 and the interleaf fed out from the interleaf feeding bobbin 2290 show that no interference occurs at the position at the start of the transfer and the position at the end of the transfer, respectively. Is shown. The whole winding device has a structure covered with a winding device clean booth 2295 using a hepa filter and a down flow for dust prevention.

In this winding device, the winding device direction changing roller 2287 is provided with a function of correcting the meandering of the long substrate. Based on a signal from a meandering detector installed between the take-up device direction change roller 2287 and the take-up adjustment roller 2288, the take-up device direction change roller 2287 is moved by the hydraulic servo to the take-up device entry roller 2286.
By waving about the axis set on the side, meandering can be corrected. Winding device direction change roller 22
The control of 87 is the movement of the roller approximately to the front 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. The servo gain depends on the transport speed of the long substrate, but generally does not require a large object. Even if a long substrate having a length of several hundred meters is wound up, its end faces are aligned with sub-millimeter accuracy.

When an electrodeposition bath or hot water is used at a temperature higher than room temperature, steam is inevitably generated. Especially when temperatures above 80 ° C. are used, the generation of water vapor is considerable. Water vapor generated from the bath surface of the tub accumulates on the bath surface of the tub and blows out vigorously from the gap in the device, sees a large amount of discharge when opening and closing the lid, and flows down as a water droplet from the gap in the device, Deteriorating the operating environment of the device. For this reason, it is preferable to forcibly suck and exhaust through an exhaust duct.

The first electrodeposition tank upstream exhaust port 2021 of the first electrodeposition tank 2066, the first electrodeposition tank midstream exhaust port 2022, the first electrodeposition tank downstream exhaust port 2023, and the second electrodeposition tank 2116 Upstream exhaust port 2071 for electrodeposition tank, middle exhaust port 20 for second electrodeposition tank
72, a second electrodeposition tank downstream exhaust port 2073, 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, a second hot water tank 23
62 through the second hot water tank exhaust port 2308.
The water vapor collected at 020 passes through an insulating flange as shown in FIG. 9 and is mostly returned to water in an electrodeposition washing washing system exhaust duct condenser 2366 and is discarded to an electrodeposition washing system exhaust duct condenser drainage drain 2368. Some are discarded to the electrodeposition water washing system exhaust 2369. If the steam contains a harmful gas, the exhaust gas should be subjected to a predetermined treatment.

In this apparatus, 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 holding tank 2115 of the second electrodeposition tank 2116 are grounded. In order to make the float potential from the ground, a base insulating flange 2365 for the electrodeposition water washing system exhaust duct and a water-insulating flange 2364 for the electrodeposition water washing system exhaust duct were provided and electrically separated.

[Substrate] The substrate material used in this apparatus is as follows.
Any material can be used as long as it is electrically conductive on the film formation surface and is not affected by the electrodeposition bath. Metals such as SUS, Al, Cu, and Fe are used. A PET film with a metal coating can also be used. Among these, SUS is excellent as a long substrate in order to perform an element formation process in a later step.

As the SUS, either a non-magnetic SUS or a magnetic SUS can be applied. The former representative is SUS304, which has excellent polishing properties, and can have a mirror surface of about 0.1 s. A representative of the latter is SUS430 of ferrite type,
It is effectively used for transport using magnetic force.

The surface of the substrate may be smooth or rough. By changing the type of rolling roller in the SUS rolling process, the surface property changes. What is called BA is close to a mirror surface, and in 2D, unevenness is remarkable. In any of the surfaces, when observed under an SEM (electron microscope), twists in units of microns may be conspicuous. As a battery substrate, rather than large undulating irregularities,
The micron-scale structure has a greater effect on the characteristics of the solar cell, both in a good direction and in a bad direction.

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. In this case, a thin film formed by a sputtering method can be used. As described above, 1000 to 2000
抵抗 If the thickness is less than the above, the resistance value may increase due to the adsorption of oxygen or water in the air. Alternatively, when immersed in a high-temperature electrodeposition bath, water adsorption occurs and the resistance increases.

However, according to an experiment by the present inventors, when zinc oxide is deposited electrochemically from an aqueous solution on a thin film of zinc oxide by sputtering, for example, to a thickness of 1 μm or more, if the subsequent drying is sufficient, a large resistance value is obtained. Is not observed. This is thought to be due to the fact that sufficient carriers could be supplied to the trap site from zinc oxide electrochemically deposited from the aqueous solution. Therefore, a thin layer of zinc oxide which is formed in advance and which has a large resistance by itself is sufficient. Of course, referring to the above-mentioned paper proposed to prevent the influence of oxygen adsorption, elements such as B, Al, In, and Ga are mixed in a sputtering target in an amount of several percent or less to increase the resistance from the beginning. A film not to be formed may be formed in advance.

[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. Resin films such as PET are made of softer Cu
It is also possible to use a thin coating of Al or Al metal. Of course, if the resin film is too hot, it melts or fuses, so it is necessary to confirm in advance that the substrate has cooled to a sufficient temperature. When using a nonwoven fabric, paper, or the like, attention should be paid to their moisture absorption in advance. As already pointed out, it takes time for the water once released to re-adsorb to the zinc oxide layer.
Storing rounded moisture-absorbing interleaves causes production instability. When long-term storage is expected using an interleaf such as a nonwoven fabric or paper, it is preferable to dry the interleaf such as a nonwoven fabric or paper before winding.

[Hot Air Drying] In the present invention, at the time of drying the deposited film, at least 30% of the moisture adsorbed on the zinc oxide is removed. Thus, a stable low-resistance zinc oxide thin film can be provided without adding a secondary additive to the aqueous solution for electrochemical deposition.

It is preferable to use warm air for drying the deposited film because the heat from the heat source can be effectively transmitted to the formed zinc oxide layer. In fact, in drying the apparatus, the total heat of the IR lamp 2313 is about 10 kW
However, it did not result in sufficient drying. This is because the reflectance of the surface on which zinc oxide is formed is 70% or more, and the SU
This was considered to be caused by 50% or more in the S plane. In the case where a material capable of lowering the reflectance can be used, or in the case where the back surface blackening treatment can be performed, sufficient heat efficiency can be expected even in the radiation drying method.

The hot-air drying used in the present invention can be applied to any one configured so that warm air flows along the substrate surface. Since SUS has poor heat conduction among metals, it is preferable to increase the surface that comes in contact with the hot air. It is necessary to increase the length of the drying section, increase the hot air blowing surface, or use the hot air blowing nozzle. It is good to increase the number.

It is inconvenient if the warm air for drying contains dust. Normally, the present apparatus does not need to be installed in a clean room, but it is preferable to remove dust from the wind when it is blown directly. For that, HEPA
It is preferable to provide a filter or the like in a part of the hot air path.

It is preferable that the temperature of the hot air be 200 ° C. or higher, whereby the temperature of the drying member, that is, the substrate in this case, can be effectively raised to a temperature at which water can be separated and removed. In addition, a low resistance can be ensured over the entire area of a long substrate.

[Transport Speed] The transport speed of the substrate is determined 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 is determined by the sum of the respective film deposition rates.

In this apparatus, 0.5 m / min to 5 m / m
Designed in the range of in, it is experimentally possible to deposit zinc oxide on a long substrate with a minimum speed of 500 m or more at a temperature of 85 ° C. with good transport at a minimum speed and a maximum speed. Prove that there is.

The transport speed is determined in consideration of the degree of drying. That is, if the transport speed is too high, the drying becomes insufficient, which is not desirable. It is preferable that the apparatus has a drying capacity corresponding to the transporting speed at which deposition can be performed. However, if it is difficult to do so due to cost or space, the transporting speed should be selected according to the drying capacity.

Although the present apparatus uses a total of about 10 kW of IR lamps, the resistance value can hardly be reduced to several Ωcm ² or less at a transport speed of 1 m / min or more by using the IR lamp alone. Only at 0.2 m / min, the resistance value was reduced.

On the other hand, in the present invention, as shown in the embodiments described later, by installing a hot air dryer as shown in FIG. The amount of heat does not stay on a part of the substrate,
Water separation and removal can be promoted uniformly, and the overall resistance value is several Ωcm ²
It can be:

[0128]

Embodiments of the present invention will be described below.

Embodiment 1 The hot air drying section shown in FIG. 1 was constructed, and the IR lamp 2313 of the electrodeposition apparatus shown in FIGS. 2 to 9 was used.
(See FIG. 7).

In the figure, reference numeral 1002 denotes a roll substrate which is transported in the direction of the arrow. Reference numeral 1003 denotes a heat insulating wall made of a SUS plate and filled with glass wool. Insulation wall 1
003 is to minimize the amount of hot air coming into contact with the outside air to prevent the temperature of the hot air from lowering and to prevent the hot air from leaking and unnecessarily heating the electrodeposition apparatus to cause damage. is there.

The hot air nozzles 1004a to 1004h
It is formed by drilling an orifice in a US pipe, and blows hot air into the heat insulation wall 1003 from the front and back of the roll substrate 1002 in the form of an air knife.

The hot air mixes recovered hot air from a hot air recovery duct 1005 for recovering hot air blown into the heat retaining wall with outside air from an outside air introduction duct 1006 for introducing outside air and controlling the temperature. Hot air is generated in the generating furnace 1008 and sent to the hot air feed path 1011. The rate of outside air introduction is controlled by an outside air control valve 1007. By always introducing a fixed amount of outside air, abnormal heating in the hot air generator 1008 can be prevented. The hot air sent to the hot air passage 1011 passes through the HEPA filter 1012 to remove dust contained therein. The warm air from which dust has been removed is further introduced into the warm air nozzle via a warm air introduction duct 1013 and a manifold (not shown).

The hot air path, that is, the hot air recovery duct 100
5. Hot air generating furnace 1008, hot air passage 1011 and HEPA
The filter 1012, the hot air introduction duct 1013, and the manifold are preferably surrounded by a heat insulating material to prevent unnecessary heat radiation and increase the efficiency of the heat source. This is also preferable in preventing an accident caused by unnecessary contact of the operator.

The hot-air generating furnace 1008 is
9 and an electric heater 1010. The heater capacity of the hot air generator 1008 used was 10 kW, and the air circulation rate was 2 m ³ / min. The diameter of the orifice formed in the SUS tube of each hot air nozzle was 0.5 mm, and seven orifices were arranged for each. The length of the substrate transfer path in the heat retaining wall was about 2 m.

The thickness of the rolled SUS substrate is 0.12 mm
And the width is 355 mm. This roll substrate is 100
When transported at 0 mm / min, the substrate temperature at the outlet of the heat retaining wall was 150 ° C. with a contact thermometer. On the other hand, the ambient temperature in the heat retaining wall was 250 ° C. When the thickness of zinc oxide electrochemically deposited from an aqueous solution was set to 1 μm, the amount of water was measured in the same manner as in the above-mentioned experiment, and the electric resistance was measured by forming an electrode. The residual water was 55%. Is 0.5 Ωcm ^2, which is a great improvement compared to a resistance value of about 90 Ωcm ² when the hot air blower is not inserted.

Whether the IR lamp is operated or not is operated, its resistance value largely depends on the presence or absence of a hot air dryer.
While it was found that the IR lamp only served as a drainer for the surface, the effect of the hot air dryer was very clear.

Example 2 The dryer (FIG. 1) of Example 1 was incorporated in the electrodeposition apparatus of FIGS. 2 to 9 in the same manner as in Example 1.

The same roll substrate as in Example 1
/ Min, and the residual moisture and electrical resistance of the same zinc oxide film were measured. The residual water content was 70% and the resistance value was 3.4 Ωcm ² , which was close to the upper limit but sufficient for use in applications such as solar cells.

Example 3 The dryer (FIG. 1) of Example 1 was incorporated in the electrodeposition apparatus of FIGS. 2 to 9 in the same manner as in Example 1. However, the heat capacity of the hot air generator was increased to 30 kW. Thus, when the ambient temperature is 350 ° C. and the exit temperature of the roll substrate is 1000 mm / min,
The temperature reached 0 ° C.

The same roll substrate as in Example 1 was used for 3000 mm.
/ Min, and the residual moisture and electrical resistance of the same zinc oxide film were measured. The residual water content was 40% and the resistance value was 0.4 Ωcm ² , and a sufficiently low resistance was achieved.
However, the roll substrate is set to 100
When the wafer was fed at a transport speed of 0 mm / min, the substrate temperature at the outlet exceeded 300 ° C., and a cooling fan was required at the subsequent stage.

[0141]

According to the present invention, there is provided an electrodeposition method in which zinc oxide is electrochemically deposited on a substrate from an aqueous solution, and the deposited film is washed with water and dried. % Of the zinc oxide electrodeposition method, which does not involve adding secondary additives to the aqueous solution for electrochemical deposition.
A stable low-resistance zinc oxide thin film can be provided regardless of the state of film formation. When a secondary additive is used, not only does it respond to chemical treatment when draining, but it can also cause changes in the electrochemical deposition state of zinc oxide and the accompanying morphology due to changes in hydrogen overvoltage and other factors. is there.

When at least 30% of the moisture adsorbed on the zinc oxide is removed by hot air, the temperature difference in the drying section can be reduced, and a high-temperature section is created in a part of the apparatus to design the apparatus. It is not subject to any restrictions that would make it harder to use or would require extra space for placement.
For example, when a radiant heat source such as an IR heater is used, the temperature of the heat source portion is extremely high, but the actual temperature rise of the drying member is not so large.

When the temperature of the hot air is 200 ° C. or higher, the temperature of the drying member, that is, the substrate in this case, can be effectively raised to a temperature at which water can be separated and removed.
In addition, even for a long substrate, a low resistance can be reliably ensured over the entire area.

When the substrate is a roll-shaped metal, it is easy to rapidly cool the temperature of the substrate once heated by hot air drying or the like, and it is possible to realize a short-time temperature increase. By this, unnecessary water separation and removal can be promoted, but without extra heating time,
Unnecessary heat is not applied to the formed film.

When the transfer speed of the substrate is 1000 mm / m
In the case of in or more, the amount of heat of the drying means can be promoted uniformly without water staying in a part of the substrate, and the resistance can be easily reduced as a whole.

Further, when zinc nitrate is contained in the aqueous solution and its concentration is 0.05 M / l or more, the unevenness of the zinc oxide surface is remarkably developed, and even in such a case, the water separation and removal of 30% is extremely possible. It is effective and has a large heating effect by means such as warm air.

When a zinc oxide thin film is formed on a substrate by sputtering prior to deposition by electrodeposition, the number of zinc oxide carriers electrochemically formed from the aqueous solution formed on the substrate is made sufficiently large. As a result, even if a thin sputtered film is likely to have a high resistance under the influence of moisture adsorption, the overall resistance can be sufficiently reduced.

In the case where the thickness of the zinc oxide thin film formed by sputtering is 2000 ° or less, the number of carriers of zinc oxide electrochemically formed from the aqueous solution formed on the upper portion can be sufficiently increased as described above. Therefore, a zinc oxide film can be effectively formed.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of a hot air dryer suitably used in the present invention.

FIG. 2 is an overall configuration diagram showing one example of a zinc oxide electrodeposition apparatus of the present invention.

FIG. 3 is a schematic view showing one example of an unwinding device in the zinc oxide electrodeposition device of the present invention.

FIG. 4 is a schematic view showing an example of a first electrodeposition tank in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 5 is a schematic view showing an example of a second electrodeposition tank in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 6 is a schematic view showing an example of a periphery of a drainage tank in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 7 is a schematic diagram showing an example from a pure water shower tank to a winding device in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 8 is a schematic view showing an example of a pure water heating tank, a compressed air system, and a drainage system in the zinc oxide electrodeposition apparatus of the present invention.

FIG. 9 is a schematic diagram showing an example of an exhaust duct system in the zinc oxide electrodeposition apparatus of the present invention.

[Explanation of symbols]

1002 Roll substrate 1003 Heat retaining wall 1004a to 1004h Hot air nozzle 1005 Hot air recovery duct 1006 Outside air introduction duct 1007 Outside air control valve 1008 Hot air generation furnace 1009 Ventilation fan 1010 Electric heater 1011 Hot air passage 1012 HEPA filter 1013 Hot air introduction duct 2001 Unwinding device Long substrate bobbin 2002 Unwinding device Interleaf winding bobbin 2003 Unwinding device feeding adjustment roller 2004 Unwinding device direction change roller 2005 Unwinding device discharge roller 2006 Long substrate 2007 Winding interleaf 2008 Interleaf winding direction 2009 Rolling Unloading device long substrate bobbin rotation direction 2010 Unloading device unloading direction 2011 Unwinding device clean booth 2012 Unwinding device 2013 Electrodeposition tank entrance turn-up roller 2 14 First Electrodeposition Tank Entry Roller 2015 First Electrodeposition Tank Exit Roller 2016 Electrodeposition Tank Folding Roller 2017 Electrodeposition Tank Entrance Folding Roller Cover 2018 First Electrodeposition Bath Holding Tank Cover 2019 2019 Electrodeposition Tank Cover 2020 Electrodeposition Rinse System exhaust duct 2021 First electrodeposition tank upstream exhaust port 2022 First electrodeposition tank midstream exhaust port 2023 First electrodeposition tank downstream exhaust port 2024 First electrodeposition tank overflow return port 2025 First electrodeposition bath surface 2026-2053 Anode of first electrodeposition tank 2054 to 2060 Anode mounting table of first electrodeposition tank 2061 Back electrode of first electrodeposition tank 2062 First electrodeposition tank stirring air introduction pipe 2063 First electrodeposition tank upstream circulation jet pipe 2064 First electrodeposition Tank downstream circulation jet tube 2065 First electrodeposition bath holding tank 2066 First electrodeposition tank 2067 First electrodeposition tank outlet shower 2068 Second electrodeposition Inlet shower 2069 Second electrodeposition tank entry roller 2070 Second electrodeposition tank exit roller 2071 Second electrodeposition tank upstream exhaust port 2072 Second electrodeposition tank middle exhaust port 2073 Second electrodeposition tank downstream exhaust port 2074 Second electrodeposition Bath surface 2075 Overflow return port of second electrodeposition tank 2076-2103 Anode of second electrodeposition tank 2104-2110 Anode mounting base for second electrodeposition tank 2111 Second electrode of second electrodeposition tank backside 2112 Second electrodeposition tank air inlet pipe 2113 Second electrodeposition tank upstream reflux jet pipe 2114 Second electrodeposition tank downstream reflux jet pipe 2115 Second electrodeposition bath holding tank 2116 Second electrodeposition tank 2117 First electrodeposition tank overflow return path 2118 First electrodeposition tank overflow Return path insulation flange 2119 First electrodeposition tank overflow Return direction 2120 First circulation tank 2121 First circulation tank heating storage tank 2122 2129 First circulation tank heater 2130 First circulation tank electrodeposition bath upstream circulation source valve 2131 First circulation tank electrodeposition bath upstream circulation direction 2132 First circulation tank electrodeposition bath upstream circulation pump 2133 First circulation tank electrodeposition bath upstream circulation Pump bypass valve 2134 First circulation tank electrodeposition bath upstream circulation pressure gauge 2135 First circulation tank electrodeposition bath upstream circulation valve 2136 First circulation tank electrodeposition bath upstream circulation flexible pipe 2137 First circulation tank electrodeposition bath upstream circulation flange insulation Piping 2138 Second electrodeposition bath holding tank cover 2139 First circulation tank electrodeposition bath downstream circulation source valve 2140 First circulation tank electrodeposition bath downstream circulation direction 2141 First circulation tank electrodeposition bath downstream circulation pump bypass valve 2142 First circulation Circulation pump downstream circulation pump 2143 1st circulation tank electrodeposition bath downstream circulation pressure gauge 2144 1st drainage tank Drainage storage tank 2145 One circulation tank electrodeposition bath downstream circulation valve 2146 First circulation tank electrodeposition bath bypass circulation flexible pipe 2147 First circulation tank electrodeposition bath bypass circulation flexible valve 2148 First circulation tank electrodeposition bath downstream circulation flexible pipe 2149 First circulation tank electrode Insulation 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 electrode Separation 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 circulation flexible pipe 2165 No. One 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 circulation system electrodeposition bath middle flow return valve 2169 No. One electrodeposition tank filter circulation system electrodeposition bath downstream return valve 2170 First drainage tank air release valve 2171 First drainage tank air release 2172 First drainage tank 2173 First drainage tank drainage valve 2174 First drainage tank drainage Collection valve 2175 Drain collection source valve 2176 Drain collection sac Filter 2177 drainage recovery pump 2178 drainage recovery port 2179 drainage tank common drainage port 2180 second drainage tank drainage valve 2181 second drainage tank drainage recovery valve 2182 compressed air inlet 2183 compressed air for electrodeposition bath stirring Pressure switch 2184 First electrodeposition tank compressed air introduction direction 2185 First electrodeposition tank compressed air main 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 First electrodeposition tank stirring air downstream control valve 2193 First electrodeposition tank stirring Air upstream control valve 2194 Second electrodeposition tank compressed air introduction direction 2195 Second electrodeposition tank compressed air Valve 2196 Second electrode press air flow meter 2197 Second electrode press air regulator 2198 Second electrode press air mist separator 2199 Second electrode press air inlet valve 2200 Second electrode press air flexible pipe 2201 second electrodeposition tank compressed air insulation pipe 2202 second electrodeposition tank stirring air upstream control valve 2203 electrodeposition tank system pure water inlet 2204 electrodeposition tank system pure water inlet valve 2205 first heating storage tank pure water introduction flexible pipe 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 Second heating storage tank pure water introduction flexible pipe 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 Electrodeposition tank Pre-introduction port 2214 Electrode tank pre-introduction valve 2215 First electrodeposition tank pre-introduction valve 2216 First electrodeposition tank pre-introduction insulation pipe 2217 Second electrodeposition tank pre-introduction valve 2218 Second electrodeposition tank pre-introduction insulation pipe 2219 No. 2 electrodeposition tank overflow return path 2220 second electrodeposition tank overflow return path insulating flange 2221 second electrodeposition tank overflow return direction 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 Second circulation tank electrodeposition bath upstream circulation direction 2234 Second circulation tank electrodeposition bath upstream circulation pump 2235 Second circulation tank electrodeposition bath upstream circulation pump bypass valve 2236 Second circulation tank electrode Electrolysis bath upstream circulation pressure gauge 2237 Second circulation tank electrodeposition bath upstream circulation valve 2238 Second circulation tank power Electrolyte bath upstream circulation flexible pipe 2239 Second circulation tank electrodeposition bath upstream circulation flange insulation pipe 2240 Second circulation tank inlet low shower flexible pipe 2241 Second circulation tank inlet low shower valve 2242 Second circulation tank electrodeposition bath downstream circulation valve 2243 Second circulation tank electrodeposition bath downstream circulation direction 2244 Second circulation tank electrodeposition bath downstream circulation pump bypass valve 2245 Second circulation tank electrodeposition bath downstream circulation pump 2246 Second circulation tank electrodeposition bath downstream circulation pressure gauge 2247 Second Circulation tank electrodeposition bath downstream circulation valve 2248 Second circulation tank electrodeposition bath downstream circulation flexible pipe 2249 Second circulation tank electrodeposition bath downstream circulation flange insulation pipe 2250 Second circulation tank electrodeposition bath bypass circulation flexible pipe 2251 Second circulation tank Electrodeposition bath bypass circulation valve 2252 Second electrodeposition bath outlet shower valve 2253 Two electrodeposition tank filter circulation return flexible pipe 2254 Second electrodeposition tank filter circulation return flange insulating pipe 2255 Second electrodeposition tank drain valve 2256 Second electrodeposition tank filter circulation source valve 2257 Second electrodeposition tank filter circulation direction 2258 No. 2 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 Two electrodeposition tank filter circulation filter 2264 Second electrodeposition tank filter circulation direction 2265 Second electrodeposition tank filter circulation direction 2266 Second electrodeposition tank filter circulation flexible pipe 2267 Second electrodeposition tank filter circulation flange insulating pipe 226 8 Second electrodeposition tank filter circulation valve 2269 Second electrodeposition tank filter circulation system electrodeposition bath upstream return valve 2270 Second electrodeposition tank filter circulation system electrodeposition bath middle flow return valve 2271 Second electrodeposition tank filter circulation system electrodeposition Bath downstream return valve 2272 Second electrodeposition tank stirring air downstream control valve 2273 Second drain tank drainage storage tank 2274 Second drainage tank 2275 Second drainage tank air release valve 2276 Second drainage tank air release 2277 First drainage Liquid tank drainage storage tank top lid 2278 Second drainage tank drainage storage tank top lid 2279 Pure water shower tank return entry roller 2280 Pure water shower tank roller 2281 First hot water tank return entry roller 2282 First hot water tank roller 2283 Second hot water tank return Entry roller 2284 Second hot water tank roller 2285 Dry turn-back roller 2286 Take-up device entry row 2287 Winding device direction change roller 2288 Winding adjustment roller 2289 Long substrate winding bobbin 2290 Interleaf unwinding bobbin 2292 Long substrate winding direction 2293 Long substrate winding bobbin rotating direction 2294 Interleaf unwinding bobbin rotating direction 2295 Winding Device clean booth 2296 Take-up device 2297 Second electrodeposition bath outlet shower 2298 Pure water shower bath back surface brush 2299 Pure water shower bath inlet surface pure water shower 2300 Pure water shower bath inlet back pure water shower 2301 Pure water shower bath outlet 2302 Pure water shower tank outlet back side pure water shower 2303 Pure water shower tank outlet surface pure water shower 2304 First hot water tank hot water heater 2305 First hot water tank exhaust port 2306 First hot water tank ultrasonic source 2307 Second hot water tank hot water storage Heater 2308 Second hot water tank exhaust port 2309 Second hot water tank outlet back surface pure water shower 2310 Second hot water tank outlet front surface pure water shower 2311 Drying unit inlet back surface air knife 2312 Drying unit inlet surface air knife 2313 IR lamp 2314 Drying unit exhaust Mouth 2315 Pure water shower tank receiving tank 2316 First hot water tank hot water holding tank 2317 Second hot water tank hot water holding tank 2318 Pure water shower tank return entry roller cover 2319 First hot water tank return entry roller cover 2320 Second hot water tank return entry roller Cover 2321 drying section cover 2322 hot water tank connecting pipe 2323 pure water shower tank pure water shower supply source 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 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 tank entrance surface pure water shower Valve 2331 Pure water shower tank inlet back pure water shower valve 2332 Pure water shower tank outlet back pure water shower valve 2333 Pure water shower tank 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 Rinsing system drainage 2337 Rinsing system pure water inlet 2338 Rinsing system pure water supply source valve 2339 Pure water heating tank 2340-2343 Pure water heating tank pure water heater 2344 Pure water heating tank pure water delivery valve 2345 Pure water heating Tank pure water delivery pump Ipass 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 Second hot water tank outlet backside shower valve 2352 No. 2 hot water tank outlet surface shower valve 2353 Drying compressed air inlet 2354 Drying compressed air pressure switch 2355 Drying compressed air filter regulator 2356 Drying compressed air mist separator 2357 Drying compressed air supply valve 2358 Drying section inlet back air knife valve 2359 Drying section inlet surface air knife valve 2360 Pure water shower tank 2361 First hot water tank 2362 Second hot water tank 2363 Drying section 2364 Electrodeposition washing system Exhaust duct Washing side insulating flange 2365 Electrodeposition washing system Air duct main insulating flange 2366 Electrodeposition rinsing system exhaust duct condenser 2367 Electrodeposition rinsing system exhaust duct heat exchange grid 2368 Electrodeposition rinsing system exhaust duct condenser drain drain 2369 Electrodeposition rinsing system exhaust 2370 Drying system exhaust duct 2371 Drying system condensation 2372 Drying heat exchange grid 2373 Drying condenser drainage drain 2374 Drying exhaust

Continuing on the front page (72) Inventor Yuichi Sonoda 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yusuke Miyamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. F term (reference) 4K029 AA02 AA25 BA49 BD09 CA05 5F051 BA14 CB11 CB15 CB27 CB30 FA02 HA03

Claims (16)

[Claims] 1. An electrodeposition method in which zinc oxide is electrochemically deposited from an aqueous solution on a substrate, and the deposited film is washed with water and dried. At the time of drying, at least 30% of water adsorbed on zinc oxide is removed. A zinc oxide electrodeposition method, characterized in that: 2. The method according to claim 1, wherein at least three of the water adsorbed on the zinc oxide are present.
2. The zinc oxide electrodeposition method according to claim 1, wherein 0% is released by hot air. 3. The zinc oxide electrodeposition method according to claim 2, wherein the temperature of the hot air is 200 ° C. or higher. 4. The method according to claim 1, wherein the substrate is a roll-shaped metal. 5. A transfer speed of a substrate is 1000 mm / min.
The zinc oxide electrodeposition method according to claim 1, wherein: 6. The zinc oxide electrodeposition method according to claim 1, wherein the aqueous solution contains zinc nitrate, and the concentration thereof is 0.05 M / l or more. 7. The zinc oxide electrodeposition method according to claim 1, wherein a zinc oxide thin film is formed on the substrate by sputtering prior to deposition by electrodeposition. 8. The film thickness of the zinc oxide thin film formed by sputtering is 2
The zinc oxide electrodeposition method according to claim 7, wherein the temperature is not more than 000 °. 9. An electrodeposition apparatus for electrochemically depositing zinc oxide from an aqueous solution on a substrate, washing the deposited film with water, and drying the deposited film, wherein at least 30% of water adsorbed on the zinc oxide is removed to a drying section. A zinc oxide electrodeposition apparatus characterized by comprising means. 10. The zinc oxide electrodeposition apparatus according to claim 9, wherein the means for releasing at least 30% of the moisture adsorbed on the zinc oxide is provided by a circulator for generating hot air. 11. The zinc oxide electrodeposition apparatus according to claim 10, wherein the temperature of the hot air generated by the hot air generating circulator is 200 ° C. or higher. 12. The zinc oxide electrodeposition apparatus according to claim 9, wherein the substrate used is a roll-shaped metal. 13. The transfer speed of a substrate is 1000 mm / mi.
The zinc oxide electrodeposition apparatus according to any one of claims 9 to 12, wherein the number is not less than n. 14. An aqueous solution containing zinc nitrate, the concentration of which is 0.05 M / l or more.
14. The zinc oxide electrodeposition apparatus according to any one of claims 13 to 13. 15. The zinc oxide electrodeposition apparatus according to claim 9, wherein a zinc oxide thin film is formed on the substrate by sputtering prior to deposition by electrodeposition. 16. The zinc oxide electrodeposition apparatus according to claim 15, wherein the thickness of the zinc oxide thin film formed by sputtering is 2000 ° or less.