TW555890B - A metallic anode oxidation treatment system utilizing a vibration flow agitation - Google Patents

Abstract

An object of the present invention is to provide an anode oxidation method with higher anodizing rate, less energy consumption and higher efficiency of oxide film formation and to provide an anodizing method in which an excellent, uniform oxide film can be obtained without burning of the metal body even if the metal body has a complicated profile. This invention provides a metal anode oxidation treatment system, which is characterized in that, in the metal anode oxidation process, (A) is disposed with vibration generation mechanism containing vibration motor; a vibration fluidly stirring mechanism coupled with the vibration generation mechanism and one-section or multiple-sections vibration vanes fixed with a vibration rod in the stirring tank vibrating at an amplitude from 0.5 to 3.0 mm and at a vibration frequency of 200 to 800 times per minute; an AC/DC shifter used to control the vibration motor vibrating arbitrarily at 10-500 Hz; and a vibration fluidly stirring device of the treatment bath of the vibration stress distribution mechanism disposed at the connection portion of the vibration generation mechanism and the vibration fluidly stirring mechanism, and (b) is to concurrently perform an aeration in the treatment bath by using air bubbles generated by a ceramic diffuser having a pore diameter of 10 to 400 mum and 30-40% of porosity.

Description

555890 A7

555890 Printed A7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) There is no significant difference between the point that the oxide film cannot be effectively formed outside the system and that when only ⑺ is used. "&Amp;" The treatment temperature is implemented at a temperature higher than room temperature. " In addition, the oxygen gas bubbles; the resistance of the surface of the object to be treated becomes large, and the voltage in the cloud is reciprocated. As a result, a large amount of electricity is accompanied by high heat, and the energy consumption is high. The current density can only reach 2 to 3A / dm2 at most. [The problem to be solved by the invention] The purpose of the present invention is to provide a high-speed anode gasification of metals such as Ming, which can save energy, and at the same time improve the film production efficiency, A method of forming an anodized film which is non-scorching, high quality and uniform even on articles with complex shapes. [Method for solving the problem] The first aspect of the present invention relates to an anodic oxidation treatment system for a metal, which is characterized in that: (A) is provided with: a vibration generating mechanism including a vibration motor; and Vibration flow stirring mechanism that causes one or more sections to be fixed on the vibration blades vibrating in the vibration tank in the mixing tank to generate vibration flow with an amplitude of 0.5 to 3.0 mm and a vibration number of 200 to 8000 times / minute; A DC-AC converter for controlling a vibration motor so that it can vibrate arbitrarily between 10 and 500 Hz; and a vibration flow stirring of a processing bath provided by a vibration stress dispersing mechanism provided at a connection portion between the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism Device, (B) As an inflatable device for the treatment bath, an inflatable device using a ceramic diffuser with an air pore size of 10 to 400 V m and a porosity of 30 to 40%. The dimensions are applicable to Chinese national standards ( CNS) A4 specification (210 X 297 mm) \-m J -------- ^ --------- ^ 9— (Please read the precautions on the back before filling this page) A7

555890 V. Description of the invention (l) Simultaneous actions. According to the present invention, as described above, the anodization is performed by the vibration flow stirring of (A) and the aeration combination of (B). Compared with the conventional technology using only aeration (B), the current density can be easily increased and anodization treatment is performed. The current density can be changed from about 2 to 3 A / dm2 in the conventional method to about 10 to 15 A / dm2. As a result, the processing time can be shortened surprisingly. The processing temperature of% polar oxidation treatment is a very important factor for energy cost and oxide film quality. In the past, only the method of aeration (B) was used. In order to form a hard acid-resistant inscription, its processing temperature must be in the range of 5 to 0 ° C. Even if it is a general acid-resistant aluminum, the temperature is preferably below 20 ° C. Invented the method of using (A) vibrational flow stirring and (B) aeration, even when forming a hard acid-resistant inscription, the processing temperature can be 10 to 20 ° C, and the general acid-resistant aluminum is 30 to 30 It can be 35 ° C, which can greatly save energy in terms of cooling energy. At the same time, in terms of the quality of the oxide film, even if the processing temperature is higher than the conventional method, amazingly good results can be obtained. The present inventors first proposed the use of a vibration flow stirring device in a plating tank in Japanese Patent Publication No. 6-71544 (Patent No. 1941498) and Japanese Patent Laid-Open Publication No. 6-220697 (Patent No. 2707530). In the electric ore tank, the metal to be mined forms a cathode, and the metal ions to be plated out on the surface of the cathode. However, water must be electrolyzed during electroplating to generate hydrogen on the surface of the cathode. In the conventional method, hydrogen existing on the surface of the cathode It will bubble, increase the resistance, and significantly reduce the current efficiency. As a result, the precipitation of metal ions is delayed, and electricity ore takes a long time. The present inventors have described the technique in the aforementioned Japanese Patent Publication No. 6-71544 (Patent No. 1941498). The proposal is to make the plating tank vibrate and flow 1 # ------------------- Order --------- (Please read the precautions on the back before filling in this Page) Printed by the Intellectual Property Bureau Employees 'Cooperatives of the Ministry of Economics This paper is printed in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 3 311303 555890 Printed by A7 Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics 4) Drop. At this time, the function of the vibrating flow stirring device is to effectively remove the air bubbles existing on the surface of the cathode, and to effectively prevent the hydrogen bubbles that hinder the precipitation of metal ions. In contrast, anodization is through the electrolysis of water, and the hydroxyl ions collected in the anode are decomposed into oxygen through discharge. This oxygen oxidizes the metal surface formed on the anode, making oxygen in a bubble state, and does not exist on the anode surface as much as possible. The function of the vibration flow stirring device in the electric ore tank is to remove the hydrogen bubbles existing on the surface of the cathode. The use of the vibration flow stirring device in the anodization will remove the oxygen bubble gas that must remain on the surface of the anode. This use can be considered as a taboo. However, completely unexpected results occurred in the actual test. That is, the oxygen generated by the electrolysis does not substantially bubble, and it is estimated that the state of the oxygen in the generator can react with the metal extremely efficiently, and a fine and uniform oxide film can be formed more quickly than the conventional method. This result is even more surprising. The second aspect of the present invention relates to an anodic oxidation treatment system for a metal, which is characterized in that: (A) is provided with a vibration generating mechanism including a vibration motor in the metal anodizing process; and one or more sections are linked with the vibration generating mechanism. A vibrating flow stirring mechanism fixed on a vibrating blade that vibrates in a stirring tank generates a vibration flow with an amplitude of 0.5 to 3.0 mm and a vibration number of 200 to 800 times / minute; it is used to control the vibration motor to make it A DC-AC converter capable of arbitrarily vibrating between 10 and 500 Hz, and a vibration flow stirring device for a processing bath provided in a vibration stress dispersing mechanism provided at a connection portion between the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism, (B) as a pair Inflator for treatment bath using a ceramic diffuser with a pore size of 10 to 400 // m and a porosity of 30 to 40%, ftm -------- Order ---- ----- (Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 size ⑽ x 297 Gongchu 4 311303 555890 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (5) (C) Used to suspend the electrode rod with the object to be processed, and use a vibration motor adjusted to 10 to 60Hz by a DC / AC converter, giving the object to be processed with an amplitude of 0.5 to 1.0mm 2. The vibrating device with a vibration number of 100 to 300 times per minute operates simultaneously. The second aspect of the present invention relates to an anodic oxidation treatment system for a metal, which is characterized in that: (A) is provided with: a vibration generating mechanism including a vibration motor in the metal anodizing step; A plurality of vibration blades fixed on a vibration blade vibrating in a stirring tank, and a vibration flow stirring mechanism that generates a vibration flow with an amplitude of 0.5 to 300 mm and a vibration number of 2000 to 8000 times / minute; used for controlling A DC-AC converter capable of vibrating arbitrarily between 10 and 500 Hz by a vibration motor; a vibration flow stirring device for a treatment bath, a vibration stress dispersing mechanism provided at a connection portion of the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism, (B) Inflation device using ceramic diffuser with a pore size of 10 to 400 m and a porosity of 30 to 40% as an aeration device for the treatment bath, (D) For hanging through The electrode rod of the object to be processed is given a shaking device with a shaking range of 10 to 100 mm and a shaking number of 10 to 30 times / minute. The fourth aspect of the present invention relates to an anodic oxidation treatment system for a metal, which is characterized in that: in the metal anodizing process, a vibration generating mechanism including a vibration motor is provided; and the vibration generating mechanism is linked to make- Multiple sections are fixed to the vibrating blades vibrating in the mixing tank, with an amplitude of 0.5 to 3.0 mm and a fine number of vibrations. _ 家 _ ($ S) A4 Secret (2 »^^ 5 311303 ---- ---- ^ --------- (Please read the precautions on the back before filling out this page) 555890 A7 B7 V. Description of the invention (6) 8000 times / minute vibration flow stirring Mechanism; a DC-AC converter for controlling the vibration motor to arbitrarily vibrate between S 10 and 500 Hz ', and a vibration flow stirring device provided at a vibration stress dispersing mechanism at a connection portion between the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism (B) As an inflation device for the treatment bath, an inflation device using a ceramic diffuser with an air porosity of ⑺ to 400 vm and a porosity of 30 to 40%, (C) for penetrating through the book The electrode rod of the treatment object is adjusted to 10 to 60 through a DC / AC converter. A vibration motor of Hz, which vibrates the object to be processed with an amplitude of 0.5 to 1.0 mm and a vibration number of 100 to 3,000 times per minute, (D) an electrode rod for hanging the object to be processed The rocking device with a shaking range of 10 to 100 mm and a shaking number of 10 to 30 times per minute is simultaneously operated. The present invention has the above-mentioned features, except that the anodizing system is the same as the conventional method. A heating device (required in winter or cold) for controlling the reaction temperature and a cooling device for the anodizing bath for removing Joule heat generated in the anodizing bath are provided. In electroplating, metal ions generated from the anode are formed on the cathode. The object to be electroplated, the metal ions are deposited to form a metal coating film. Since the present invention is anodized, the object to be treated is electro-mineralized to form an anode on the contrary. It is self-oxidized by the oxygen generated from the anode. An oxide film is formed on the metal surface of the alloy. The technical ideas of the two are fundamentally different. In the present invention (A), the vibration flow stirring device for the processing bath is divided into two parts. The vibration generating mechanism of the vibration motor; linked with the vibration generating mechanism 311303 Please order ^ Zhang size is suitable for the national standard of the country ^ S) A4 specifications ⑽ χNuo Chu Chu) 555890 A7 B7 V. Description of the invention (7) and fixed one or more sections A vibrating flow stirring mechanism that generates a vibrating flow at a vibration blade vibrating in a stirring tank with an amplitude of 0.5 to 3.0 mm and a number of vibrations of 2000 to 8000 times / min; used to control A vibration motor allows it to vibrate arbitrarily between 10 and 500 Hz, preferably between 30 and 60 Hz, and more preferably between 30 and 40 Hz; a DC-AC converter; and a vibration generating mechanism provided with the vibration flow The vibration stress dispersing mechanism of the connection part of the stirring mechanism is ideal. The output power (w number) of the vibration motor can be selected according to the liquid volume of the treatment bath. For details, refer to Japanese Patent Application Laid-Open No. 8-173785 [0016]. A ceramic diffuser was used for the aeration device (B) in the treatment bath. The Joule heat generated in the system can be dissipated through the air diffusing tube, and the function of inflation is south and suitable. The majority of diffuser tubes with air holes of about 1 mm are installed in synthetic resin tubes such as PVC. The air particles are too large to effectively remove the electrolysis heat and the resistance will vary. Since the inflator used in the present invention uses a porous tube made of ceramics as a diffuser, the above problems can be solved. The above-mentioned ceramic porous tube is preferably a high-temperature-fired ceramic tube such as alumina abrasive particles with a trade name of Arendam as a bone material. The air pore diameter of the ceramic diffuser tube is 10 to 400 vm, especially 10 to 120 / The zm is ideal, and the porosity (ratio to surface area) is preferably about 30 to 40%. The inner diameter of the Tao Jingqi diffuser is usually 50 to 100 mm, and the length is close to the length of the treatment bath, usually about 1000 to 1 500 mm. There is no particular limitation on the setting method. When using a plurality of branches, the air bubbles generated by inflation are uniformly surrounded by a ceramic diffuser as if to be treated. The paper dimensions are applicable to China National Standard (CNS) A4 specifications ⑵χχ297 Issue 7 311303 555890 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (8) Taken. When the air diffusing tube is parallel to the air diffusing tube, the interval is preferably 100 to 120 mm. The vertical distance between the air diffuser and the object to be processed is usually preferably 100 to 300 mm. As long as each condition is properly set, the inflation can be strengthened about twice as much as in the past. As a necessary condition of the above (C), the number of Hz of the vibration motor used to vibrate the electrode rod is preferably 50 to 65% of the number of Hz of the vibration motor of (A), and the number of Hz is 10 to 60 Hz. It is preferably 20 to 35 Hz, and the amplitude is 0.5 to 1.0 mm. This vibration is to vibrate the object to be processed, rather than to flow the processing liquid. As a necessary condition of the above (D), the object to be processed is shaken by hanging the electrode rod with the object to be processed, and the shaking range is 10 to 100 mm, preferably 20 to 60 mm, and the number of shaking is about 10 to 30 times / minute. More ideal. Examples of the metal subject to the present invention include aluminum, its alloy, magnesium, its alloy, titanium, its alloy, sharp, its alloy, group, its alloy, zirconium, its alloy, zinc, and its alloy. The aluminum alloy in the present invention may be any alloy that forms an anodized film through anodization. Specific examples include alloys such as aluminum-silicon (Al-Si), aluminum-magnesium (A1-Mg), aluminum-magnesium-silicon (Al_Mg-Si), and aluminum-zinc (Al-Zn). In order to perform anodizing treatment on these metals, a known pre-treatment step is provided. Examples of the pretreatment process include the following six. (1) Degreasing-washing (2) Degreasing-washing (-etching-washing) _decontamination-washing (3) mechanical polishing-degreasing-washing (4) mechanical polishing-degreasing-washing-etching-washing-decontamination-washing The paper size of the table applies to the Chinese National Standard (CNS) A4 specification (210 x 297 public love) 8 311303 (Please read the precautions on the back before filling in this page) ▼ Packing -------- Order · 1 ΊΊΊΊΦΤ

... I 555890 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (9) (5) Degreasing-washing-electrolytic polishing or chemical polishing-washing-removing oxides or decontamination-washing (6) Mechanical polishing-degreasing-water washing-electrolytic polishing or chemical polishing-water washing-removing oxides or decontamination-water washing includes various processing steps, reagents, and processing conditions for anodizing or post-treatment of aluminum or its alloys An example is shown in Table 1 below. [Table 1] Process_Reagent_Processing conditions (1) Degreasing solvent degreasing 40 ° C, 5 minutes 11 (2) Washing water room temperature, 1 minute (3) Etching NaOH (50g / L) room temperature, 5 minutes 12 (4) Washing water at room temperature, 1 minute (5) Decontamination HN0 (5%) room temperature, 1 minute (6) Washing water at room temperature, 1 minute (7) Anodizing H2S04 (200g / L) Room temperature 5 minutes 13 (8) Washing water at room temperature, 1 minute (9) Sealing treatment pure water (boiling water) immersed at 95 ° C, 15 minutes (10) Dry and naturally dry, 10 minutes 1 / ----- -------------- Order --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) 9 311303 1 1 The degreasing method can also use organic solvents (such as volatile oils), aqueous surfactants, acid aqueous solutions (such as 5 to 25 W / V% sulfuric acid aqueous solution), and alkaline aqueous solutions (such as NaOH 5 to 20W). / V%), phosphate aqueous solution or electrolytic cleaning. * 2 Alkali method (for example, NaOH 5 to 25W / V%), alkali phosphate method (for example, NaOH 3 to 8W / V%, sodium phosphate 5 to 10W / V%), chromium sulfate method, and the like. 555890 A7

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A7

555890 V. Description of the Invention For the 160 litre treatment bath, the aeration volume of the (U) tube is preferably greater than 1208. "In the current situation, ceramic stomata with a porosity of 30 to 40% are actually the highest performance snorkels. However, even for high-performance snorkels, the length of a stigma tube is limited to 150mm. If it is longer than this length, the air cannot be uniformly ejected. When the object to be treated is longer than a diffuser, according to the configuration of the diffuser as shown in Fig. 19, it can be inferred that the ceramic diffuser is inflated in the longitudinal direction and can be uniformized. As shown in Fig. 19 The distance fl and ρ between the air diffuser and the air diffuser shown are preferably about 100 to 120 mm. The pi is preferably about 50 mm or more. Therefore, the inflation in the treatment bath can be uniformized (refer to FIG. 19). In the anodic oxidation of the present invention, reaction heat is generated due to the oxidation reaction. If the processing liquid is not cooled to a certain degree, the temperature of the processing liquid cannot be maintained at a certain level. In coating, it is known that the properties of the film formed by the temperature rise of the treatment liquid are deteriorated, and if the temperature is too low, the oxide film may be cracked or cracked. According to the present invention, compared with the prior art, it can form a polar Superior anodized film In addition, according to the present invention, compared with the conventional method, even if the processing temperature is 10 to 5 ^ higher, an oxidation film comparable to the oxide film obtained by the conventional method can be formed. Anodizing can usually be performed at a temperature below 35 ° C, preferably at a room temperature of about 30 ° C, and when the general oxide film of an aluminum alloy is to be formed, it can usually be below 20 ° C, preferably 15 ° C. : Left and right processing. When a hard oxide film is to be formed, it is usually 10 to 15 -------------------- Order --------- (Please Read the notes on the back before filling out this page} Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 11 311303 555890 Ministry of Wisdom A7 V. Description of the invention (anodic oxidation is performed at ι0 ° C. In the present invention, a cooling device is provided for cooling the treatment liquid. The cooling device

A general cooling heat exchanger is used, and the processing liquid is preferably circulated through the cooling device. T The anodizing treatment solution for various metals represented by Ming or its alloys usually uses known chromic acid, boric acid, ammonium borate, sulfuric acid, phosphoric acid, oxalic acid, benzoic acid, amino acids, citrate, tartaric acid, formic acid Acid solution composed of acids such as,, etc. After the anodization, the porous surface is treated, that is, the sealing process. In the present invention, the same sealing process is performed (refer to the "Gold plating technology manual" issued by the Japan Industrial News Agency on July 25, 1997. To 600 pages) is ideal. The sealing treatment in the present invention can be performed, for example, by a water vapor sealing treatment, a metal salt sealing treatment, an electrode deposition coating coating, a sealing treatment using a dye or a pigment, or sealing the holes. Sealing treatment of the combination.口 The specific example of the invention in the scope of patent application of the present invention is No. 1! See Figure 3. Figure 1 is a side view, Figure 2 is a front view, and Figure 3 is a top view. 1 is a treatment bath, 4 is a vibration motor, 16 is a vibration rod, 17 is a vibration blade, 5 is a cathode, 6 is an anode, and 12 is a ceramic diffuser for inflation. Figures 4 to 6 are specific examples of item 4 of the patent application scope of the present invention. Corresponding to the scope of the patent application, if necessary, the device of (C) and / or 中 suspends the use of the device of item 1 or 2 of the patent scope. As the scale of application, the national standard of country f is applicable (CM · Specification ⑵〇χ f ^ y 12 311303 J > -------------------- Order ------ --- (Please read the precautions on the back before filling out this page) 555890 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (U) When using the device in the scope of the patent, the shaking device is provided with The rocking motor 3, the rocking support frame 2 that shakes in accordance with the rocking of the rocking motor, and the cathode hanger 5 which is fixed to the rocking support frame 2 by the cathode rod support 13 and also serves as a cathode. The object to be processed is electrically and physically They are all firmly connected and fixed to the above-mentioned hanging hanger 5 which also serves as a cathode. When the object to be processed is light, a support frame electrically connected to the anode is provided, and then the wire is used to fix the object to the support frame, etc. The fixing method is ideal. A vibration motor 14 for giving vibration to the support frame 2 for vibration is fixed at an appropriate position of the support frame for vibration, and the vibration of the vibration motor 14 causes the support frame 2 for vibration to be vibrated to transmit vibration to Structure of the object to be processed. On the other hand, it is shaken by the swing motor 3 It is conveyed to the supporting frame 2 for shaking, and the anode body is shaken. At this time, the amplitude of the shaking is 10 to 100 to ^, preferably 20 to 60 mm, and it is slowly shaken at a rate of 10 to 30 times / minute. In this specific example, the shaking direction is the left-right direction of Fig. 4 or 5. For one of the vibrational flow stirring devices of the bath, for example, as shown in Figures 7 and 8, the main body of the vibrational flow stirring device is not limited to this example, and can be used. Patent applications of the present inventors are Japanese Patent Application No. 6-304461, Japanese Patent Application No. 6-312124 (Patent No. 2762388), Japanese Patent Application No. 6-330395 (Japanese Patent No. 2992177), Japanese Patent Application No. 8.173785, Japanese Patent Application No. 9 4 The vibration flow stirring device disclosed in 〇482 (Patent No. 2911393) and Japanese Patent Publication No. 6-71544 (Patent No. 1941498). The vibration stress dispersing mechanism of the vibration flow stirring device is, for example, a vibration generating device and a vibration rod. The rubber ring of the connecting part is set around the vibrating rod. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love) U 311303 ---------------- --- Order --------- (Please read the notes on the back before filling (This page) 555890

V. Description of the invention (14) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 311303. Its length is longer than the diameter of the vibrating rod, usually 3 to 8 in diameter and its thickness is 1.3 to 3 in thickness. Hey, Shi, Gankou • ^ Several are ideally about 1 to 2.5 times thick. From another point of view, when the diameter of the vibrating rod is 16 to 16 mm, the thickness of the rubber ring is preferably 10 to 15 mm. When the diameter of the vibrating rod (round rod) is 20 to 25 mm, the thickness of the rubber ring is 20 to 30mm is ideal. In the case where a rubber ring is not used, the vibration stress is concentrated near the joint between the vibration transmitting member and the vibrating rod, and there is a problem that the vibrating rod is easily broken. At this time, if a rubber ring is inserted there, the problem can be solved. The material of the above-mentioned vibrating blade plate is preferably thin metal, elastic synthetic resin, rubber, etc., and its thickness may be such that at least the head end portion of the blade plate is shaken by the vibration of the vibration motor up and down (in a wave-like state) The thickness of these systems imparts vibration and flow to these systems. Metal Vibration Blades can be made of titanium, aluminum, steel, steel, stainless steel and their alloys. Examples of the synthetic resin include polycarbonate, vinyl resin, and polypropylene. In order to improve the vibration effect transmitted by the vibration energy source, there is no particular limitation on the thickness. 'Generally, it is 0.2 to 2 mm when using metal and 0.5 to 10 mm when using plastic. If the thickness is too thick, the effect of vibrational flow stirring will be reduced. When the material of the vibrating blade plate is made of elastic synthetic resin, rubber, etc., there is no particular limitation on the thickness. Generally, it is preferably 1 to 5 mm, and when metal stainless steel is used, it is 0.2 to 1 mm, and 0.5 mm is more preferable. The amplitude of the vibration plate is 2 to 30 mm, preferably 5 to 10 mm. One or more sections can be installed for the vibration shaft. Corresponding to the scale of the processing liquid, China's 1S ^ ns) A4 specification (X 297 public love) -------------------- Order --------- ^ 9— (Please read the notes on the back before filling out this page) 555890 B7 V. Description of the invention (15) Multiple blades can be used without vibrating. When the number of multi-stages is increased, the load of the vibration motor becomes larger, and the vibration amplitude becomes smaller, and the vibration motor generates heat. Note The vibrating blades can be installed at right angles to the vibrating rod, and when the right-angle direction of the vibrating rod is 0, they are inclined in the direction of (+) or (a), preferably 10 to 20. Ideal installation (refer to Figures 7 and 9). The vibrating blade fixing member and the vibrating blade may be inclined and / or bent integrally as viewed from the side of the vibrating shaft. Even when it is curved, the entire tilt can be 5 to ⑽ degrees, especially || It is ideal to tilt 10 to 20 degrees. —The vibration blade can be clamped from the upper and lower sides via the vibration blade fixing member, and fixed to the vibration rod to form a vibration blade portion. Specifically, a. The above-mentioned vibrating blade can be cut by threading the vibrating rod, and then locked and fixed with screws. When pressed, the vibration blade fixing members 18 and 18 are locked with screws 24 and 24, and the vibration blade 17 is preferably fixed. When tilting and / or bending the vibration blade portion, in most of the vibration blade portions, tilt and / or bend the two pieces below, and tilt and / or bend the other blades upward. Through these operations, the bottom of the treatment bath can be performed to prevent accumulation in the bottom. Moreover, it is not desirable to remove the above-mentioned downwardly-bending vibration blade when only the bottom of the treatment bath is stirred. For example, Shen Dianwu and other unwanted components accumulate in the bottom to prevent the sediment from spreading, and it is more convenient to remove it from the bottom. In addition, in order not to let out the generated gas too early, the vibration blade plates can all be bent at an angle of ^ or downward. i Zhang Ji SiT? iii ^ NS) A4 specifications ⑽χ 297 issued) 311303 555890 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (1) The vibration flow stirring device can be as shown in Figures 12 and 13 The illustration is only provided on one side of the treatment bath, but as shown in Figs. 1 to 5 on both sides of the treatment bath, the bath can be uniformly flowed and stirred in accordance with a large bath. The vibrating flow stirring devices described so far are all vibrating blade up-and-down vibration types, but there are also patent applications such as Japanese Unexamined Patent Publication No. Hei 6.304461 or Figure 10 and Figure 丨 丨The vibration direction is shown in the horizontal direction, and the vibration blade 17 is installed in the treatment bath! The bottom of it. At this time, the vibration motor 27 provided on the left side of FIG. 11 is used as the center. In order to obtain the balance between the left and right weights, it is desirable to provide a weight balancer 26 having a balance with the left weight. When the vibration flow stirring device is arranged near one side of the treatment bath, the length of the vibration blade is longer in the wider direction of the bath, and shorter in the shorter direction of the bath, and the intensity of the flow can be adjusted. The vibrating rod can be directly connected to the vibration motor, but the inventors have adopted the vibration related to the invention as disclosed in JP-A-6-304461 or JP-A-6-330395 (Patent No. 2992177) via the vibration frame. Communication to the form of a vibrating rod. As shown in FIG. 9, if there are fluorine-based polymer films 23 and 23 between the vibration blade 17 and the vibration blade fixing members is and 18, the damage rate of the vibration blade can be greatly reduced under long-term use, which is ideal. . Examples of the fluorine-based polymer include polytetrafluoroethylene (PTFF), tetrafluoroethylene / hexafluoropropylene copolycondensate (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolycondensate (PFA), and polytrifluoroethylene Ethylene (PCTFE), polyvinylidene fluoride (PvdF), polyvinyl fluoride, ethylene / tetrafluoroethylene copolycondensate (ETFE), ethylene / gas trifluoroethylene copolycondensate, propylene / tetrafluoroethylene copolycondensate, etc., A fluorine-based rubber is also preferable. -------- ^ --------- (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 specification (21〇X 297) ) 16 311303 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 555890 A7 ------ B7 V. Description of the invention (π) In the present invention, the device provided with the above (A) and (B) can be used 'The devices of (A), (B), (C) above, the devices of (A), (B), (D) or the devices of (A), (B), (〇, (D) above, will Continuous and / or automatic system for the object to be moved in each treatment bath at a certain time. It is ideal to use at least the device of (A) above for the baths required for each treatment bath before or after treatment. If (A ) + (B), (A) + (B) + (C), (A) + (B) + (D), or (A) + (B) + (C) + (D) are of course effective. The above-mentioned (A), (A) + (B), (A) + (B) + (C), (A) + (B) + ( D) or (A) + (B) + (C) + (D) devices, especially in the polishing process selected from the group consisting of degreasing process, electrolytic polishing and chemical polishing It is ideal to use in at least one of the processes and hot-water sealing treatment process. Even if it is used in any process, the efficiency of the process can be improved separately. When electrolytic vibration is not used (A), the composition of the bath is Using dish acid (H3P04) (89% aqueous solution) 600 g / L sulfuric acid (H2S04) 400 g / L glycerol G / L, the current density is 10 to 16A / d m2, the voltage is 5 to 20V, and the processing temperature is It takes 10 to 15 minutes at 90 to 100 ° C, and when the vibrational flow stirring device of (A) is used for electrolytic polishing, the bath composition is phosphoric acid (89%) 300 g / L sulfuric acid 200 g / L glycerol 10 G / Liter Φ t ------------------- Order --------- ^^^ 1 (Please read the precautions on the back before filling this page) Paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 17 311303 555890 A7

V. Description of the invention (18) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition to reducing the concentration, the processing temperature can be 50 to 600c and the processing time can be saved to 7 to i minutes, which is very economical. When these electrolytic polishing processes are used, the appearance and gloss of the obtained oxide film can also be improved. In chemical polishing, the same tendency as that of electrolytic polishing has been confirmed. It can significantly reduce the processing temperature and improve the appearance and gloss of the obtained oxide film. [Examples] The present invention will be described below with examples, but the present invention is not limited to these examples. In this embodiment, the system shown in FIG. 17 is used. Of course, when the devices of FIGS. 1 to 3 are used, the state in FIG. 17 and the non-existing state and the inactive state are used. When the size of the test plate or test piece is small, the test plate or test piece is fixed to a support frame connected to the anode via a wire. The devices of (C) and (D) act on the support frame. Example 1 As shown in Figs. 1 to 3, a vibration stirring device (A) and an aeration device (B) were installed in a treatment bath 1 for anodizing. The dimensions, capabilities, etc. of each device are described below. In order to maintain a constant temperature of the processing liquid, the processing bath is connected to a cooling heat exchanger for cooling the processing liquid and a circulating pump capable of drawing out the processing liquid and passing it through the cooling heat exchanger by a pipe. (1) Anodizing bath: 500 m wide, 750 m long, and 550 mm high made of heat-resistant gasified vinyl resin. (2) Vibration stirrer: Structure shown in Figure 1 to 2. Vibration α-Mixer type 3, 250Wx 200Vx 3-phase vibration motor is a Ulas vibrator KEE 3.5-2B type 250W, with DC AC ------------------- Order- -------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 18 311303 555890 Employees ’Intellectual Property Bureau of the Ministry of Economy Consumption Cooperative printed A7 V. Description of the invention (D) Current transformer (0.4KW) Vibrating blade: effective area is 300x100mm thick and 5mm5 pieces, a = \ 5 ° (only the lower section is downward, the rest are all upward) ) The amplitude of the vibration blade is 1.5mm. (3) Air diffuser ·· The micro-inflator BM-100 (inner diameter: 50mm, outer diameter: 75mm, length: 45mm), air vents "Torque volume specific gravity ·· 2 to 2.5 (2) to 2 / 2.5 (4) air blower: Rotary air pump, output power 15w, air ejection volume 120 liters / (5)% polar oxidation bath ·· Containing liquid volume of 160 liters of sulfuric acid 2,000 g / liter, aluminum 4 gram / liter (6) Cathode plate: 4 pieces of nameplate 60 mm wide, 20 mm thick, and 50 mm long (7) Test plate: Pure nameplate equivalent to the object to be treated (A11〇p, JISH400, silicon + iron: 10% or less, copper: 0.05 to 0.02%, manganese · 5% or less, word: 0.10% Below, Ming: 99.00% or more) 100mm in length, 100mm in width, and 1.5mm in thickness (8) Test plate hanger · Fix the test plate to the anode frame with aluminum wire (see Figure 21) (9) Heat exchange for cooling Device: Automatic direct-cooling type rapid cooling device with cold pad 4010 kcal / hour, motor 1.5kw caliber 25A manufactured by Showa Lead Iron Co., Ltd. (10) Circulation pump for heat exchanger: magnet pump maximum injection capacity 120 liters / Min, Max Head 8.6m, 200V, output power 265W, 1 27A, (Yimu paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^ ------ 311303 ----- --- 1 --------- (Please read the notes on the back before filling out this page) 555890 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 20) Vache MD-100RM)

(11) Rectifier: Silicon rectifier for electroplating rated 60V-100A, 6.0kw, AC input 200V, 21.2A, 7.34KVA

[Ultra-Mini DC Power Supply Device MB7C_6〇0-01 Central Manufacturing Co., Ltd.] (12) Distance between electrodes: 〇〇mm (13) < Configuration of processing bath > Degreasing bath-water bath-remaining bath- Water bath-Decontamination bath-Water bath-Anodizing bath-Water bath-Sealing treatment bath-Drying bath (Note) Etching bath: Caustic 50 g / L, RT 5 minutes Decontamination bath: 5% nitric acid, RT 1 minute seal Pore treatment bath: 15 minutes of boiling water of ion-exchanged water < anodizing conditions > The number of Hz of vibration flow stirring is 37Hz (250W x 200V X 3 phase vibration, DC AC converter 0kw) Under the aerated condition, under the above-mentioned aeration condition, the anode voltage was 20V and the temperature of the treatment bath was 2 ° C under the current density as shown in FIG. 20, and anodizing treatment was performed for 8 minutes. 20 / zm was obtained by this. An anodized film, the film is fine and the surface gloss is good. These results are shown in Table 1. Comparative Example 1 -1 Except that the vibration stirring device of Example 1 does not operate and the current density is 2 A / d m2, it is implemented Example 丨 the same operation, the film thickness of the anodized film is the same as that of Example 1 Same as 20 // m, the time required is 4〇 ------------ * ------- order --------- (Please read the back first Please pay attention to this page, please fill in this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 20 311303 Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 555890 A7 _ B7_ V. Description of the invention (21) The results are shown in Table 2. Comparative Example 1-2 Except that the vibration stirring device of Example 1 did not operate, the current density was 2 A / d m2, and the vibration device was connected to the anode, and adjusted to 40 Hz through a DC / AC converter. The same operation as in Example 1 was performed except that the amplitude of the object to be treated was 0.5 to 1.0 mm and the number of vibrations was 200 times per minute. The treatment was performed until the film thickness of the anodic oxide film was equal to 20 " m as in Example 1. The required time is 20 minutes, and the results are shown in Table 2. The comparative values of Example 1 and Comparative Example 1-1 and Comparative Example 1-2 are shown in Table 2 below. [Table 2] Current density A / dm Time at 20 / z * 1 Appearance (HV) * 2 _Corrosiveness * 3 Dyeability * 4 Financial wear * 5 Example 1 10 8 minutes gloss good 430 100h good 1200 Comparative example 1-1 2 40 minutes gloss difference 350 48h slightly better 800 Comparative Example 1-2 2 20 minutes gloss 400 60h slightly better 900 * 1 Anodized film thickness: eddy current method based on JIS H8680-1979 * 2 hardness: according to JIS H8682-1988 Vickers Hardness Tester (HV) Hard Coating Test * 3 Corrosion Resistance Test: Based on JIS-H8681-1988, Evaluation No. 9 * 4 Dyeability: Food water-soluble dye red 0.5%, JIS H8685-1988 * 5 Abrasion resistance: Based on JIS-H8682-1988 (reciprocating plane abrasion test) as the standard, but the load is 400 ± 10gf (3.92 soil 0.09N) in general anodized film, in hard anodized film At 2000 ± 50gf (19.6 ± 0.49N) Comparative Example 1 -2 is not better than Example 1 and can be considered as the aluminum surface in liquid k: ------------------ -Order --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 21 311303 555890

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The current density of Comparative Example 1 stops at 2A / d m2, and the motor's degree of Example 1 can be increased to relatively! 〇A / d m2, the anodic oxidation rate of Example 1 is about 5 times that of Comparative Example 1, and the hardness of the anodic oxide film, the corrosion resistance and steep dyeing, and the abrasion resistance of any of Example 1 are all It is higher than Comparative Example 1. The 10 // m, 15 // twisted anodized films also obtained almost the same results. Example 2 All conditions (1) to (13) of Example 1 are the same. Anodization was performed under the following anodizing conditions according to the apparatus of Figures 1 to 3. < Anodic oxidation conditions > The Hz number of vibration flow stirring is 37 Hz (150Wx 200V X 3-phase, DC flow converter 0kw), and the vibration flow stirring of the bath is performed, and the anode voltage is 15V under the above aeration conditions. 3. The temperature of the treatment bath was 30 ° C for 5 minutes. The results are shown in Table 3. Comparative Example 2 Anodization was performed for 5 minutes in the same manner as in Example 2 except that the vibration stirring device of Example 2 was not operated (Comparative Example 2-1). Anodization was performed in the same manner until the film thickness of the anodized film was the same as that in Example 2 (Comparative Example 2_2). These results are shown in Table 3. Comparative Example 3 Except that the vibration device was connected to the anode and adjusted to 40 Hz via a DC / AC converter, the amplitude of the object to be treated was 0.5 to 1.0 mm, and the number of vibrations was | -------- ^ — ( Please read the notes on the back before filling this page.) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 22 311303 555890

5. Description of the invention (23) [Table 3] Anodization was performed in the same manner as in Example 2 except that the vibration flow stirring of (A) in Example 2 was stopped at 200 times / min. However, Comparative Example 3-1 was anodized at a current density of 5 A / d m 2 for 5 minutes, and Comparative Example 3_2 was anodized at a current density of 10 A / d m 2 for 10 minutes. Current density A / dm Time & temperature Film thickness (* quot) Appearance hardness (HV) * 2 Salt spray resistance * 6 Example 2 15 5 minutes 30 ° C 15 β Gloss 350 48h Comparative Example 2-1 3 5 Min. 30 ° C 5 // Non-uniform 330 24h Comparative Example 2-2 3 20 minutes 30 ° C 15 β A matte crack can not be measured Cannot be measured Comparative Example 3-1 5 5 minutes 30 ° C Ί β Matte 300 No Measurement Comparative Example 3-2 10 10 minutes 30 ° C 15 β system less 320 24h * 6 Salt water spray resistance: Based on jis K5400 evaluation, the anodic oxidation rate of Example 2 can be about 4 times faster than Comparative Example 2-2 An oxide film with sufficient gloss and durability can be formed. In Comparative Examples 2-1 or 2-2 of the conventional method, if the temperature of the processing bath reaches 30 ° C, a practical anodized film cannot be obtained. Example 3 Except for the test plate of (7) in Example 1, a rigid aluminum plate (A5052P, JIS H400, silicon: 0.25% or less, iron: 0.04% or less, copper ... 0.01%, manganese: 〇.01% Below, magnesium: 2.2 to 2.8%, chromium: 0.15 to 0.35%, zinc: 0.10 / 0 or less) was replaced in accordance with Example 1 to produce an anodized film having a film thickness of 20 // m. The results are shown in Table 4. 1L Comparative Example 3 Except that the vibration stirring device of Example 3 does not work and Example 3 I ------------------ C Please read the precautions on the back before filling in this Page} --Order --------- Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 23 311303 555890 A7 B7 V. (24) In the same manner, anodization is performed until an anodized film having a thickness of 20 is obtained. The results are shown in Table 4. [Table 4] Current density A / dm Time film thickness * 1 Appearance example 3 Comparative example 3 Hardness (HV) * 2 Salt spray resistance * 6 Dyeability * 4 Wear resistance * 5 15 3.5 8 minutes 30 minutes 2 β 20β Good gloss Less gloss 460 350 150h 42h Good slightly uneven 800 600 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs t In hard anodizing, Example 3 can form the same thickness about 4 times faster than Comparative Example 3 The oxide film has excellent characteristics, appearance, hardness, dyeability, and abrasion resistance. Example 4 Using the device of Example 1, an aluminum plate A5052 was used for the test plate, and the bath temperature of the anodizing treatment bath was changed at various current densities of 8 A / d m2 to produce a film thickness of 1 5 " in of & The oxide film 'measures the hardness of the film thickness. The results are shown in Figure 16. 〇 is Example 4. Comparative Example 4 The operation was repeated in accordance with Example 4 except that the vibration stirring device of Example 4 did not operate (current density was 1.5 A / d m2). The results are shown in Figure 16. • For Comparative Example 4. The evaluation is compared with Comparative Example 4, and it is determined that the hardness of the coating film of Example 4 is relatively high under the same conditions of the corresponding processing bath temperature. Therefore, if an oxide film with the same hardness as the comparative example is to be obtained, the temperature of the processing bath can be compared The example is high, and is particularly advantageous to the present invention in terms of cooling energy and processing time. Example _ This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 24 311303 I -------- Order --------- (Please read the note on the back first Matters refill this page} 555890 A7

V. Description of the invention (25)

7 The wall face is an L-shaped wall part of the scale product depression. 8 The bottom is the scale product depression. The bottom is the same as in Example 1. An irregular pit exists between 3 to 15 mm and a depth of about 15 to 20 mm.) Anodizing is performed to produce an anodized film having a thickness of bp. The results are shown in Table $. Comparative Example 5 The operation was repeated in accordance with Example $ except that the vibration mixing device of Example 5 did not operate. The results are shown in Table 5. [Table 5] All the recessed parts of Example 5 also formed a uniform oxide film. Even in Comparative Example 5, the oxide film of the recessed parts was still much thinner than the other parts even with 4 times the processing time of Example 5, leading to the whole. The thickness was uneven and the hafnium oxide did not have the gloss as in Example 5. It is also effective according to the present invention for articles having depressions such as Wnm in width and 10 to 15 mm in depth. The processing time of Example $ is about 1/4 of that of Comparative Example 5. Except that the treatment temperature in Example 5 was changed to 3 (rc, and the amount of air sprayed through the air diffuser was changed to 240 liters / minute), the operation was repeated in accordance with Example 6. The time required for the oxidation treatment film to become 15 // m was 5 minutes. .If anodizing can be performed under these conditions, the continuous belt can be used from pre-processing to post-processing -------- order --------- (Please read the precautions on the back before filling This page} Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 public love) 25 311303 555890 A7 B7 V. Description of the invention (26) Principle, no need to use a catheter In the same manner, the electrode deposition coating process can be performed in the same manner. Comparative Example 6 Repeated operation according to Example 6 except that the vibration stirring device of Example 6 does not operate. The oxide film is very uneven, has many irregularities, and is not practical. Example 7-1 is an example of using a small system as shown in Figures 12 to 14 as opposed to the large system shown in Figures 4 to 6. Install a vibration stirring device, (B) aeration device, (C) in the anodizing bath In order to impart a swing to the object, And (D) a device for vibrating the object to be treated via a sling. In addition, in order to maintain a constant temperature of the treatment liquid, a heat exchanger for cooling the treatment bath and the cooling treatment liquid that can cool the treatment liquid are connected by a duct, and the treatment liquid can be drawn out and made It passes through the circulation pump of the cooling heat exchanger. Other conditions are used to conduct experiments as described below, and the results are summarized in Table 6. < Configuration of treatment bath > Degreasing bath (〇) —water bath—etching bath—water bath— Decontamination bath (〇)-water bath-anodizing bath (◎)-water bath-plugging treatment bath (〇)-drying bath. The bath marked with ◎ is to install the above (A), (B), (C), (D) Each device. The bath marked with “0” is only installed with the above (A). Also, tap water (normal temperature) is used for water bathing. ≪ Processed object (anode) > Pure nameplate (500mmx 200mmx 10mm) 1 piece Anode and cathode distance: 100mm (Please read the precautions on the back before filling this page)

Aw ----- 11111 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 26 311303 A7

555890 V. Description of the invention (27) < Cathode > Pure nameplate (500mmx 60mmx 20mm) 8 pieces of anode and cathode are located at the center of the treatment bath, and the two sides of the treatment bath are separated from the anode by 100mm. Install 4 cathodes (refer to Figure 15). The upper part of the anode was mounted 70 mm below the liquid surface, and the lower part was mounted 70 mm above the bath floor. < Treatment bath for anodizing > Bath size (inner size): width 50〇111111 parent 7 50〇11111 ^ 5 50111111 (approximately 168 liters) vibration mixer vibration motor: 250Wx 200VX 3 phases 1 unit (commodity Name Yuras vibrator: manufactured by Murakami Seiki Co., Ltd. and sold by Yaskawa Commercial Co., Ltd.) Vibration blade: effective area 300 × 150mm, thickness 0.6mm, 6 pieces, α = 15 ° (only the lower section is downward, and the rest are upward) Vibration Blade Amplitude: 1.5mm Vibration Frequency: 37Hz (adjusted via DC / AC converter) Inflator uses 3 ceramic diffuser tubes with an outer diameter of 75mm, an inner diameter of 50mm, a length of 450mrn, and an air aperture of about 200mm. . Rotary air pumps with a porosity of 40 / 〇, an air blow-out volume of about 120 liters / min, and a wheel output power of 150 W were used. The shaking device is given 20 times / min via a motor with a reducer or a drum motor. The paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) '-27 311303 ------- ------------- Order --------- W & WI Γ% Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Trade name new cold lining SA3-2 1.5KW high) 555890 A7 —B7 V. Description of the invention (28) 40mm wide after shaking. A vibration device with a shaking device is provided. The vibration motor 14 is fixed to a proper position of the supporting frame 2 for swinging. The vibration motor 14 is vibrated at 30 Hz and an amplitude of 0.8 mm via a DC / AC converter. Composition of anodizing bath (capacity about 150 liters, liquid height of 400mm) and anodizing conditions Sulfuric acid: 200 g / litre Chain content: about 4 g / litre Processing conditions: As shown in Table 1, the cooling heat exchanger Showa Lead iron (stock) company manufacturing capacity · 4010 kcal / hour using circulating pump

Maximum flow rate 120 liters / minute, 265W, 1.27A degreasing bath (inside dimensions of the bath: 500x 75〇X 550mm, width X table X Tobacco degreasing agent: Use Deknin S800 (naphthenic petroleum solvent) bath temperature and Time: 40 ° C, 5 minutes touch etch bath (internal dimensions of the bath ·· 500χ 750χ 550) Sulfuric acid (sg1.84) 500ml / litre phosphoric acid (sg1.74) 100ml / litre chromic anhydride 30g / litre bath temperature And time 65 ° C, 10 minutes ----------------- ^ 9— (Please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS ) A4 size (210 X 297 mm) 28 311303 555890 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (29) Decontamination bath 5% nitric acid solution sealing bath immersed in the boiling of ion exchange water Liquid Example 7-2 Repeated operation was performed in accordance with Example 7-1 except that the vibration device (C) and shaking device (D) of the object to be processed did not operate. The results are shown in Table 6. [Table 6] Appearance weather resistance Property * 9 Dyeing property * 4 Salt spray resistance% Example 7-1 Good 500 hours Uniformity Good 140 hours Example 7-2 Good 300 Small Excellent uniformity 96 hours * 9 Weather resistance ·· According to (aging tester) jis-K 5400 Example 8-1 As shown in Figures 4 to 6, use a vibration stirring device (A) and an aeration device (B) The processing device of the vibration device (C) and the shaking device (D) of the processed object.

Anodizing bath: 500mmx 1250mmx 750mm (width x length x still) Anodizing bath: about 340 liters Anodizing bath composition: 200 g / L of sulfuric acid, 4 g / L of cathode plate: 10 pieces of name plate (500mmx 60mmx 20mm) Use anode plate for vertical row: use 500mmx 200mmx 10mm aluminum as the quilt ------------------- Order --------- ^ 9. (Please read the Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 × 297 mm) 29 311303 555890 Printed by A7 of the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (30) Position relationship between the cathode plate and the anode plate: The anode is installed in the center of the processing bath, and five cathodes are installed at positions 100 mm away from the anode on both sides of the processing bath (refer to FIG. 15). The upper part of the anode is 70 mm below the liquid surface, and the lower part is installed on the bottom of the bath 7011111. Vibration stirring device (A): Vibration motor: 400Wx 200Vx 3 phases and 2 units (brand name Ulas actuator) Vibrating blade · Effective area 300 × 150mm, thickness 6 mm, installation angle 15 ° Vibration blade amplitude: 1.5 mm Vibration frequency: 37Hz (Controlled by DC-AC converter) Inflator: 3 ceramic diffuser tubes with an outer diameter of 75mm, an inner diameter of 50mm, a length of 800mm, and an air hole diameter of about 200 μm. Each unit has a porosity of 40% and an air blowout volume of about 200 liters / minute. Vibration device (c) for vibrating the object to be processed. The vibration motor (40 W) 14 is fixed at an appropriate position of the support frame 2 for swinging, and the vibration motor 14 is passed through a DC / AC converter at 30 Hz and an amplitude of 0.8. mm vibration. Swing device (D): Gives a 40mm wide front and rear shake by a speed reducer motor or a barrel motor at 20 times / minute. Cooling heat exchanger: _Dimensions are applicable to China ^ standard (CNS) A4 specifications ⑽ x 297 public hair) 311303 -------- Order --------- ^ 9— CPlease read the first > I will fill in this page again if necessary] 555890 A7 B7 V. Description of the invention (31) Automatic lining of the cold lining: 4010 kcal / hour, 1.5 kw of motor, 2 5 A circulating pump for heat exchanger: Magnet pump maximum flow 120 liters / minute, Max Head 8.6m, 200V output 265W, 1.27A, rectifier:

Hi-Hi DC power supply device 60 V, 100 A, 6. Okw AC input, 200 V, 21.2 A, 7.35 KVA Process: configured according to Table 1 In addition, the device of this embodiment is also provided with a degreasing bath and a sealing bath. The results are shown in Table 7.

Example U Except that (C) and (D) are inoperative in Example 8-1, the operation is repeated in accordance with Example 8-1. The results are shown in Table 7. %-* -------------------- Order --------- (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau. Weather resistance * 9 Dyeability * 4 Resistance to salt water spray * 6 Implementation Example 8_1 Good 500 hours uniformity 140 Good examples 8-2 Excellent 300 hours Uniformity 96 hours Implement your use The same device as in Example 84 was used. Aluminum (A5052 plate) (size 5000x200mm 10mm) was used as the object to be treated, and the anodizing conditions were the sulfuric acid bath of Example 8 at a processing temperature of 7t: and a current density of i5A / d. Anodizing for 10 minutes

311303 555890 V. Description of the invention (32 The aluminum plate obtained in Example 9-1 is divided as shown in FIG. 18, and the thickness (// m) and hardness of the oxide film in each central part are measured. The results are shown in Table 8. [Table 8] Film thickness

44.7 44.7 44.5 j5.2 — 44.9 Average film thickness 44.7 Minimum thickness 44.1 Maximum film thickness 45 2 [Table 9] 44.1 44.4 44.5 44.9 44.9 44.7 519 509 520 527 511 519 514 521 521 526 516 512 512 516 520 512 518.0 511.0 527.0 Minimum Hardness Maximum Hardness -------------------- Order --------- (Please read the precautions on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Bureau employee consumer cooperative printed Example 9-2 Except that only the vibrating flow stirring device and the inflatable device acted in Example 9-1, the operation was repeated in accordance with Example 9-1. The thickness and hardness of the obtained oxide film on the aluminum surface are described below. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 32 311303 555890

Invention Description (

[Table 11] Hardness (HV) 405 400 411 401 397 401 398 406 410 400 410 401 415 402 402 卞 Θ Dendity 404.0 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economics The minimum hardness 397.0 The maximum hardness 415.0 From comparison table 8 to 11 It can be seen that compared with the embodiment 9_2 of the above-mentioned (A) and (B) device operation of the scope of the present invention patent application, the above-mentioned (A), (B), (C), ( D) In Example 9-1 in which all four devices are operated, even if the anodization is performed at the same temperature and the same time, a film thickness of 2 / 10ths is more uniform, and the Vickers hardness is about 3 / 10ths. The high value indicates the superiority of the fourth item in the scope of patent application. Example 10 is a large-scale example of the combination of (A) and (B) of Example 1. (1) Anodizing bath: made of heat-resistant gasified vinyl resin (700m in width, 1000m in length, 700mm in height) ____ This paper size is applicable to China National Standard (CNS) A4 (210 X 297) 33 311303 -------- Order --------- (Please read the notes on the back before filling this page) 555890 A7

V. Description of the invention (34) (2) Vibration mixer: printed in Figure 1 to 2 by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, printed by Japan Dekenen Co., Ltd., super vibration α _ mixer α _5 type 1. Vibration motor is one ÖLAS vibrator KEE 10_2B type 750W, with DC AC converter (1KW) vibrating blade: effective area 300x 150mm thickness 0.6mm 6 pieces, α = 15. (Only the lower section is downward, the rest is upward.) Amplitude of the vibration blade: 1.5mm (3) Diffuser • Micro-inflator (BM-100) made by Japan Deknen Co., Ltd. The distance between the 3 diffuser tubes ( (Inner diameter: 50mm, outer diameter: 75mm, length: 700mm) Air permeation capacity is 12,000 liters / minute, porosity is 33 to 38%, and porosity is 50 to 60 // m. Volumetric specific gravity: 2 · 2 to 2 · 5 (each) (4) Blowing air pipe: Rotary air pump, i50w output power, 120 liters / min. (5) Anodizing bath ·· Containing liquid volume 420 liters, sulfuric acid 〇〇 Gram / liter, aluminum 4 gram / liter (6) Cathode plate: 10 pieces of aluminum plate (7) Test body · The equivalent of the processed part Cast automotive parts (most bumps) Size '250mmx 750mmx 500mm (8) Cooling heat Exchanger: Cold-lined automatic direct-cooling rapid cooling device 4010 kcal / hour, motor 1.5kw, caliber 25A (Showa Lead Iron Co., Ltd.) (9) Circulating pump for heat exchanger: magnet pump This paper is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) 311303 -------- Order --------- (Please read the precautions on the back first (Fill in this page again) 34 555890 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (35) Maximum flow 120 liters / minute, Max Head 8.6m, 200V output 265W, 1.27A, (Ivac) MD-100 RM) (10) Rectifier: Hi-MiN DC power supply device rated 60V-100A, 6.0kw, AC input 200V, 21.2A, 7.34KTA, Central Manufacturing Co., Ltd. MB7C-600-01 (11) Distance between electrodes: 100mm (12) < Configuration of treatment bath > Degreasing bath—water bath—etching bath—water bath—decontamination bath—water bath—anodic oxidation bath—water bath—sealing treatment bath—drying bath ( Note) Etching bath: caustic 50 g / litre, RT 5 minutes decontamination bath: 5% nitric acid, RT 1 minute sealing treatment bath: ion-exchanged boiling water 30 minutes, current density: 5A / d m2 A uniform anodized film with an average film thickness of 20 / zm can be obtained under the conditions of a bath temperature of 30 ° C, a total air discharge of 120 liters / minute, a vibration flow of 40 Hz, and a processing time of 8 minutes. Scorching occurs when vibrating the flow stirring device (A), and good anodic oxygen cannot be obtained Membrane, and the voltage will increase from 200V to 250V. Example 11 The same type of device as in Example 10 was used, but the following items were changed. (1) Anodizing bath: 700mmx 1000mmx 700mm (high) (2) Test body : LOOmmx 500mmx 300mm (height) (3) Diffuser: BM-100 of Japan Dekenen Co., Ltd., porosity 33 to 38%, porosity 50 to 60 // m, air discharge 120 liters / Points, ------------------- Order --------- ^^^ 1 (Please read the notes on the back before filling this page) This paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 35 311303 555890 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (36) 50m_ (inner diameter) 70m (outside (Obtained), length of 3 mm, air diffuser interval of 120mm, it takes 5 minutes when the temperature of the anodizing bath is 30 ° C and the total air discharge is 120 liters / min. Anodized film with uniform film thickness at any part. When the vibration flow stirring device (A) is not used, if the air ejection amount is more than 60 liters / minute, because the anodized film becomes non-uniform, the air ejection amount cannot be increased further and scorch occurs, and the current density cannot be increased. . [Effects] (1) Compared with the conventional method, according to the present invention, scorching does not occur and a high-speed processing of 3 to 5 times can be realized, which can greatly reduce the processing time of anodization, so it can also save energy. . In addition, if the system in the scope of patent application Nos. 5 to 7 is adopted, the overall processing time can be further shortened. (2) According to the present invention, the Vickers hardness of the anodized film can be greatly improved. (3) According to the present invention, an anodized film with high uniformity can be obtained. Therefore, the present invention is advantageous for manufacturing a photosensitive drum (OPC drum) and the like. (4) Therefore, as long as osmium oxide with the same level of quality is obtained, the temperature of anode oxidation treatment Luo can be 5 to 10 ° C higher than the previous method, and the capacity of the cooler is also small, which is ideal. Specifically, when forming a hard oxide film, the conventional method is -5 ° C to 5 ° C and the present invention is 10 to 15 ° C, which is ideal. Moreover, when forming a general oxide film, the conventional method is about 20 ° C. In the present invention, it is preferably 30 to 35 ° C. ------------ · I ------ Order --------- (Please read the notes on the back before filling out this page) This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) 36 311303 555890 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (37) (5) Even if there are most concavo-convex items or small holes below 10mni ( Through holes or blind holes), even the inside of the recess or small hole can be fully anodized, and a uniform oxide film can be formed in the recess or small hole. Therefore, it is advantageous for anodizing treatment of metal plates with unevenness, anodizing treatment of complicated parts such as engine related parts, heat exchangers. (6) The oxide film obtained according to the present invention is more lustrous and harder than the hafnium oxide obtained at the same processing temperature according to the conventional method, so it has abrasion resistance, corrosion resistance, weather resistance and uniformity of the oxide film. Also high. (7) If the amount of air sprayed during inflation is more than a certain level, the anodic oxide film will become non-uniform, so the amount of sprayed is limited. However, the present invention uses the vibration flow stirring method in combination, so far the limit of the amount of air sprayed It can be greatly increased, and as a result, the temperature of the bath can be further decreased, and the current density can also be increased (8) The dyeability of the oxide film obtained according to the present invention is good. [Brief description of the drawings] Fig. 1 is a side view of a specific example of a device used in item 丨 of the patent application scope of the present invention. Figure 2 is a front view of the device of Figure 1. Figure 3 is a top view of the device of Figure 1. FIG. 4 is a side view of a specific example of the device used in item 4 of the patent application scope of the present invention. Figure 5 is a front view of the device of Figure 4. Figure 6 is a top view of the device of Figure 4. Figure 7 is a sectional view taken along line X-X in Figure 5. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 37 311303 -------------------- Order -------- -(Please read the notes on the back before filling out this page) 555890 A7

V. Description of the invention (38) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 8 is a γ-γ cross-sectional view of Figure 6. Fig. 9 is a sectional view of an enlarged portion of a state where the vibration blade is fixed to the vibrating rod. Fig. 10 is a plan view of an example of a horizontal vibration stirring device. Figure 11 is a sectional view of Figure 10. Fig. 12 is a plan view of another specific example of the device used in the present invention. Figure 13 is a front view of the device of Figure 12. Fig. 14 is a side view of the device of Fig. 12; Fig. 15 is a plan view of an anode and cathode arrangement example. Fig. 16 is a graph showing the relationship between the temperature of the anodizing bath in Example 4 and Comparative Example 4 and the Vickers hardness of the obtained oxide film. Fig. 17 is a flowchart (A) to (D) of the system used in the embodiment of the present invention corresponding to the symbols used in the scope of patent application. Fig. 18 is a method of distinguishing an aluminum plate and a measurement portion. Fig. 19 is a configuration diagram of the air diffuser in a large-scale treatment bath. Fig. 20 is a graph comparing the change of the set current density of the anodizing soft start. Fig. 21 is a side view of the test plate fixing device used in the embodiment. [Explanation of symbols] 1 treatment bath (possibly with pre-treatment bath or post-treatment bath) 2 support frame for shaking 3 swing motor for shaking support frame for swing 4 vibration motor of vibration stirring device ------ ------------- Order --------- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 38 311303 555890 A7 V. Description of the invention (39) 5 7 9 10 11 13 14 16 18 20 22 24 26 28 30 32 33 Anode 6 Sliding electrode support 8 Device bracket sent to the air tube for compression Air inlet heater η Cathode rod support Vibration of shaking support frame Vibration rod vibration blade fixing member Spring lower support frame Screw balancer Electric heater cathode bus bar support Connection portion test plate 34 hanging from anode 6 17 19 21 23 25 27 29 31 Cathode shaker frame 17 19 21 23 25 27 29 31 Dispersion tube motor vibration blade Vibration stress dispersing mechanism Upper support frame Fluoropolymer polymer 臈 Vibration transmission frame Support screw with screw Air compressor anode aluminum wire D I ϋ ϋ ϋ ϋ ί mmte i · — · Ϋ in 1 J, I ϋ (Please read the notes on the back before filling out this page) S-. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, this standard applies to the Zhongguanjia Standard (CNS) A4 Specification (210 X 297 Gongchu311311

Claims (1)

Patent application range 2. 555890 A metal anodizing treatment system and system, characterized in that: (A) is provided with a vibration generating mechanism including a vibration motor in the metal anodizing process, and is linked with the vibration generating mechanism so that One or more sections are fixed on the vibration blades vibrating in the mixing tank, and the vibration flow stirring mechanism that generates vibration flow with an amplitude of 05s30mm and a vibration number of 200 to 800 times / minute is used to control the vibration motor to make it A DC-AC converter capable of arbitrarily vibrating between 10 and 5000; and a vibration flow stirring device for a processing bath, a vibration stress dispersing mechanism provided at a connection portion between the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism, And (B) As an inflation device for the treatment bath, an inflation device using a ceramic diffuser with a pore size of ˜400 to m and a porosity of 30 to 40% operates simultaneously. A metal anodizing treatment system, characterized in that in the metal anodizing process, (A) is provided with: a vibration generating mechanism including a vibration motor; and one or more sections are fixed to be vibrated in a stirring tank in conjunction with the vibration generating mechanism. The vibration blade on the vibrating arm is a vibration flow stirring mechanism that generates vibration flow with an amplitude of 05 to 30 mm and a number of vibrations of 200 to 800 times / minute; it is used to control the vibration motor so that it can reach 10 to 50. DC-to-AC converter for any fish vibration between 0 Hz; and a vibration flow stirring device for a processing bath provided in a vibration stress dispersing mechanism provided at a connection portion between the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism, (B) as a processing bath The air hole used by the inflatable device is based on the paper size and applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I -------- t --------- line (please first (Please read the notes on the back and fill in this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 555890 6. Inflatable device made of ceramic diffuser with a patent scope of 400 vm and a porosity of 30 to 40%. (C) A vibrating motor that is adjusted to 10 to 60 Hz through a DC / AC converter through an electrode rod that hangs the object to be processed, and the object to be processed has an amplitude of 0.5 to 1.0 mm and a vibration number of 100 to 3 The vibration device which vibrates at 00 times / minute operates simultaneously. 3. A metal anodizing treatment system, characterized in that in the metal anodizing process, the thread (A) is provided with a vibration generating mechanism including a vibration motor; and one or more sections are fixed in linkage with the vibration generating mechanism. The vibration blade that is vibrating in the stirring tank is a vibration flow stirring mechanism that generates vibration flow with an amplitude of 05 to 30 mm and a number of vibrations of 200 to 800 times / minute; it is used to control the vibration motor so that A DC-AC converter with arbitrary vibration between 10 and 5000; and a vibration flow stirring device for a treatment bath, a vibration stress dispersing mechanism provided at a connection portion between the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism, (B) As an inflatable device for the treatment bath, the aeration device is a ceramic air diffuser printed to 400 / zm and a porosity of 30 to 40% by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and (C) for transmitting The electrode rod of the object to be processed is hung, and the object to be processed is shaken with a shaking range of 10 to 100 mm and a shaking number of 10 to 30 times per minute. 4. A metal anodizing treatment system, characterized in that during the metal anodizing process, the paper size is adapted to the financial standards (CNS) A4 specification ⑵Q χ as public love) 41 311303 555890 Intellectual Property Bureau staff of the Ministry of Economic Affairs employee consumption Printed by the cooperative A8 B8 C8 D8-~ ------ 6. Scope of patent application (A) Provided: Vibration generating mechanism including vibration motor; Linked with the vibration generating mechanism to fix one or more sections to vibration in the mixing tank The vibrating blade on the vibrating arm is a vibration flow stirring mechanism that generates vibration flow with an amplitude of 05 to 30 mm and a number of vibrations of 200 to 800 times / minute. It is used to control the vibration motor so that it can reach 10 to 50. DC-AC converter with arbitrary vibration between 0Hz; and vibration flow stirring device for the processing bath provided at the vibration stress dispersing mechanism of the connection part of the vibration generating mechanism and the above-mentioned vibration flow stirring mechanism, (B) as the processing bath Inflator using ceramic diffuser with a pore diameter of up to 400 // m and a porosity of 30 to 40%, (C) Electrode rod for hanging the object to be treated A vibration motor adjusted to a frequency of 10 to 60 Hz by a DC / AC converter is used to provide a vibration device having a vibration amplitude of 0.5 to 1.0 mm and a vibration number of 100 to 3,000 times per minute, and ( D) The swinging device for suspending the object to be processed through the electrode rod to give the object to be shaken with a swing width of 10 to 100 mm and a shaking number of 10 to 30 times per minute simultaneously operates. 5. A metal anodizing treatment system, characterized in that in at least one of the metal anodizing step plus the pre-processing step and / or the post-processing step, only the device of (A) is operated, and the above-mentioned ( A), (W devices operate simultaneously, the devices (A), (B), and (C) operate simultaneously, the devices (A), (B), and (D) operate simultaneously or the above ( The devices of A), (B), (C) and (D) operate simultaneously. 11 -------- Order --------- line (please read the precautions on the back before filling in this Page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 42 311303 555890 6. Scope of patent application 6. The metal anodizing treatment system according to item 5 of the scope of patent application, wherein the above-mentioned pre-treatment process and post-treatment process are degreasing processes and polishing processes selected from the group consisting of electrolytic polishing and chemical polishing. Or at least one of the hot water sealing treatment processes. 7. The metal anodizing treatment system according to any one of claims 1 to 6, wherein the object to be processed made of metal is a depression or penetration having the narrowest width of the gap portion or a pore diameter of less than 10 mm Hole. --------------------- Order --------- line (please read the notes on the back and fill in this page) Intellectual Property Bureau of the Ministry of Economic Affairs The paper size printed by the employee consumer cooperative is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 311303 43