JP6691241B2 - Chemical conversion method to reduce undulation of low voltage chemical foil - Google Patents
Chemical conversion method to reduce undulation of low voltage chemical foil Download PDFInfo
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- 239000011888 foil Substances 0.000 title claims description 172
- 239000000126 substance Substances 0.000 title claims description 136
- 238000006243 chemical reaction Methods 0.000 title claims description 112
- 238000000034 method Methods 0.000 title claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 67
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 67
- 239000011976 maleic acid Substances 0.000 claims description 67
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 62
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 47
- 239000001741 Ammonium adipate Substances 0.000 claims description 47
- 235000019293 ammonium adipate Nutrition 0.000 claims description 47
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 230000028161 membrane depolarization Effects 0.000 claims description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 16
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 16
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
- 150000002910 rare earth metals Chemical class 0.000 claims description 16
- 238000005530 etching Methods 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/12—Anodising more than once, e.g. in different baths
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- ing And Chemical Polishing (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Chemical Treatment Of Metals (AREA)
Description
本発明は、低圧用化成箔のアンジュレーションを減軽する化成方法に関する。 TECHNICAL FIELD The present invention relates to a chemical conversion method for reducing the undulation of a low pressure chemical conversion foil.
従来の低圧用アルミニウム電解コンデンサ用の化成箔の製造方法は、電圧によるエッチング箔を濃度３〜１０ｗｔ％アジピン酸アンモニウム溶液に直接入れ、温度が７０℃で、電流密度が５００ｍＡ／ｃｍ２で化成電圧１０Ｖで５〜７ｍｉｎ化成した後、再び同じ溶液条件で化成電圧４０Ｖで５〜７ｍｉｎ化成し、化成電圧８０Ｖを経て７〜１０ｍｉｎ化成し、化成電圧１００Ｖで１５〜２０ｍｉｎ化成し、取り出して水洗し、５ｗｔ％りん酸溶液６０℃によって２〜５ｍｉｎ浸漬して脱分極処理し、取り出して水洗し、修復のために化成槽に入れて化成電圧１００Ｖで５〜７ｍｉｎで一次修復のために化成し、取り出して水洗し、４００〜５００℃で１〜２ｍｉｎ熱処理し、再び修復のために化成槽に入れて化成電圧１００Ｖで二次修復のために化成した後に乾燥して低圧用化成箔を得ることである。このような低圧用化成箔の製造方法による製品の型が波形であるので、下流の裁断に影響し、製品の有効な使用面積が小さくなる。 The conventional method for producing a compound foil for a low voltage aluminum electrolytic capacitor is as follows: the etching foil by voltage is directly put into a solution of ammonium adipate having a concentration of 3 to 10 wt%, the temperature is 70 ° C., the current density is 500 mA / cm 2 , and the compound voltage is 500 mA / cm 2. After forming at 10V for 5 to 7min, forming again at the forming solution voltage of 40V for 5 to 7min under the same solution conditions, forming formation voltage of 80V and forming for 7 to 10min, forming formation voltage of 100V for 15 to 20min, taking out and washing with water, A 5 wt% phosphoric acid solution is soaked in 60 ° C. for 2 to 5 minutes for depolarization treatment, taken out, washed with water, put in a chemical conversion tank for repair, and subjected to chemical conversion voltage of 100 V for 5 to 7 minutes to perform primary repair and take out. Washed with water, heat-treated at 400-500 ° C for 1-2 minutes, put again in the chemical conversion tank for repair, and perform secondary repair at a chemical conversion voltage of 100V. Therefore, it is to obtain a low-pressure formed foil by drying after forming. Since the mold of the product produced by such a method for producing a low-pressure formed foil is corrugated, it affects downstream cutting and reduces the effective use area of the product.
本発明の目的は、上記の局限を克服し、低圧用化成箔のアンジュレーションを減軽し、化成箔の有効な幅を増加して且つ端部の各種指標が優れる化成処理方法を提供することにある。 An object of the present invention is to provide a chemical conversion treatment method which overcomes the above limitations, reduces the undulation of the low-pressure chemical conversion foil, increases the effective width of the chemical conversion foil, and is excellent in various end edge indicators. It is in.
本発明は、
低圧用エッチング箔を０．１〜３０ｗｔ％γ−ブチロラクトンと０．１〜２ｗｔ％マレイン酸混合水溶液に入れ、温度が４０〜６０℃で０．５〜５ｍｉｎ浸漬処理する前処理と、
前処理されたアルミ箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸溶液に、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ２で、電圧が２０〜１７０Ｖの印加電圧の２０％の状態で、陽極を５〜１０ｍｉｎ酸化して第一の化成箔を得る技術的工程と、
第一の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ２で、電圧が印加電圧の４０％の状態で、陽極を５〜１０ｍｉｎ酸化して第二の化成箔を得る技術的工程と、
第二の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸の溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ２で、電圧が印加電圧の６０％の状態で、陽極を５〜１０ｍｉｎ酸化して第三の化成箔を得る技術的工程と、
第三の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸の溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ２で、電圧が印加電圧の８０％の状態で、陽極を５〜１０ｍｉｎ酸化して第四の化成箔を得る技術的工程と、
第四の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸の溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ２で、電圧が印加電圧の１００％の状態で、陽極を５〜１０ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗する技術的工程と、
第五の化成箔を３〜６ｗｔ％りん酸水溶液に入れ、４０〜７０℃で２〜５ｍｉｎ浸漬し、取り出して水洗する脱分極処理と、
脱分極処理後のアルミ箔を０．１〜０．６％リン酸水素ニアンモニウム溶液に入れ、７５〜９０℃、１００％印加電圧で５〜１０ｍｉｎ修復化成し、修復された化成箔を得て、取り出して水洗する一次修復のための化成と、
修復された化成箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が０．１〜５ｗｔ％で、温度が５０〜９０℃で、０．５〜６ｍｉｎ浸漬処理して、中間処理箔を得て、希土無機塩がＬａ（ＮＯ３）３、Ｓｃ（ＮＯ３）３、Ｃｅ（ＮＯ３）３、Ｐｒ（ＮＯ３）３、Ｎｄ（ＮＯ３）３、Ｅｕ（ＮＯ３）３等のうちの一つ又は複数である中間処理と、
中間処理箔を４００〜５５０℃のオーブンに入れ、１〜３ｍｉｎ処理して、熱処理箔を得る熱処理と、
熱処理箔を０．１〜０．６％リン酸水素ニアンモニウム溶液に入れ、７５〜９０℃、１００％の印加電圧で５〜１０ｍｉｎ、修復のために化成し、取り出して水洗し、乾燥して製品を得る二次修復のための化成との技術的工程とを含む、低圧用化成箔のアンジュレーションを減軽する化成方法という技術的手段によって実現される。
The present invention is
A pretreatment in which the low-voltage etching foil is placed in a mixed aqueous solution of 0.1 to 30 wt% γ-butyrolactone and 0.1 to 2 wt% maleic acid, and immersed at a temperature of 40 to 60 ° C. for 0.5 to 5 minutes,
The pretreated aluminum foil was applied to a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid at a temperature of 60 to 80 ° C., a current density of 10 to 100 mA / cm 2 , and a voltage of 20 to 170 V. Under a condition of 20% of the applied voltage of 5), the anode is oxidized for 5 to 10 minutes to obtain a first chemical conversion foil,
The first formed foil is placed in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, the temperature is 60 to 80 ° C., the current density is 10 to 100 mA / cm 2 , and the voltage is the applied voltage. In the state of 40%, a technical process of oxidizing the anode for 5 to 10 minutes to obtain a second chemical conversion foil,
The second chemical conversion foil is placed in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, the temperature is 60 to 80 ° C., the current density is 10 to 100 mA / cm 2 , and the voltage is the applied voltage. In the state of 60% of the above, the technical step of oxidizing the anode for 5 to 10 minutes to obtain the third chemical conversion foil,
The third chemical conversion foil is placed in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, the temperature is 60 to 80 ° C., the current density is 10 to 100 mA / cm 2 , and the voltage is the applied voltage. In the state of 80% of the above, the technical process of oxidizing the anode for 5 to 10 minutes to obtain the fourth chemical conversion foil,
The fourth chemical conversion foil is placed in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, the temperature is 60 to 80 ° C., the current density is 10 to 100 mA / cm 2 , and the voltage is the applied voltage. In the state of 100% of the above, the technical step of oxidizing the anode for 5 to 10 minutes to obtain a fifth chemical conversion foil, taking out and washing with water,
Depolarization treatment in which the fifth chemical conversion foil is placed in a 3 to 6 wt% phosphoric acid aqueous solution, immersed at 40 to 70 ° C. for 2 to 5 minutes, taken out and washed with water,
The aluminum foil after the depolarization treatment was placed in a 0.1-0.6% diammonium hydrogen phosphate solution and subjected to repair chemical formation at 75 to 90 ° C. and 100% applied voltage for 5 to 10 minutes to obtain a restored chemical foil. , Take out and wash with water for the primary restoration,
The restored chemical foil is put into a rare earth inorganic salt solution having a crystal grain refining effect, and the concentration is 0.1 to 5 wt%, the temperature is 50 to 90 ° C., and the dipping treatment is performed for 0.5 to 6 minutes. An intermediate treated foil is obtained, and the rare earth inorganic salt is La (NO 3 ) 3 , Sc (NO 3 ) 3 , Ce (NO 3 ) 3 , Pr (NO 3 ) 3 , Nd (NO 3 ) 3 , Eu (NO). 3 ) an intermediate process which is one or more of 3 and the like;
Put the intermediate treated foil in an oven at 400 to 550 ° C., treat it for 1 to 3 minutes to obtain a heat treated foil, and
The heat-treated foil is put in a 0.1-0.6% diammonium hydrogen phosphate solution, formed for restoration at 75-90 ° C. and 100% applied voltage for 5-10 min, taken out, washed with water, and dried. It is realized by the technical means of a chemical conversion method for reducing the undulation of the low-voltage chemical conversion foil, which includes a technical step of chemical conversion for secondary restoration to obtain a product.
上記のことをまとめると、本発明は、低圧用化成箔のアンジュレーションを減軽し、化成箔の有効な幅を増加して且つ端部の各種指標が優れ、製品の端部がより平らで利用率が高く、中央部とのばらつきが小さく、製品の均一性を高めるというメリットを有する。 Summarizing the above, the present invention reduces the undulation of the low-pressure forming foil, increases the effective width of the forming foil and is excellent in various indicators of the end, and the end of the product is flatter. It has the advantages of high utilization rate, small variation from the center, and improved product uniformity.
本発明に対する理解を深めるために、以下、実施例を組み合わせて本発明を一層詳しく説明し、当該実施例は、本発明を解釈するためのものだけで、本発明の保護範囲を限定するものではない。 In order to deepen the understanding of the present invention, the present invention will be described in more detail in combination with examples below, and the examples are only for interpreting the present invention and do not limit the protection scope of the present invention. Absent.
実施例１：前処理：低圧用エッチング箔を５ｗｔ％γ−ブチロラクトンと０．２ｗｔ％マレイン酸混合水溶液に入れ、温度が４０℃で５ｍｉｎ浸漬処理する。前処理されたアルミ箔を７ｗｔ％アジピン酸アンモニウムと０．０５ｗｔ％マレイン酸溶液に、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が５ｖで、陽極を５ｍｉｎ酸化して第一の化成箔を得る。第一の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０５ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が１０ｖで、陽極を５ｍｉｎ酸化して第二の化成箔を得る。第二の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０５ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が１５ｖで、陽極を５ｍｉｎ酸化して第三の化成箔を得る。第三の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が２０ｖで、陽極を５ｍｉｎ酸化して第四の化成箔を得る。第四の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が２５ｖで、陽極を１５ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗する。脱分極処理：第五の化成箔を６ｗｔ％りん酸水溶液に入れ、４０℃で３ｍｉｎ浸漬し、取り出して水洗する。一次修復のための化成：脱分極処理後のアルミ箔を０．１％リン酸水素ニアンモニウム溶液に入れ、８０℃、２５ｖ電圧で５ｍｉｎ、修復のために化成し、修復された化成箔を得て、取り出して水洗する。中間処理：修復された化成箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が０．１ｗｔ％で温度が５０℃で６ｍｉｎ浸漬処理して、中間処理箔を得る。ここで、希土無機塩はＬａ（ＮＯ３）３、Ｓｃ（ＮＯ３）３、Ｃｅ（ＮＯ３）３、Ｐｒ（ＮＯ３）３、Ｎｄ（ＮＯ３）３、Ｅｕ（ＮＯ３）３等のうちの一つ又は複数である。熱処理：中間処理箔を４００℃のオーブンに入れ、３ｍｉｎ処理して、熱処理箔を得る。二次修復のための化成：熱処理箔を０．１％リン酸水素ニアンモニウム溶液に入れ、８０℃、２５ｖ電圧で５ｍｉｎ、修復のために化成する。取り出して水洗し、乾燥して製品を得る。 Example 1: Pretreatment: An etching foil for low pressure is placed in a mixed aqueous solution of 5 wt% γ-butyrolactone and 0.2 wt% maleic acid, and immersed at a temperature of 40 ° C for 5 minutes. A preformed aluminum foil was oxidized with a 7 wt% ammonium adipate and a 0.05 wt% maleic acid solution at a temperature of 70 ° C., a current density of 20 mA / cm 2 , a voltage of 5 v, and an anode for 5 min to oxidize the first formed foil. To get The first formed foil was placed in a 7 wt% ammonium adipate and 0.05 wt% maleic acid solution, and the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 10 v, and the anode was oxidized for 5 minutes to form the second formed foil. To get The second formed foil was placed in a 7 wt% ammonium adipate and 0.05 wt% maleic acid solution, and the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 15 v, and the anode was oxidized for 5 min. To get The third chemical conversion foil was placed in a 7 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 20 v, and the anode was oxidized for 5 min to obtain the fourth chemical conversion foil. To get The fourth chemical conversion foil was placed in a 7 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 25 v, and the anode was oxidized for 15 min to form the fifth chemical conversion foil. Obtain, take out and wash with water. Depolarization treatment: The fifth chemical conversion foil is put in a 6 wt% phosphoric acid aqueous solution, immersed at 40 ° C. for 3 minutes, taken out, and washed with water. Chemical conversion for primary repair: The aluminum foil after the depolarization treatment is placed in a 0.1% diammonium hydrogen phosphate solution, and chemical conversion is performed for 5 minutes at a temperature of 25 ° C. and a voltage of 25 v to obtain a modified chemical foil. Remove and wash with water. Intermediate treatment: The restored chemical conversion foil is put into a rare earth inorganic salt solution having a crystal grain refining effect, and subjected to immersion treatment at a concentration of 0.1 wt% at a temperature of 50 ° C. for 6 minutes to obtain an intermediate treatment foil. Here, rare earth inorganic salt La (NO 3) 3, Sc (NO 3) 3, Ce (NO 3) 3, Pr (NO 3) 3, Nd (NO 3) 3, Eu (NO 3) 3 , etc. One or more of these. Heat treatment: The intermediate treated foil is placed in an oven at 400 ° C. and treated for 3 minutes to obtain a heat treated foil. Chemical formation for secondary repair: The heat-treated foil is put in a 0.1% diammonium hydrogen phosphate solution and subjected to chemical formation for repair at 80 ° C. and 25 V voltage for 5 minutes. It is taken out, washed with water and dried to obtain the product.
実施例２：前処理：低圧用エッチング箔を１５ｗｔ％γ−ブチロラクトンと１ｗｔ％マレイン酸混合水溶液に入れ、温度が５０℃で３ｍｉｎ浸漬処理する。前処理されたアルミ箔を１０ｗｔ％アジピン酸アンモニウムと０．１ｗｔ％マレイン酸溶液に、温度６０℃、電流密度５０ｍＡ／ｃｍ２で、電圧が１０ｖで、陽極を７ｍｉｎ酸化して第一の化成箔を得る。第一の化成箔を１０ｗｔ％アジピン酸アンモニウムと０．１ｗｔ％マレイン酸溶液に入れ、温度６０℃、電流密度５０ｍＡ／ｃｍ２で、電圧が２０ｖで、陽極を７ｍｉｎ酸化して第二の化成箔を得る。第二の化成箔を１０ｗｔ％アジピン酸アンモニウムと０．１ｗｔ％マレイン酸溶液に入れ、温度６０℃、電流密度５０ｍＡ／ｃｍ２で、電圧が３０ｖで、陽極を７ｍｉｎ酸化して第三の化成箔を得る。第三の化成箔を１０ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度６０℃、電流密度５０ｍＡ／ｃｍ２で、電圧が４０ｖで、陽極を７ｍｉｎ酸化して第四の化成箔を得る。第四の化成箔を１０ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度６０℃、電流密度５０ｍＡ／ｃｍ２で、電圧が５０ｖで、陽極を２０ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗する。脱分極処理：第五の化成箔を３ｗｔ％りん酸水溶液に入れ、７０℃で５ｍｉｎ浸漬し、取り出して水洗する。一次修復のための化成：脱分極処理後のアルミ箔を０．３％リン酸水素ニアンモニウム溶液に入れ、８５℃、５０ｖ電圧で７ｍｉｎ、修復のために化成し、修復された化成箔を得て、取り出して水洗する。中間処理：修復された化成箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が３ｗｔ％で温度が７０℃で３ｍｉｎ浸漬処理して、中間処理箔を得る。ここで、希土無機塩はＬａ（ＮＯ３）３、Ｓｃ（ＮＯ３）３、Ｃｅ（ＮＯ３）３、Ｐｒ（ＮＯ３）３、Ｎｄ（ＮＯ３）３、Ｅｕ（ＮＯ３）３等のうちの一つ又は複数である。熱処理：中間処理箔を４８０℃のオーブンに入れ、２ｍｉｎ処理して、熱処理箔を得る。二次修復のための化成：熱処理箔を０．３％リン酸水素ニアンモニウム溶液に入れ、８５℃、５０ｖ電圧で７ｍｉｎ、修復のために化成し、取り出して水洗し、乾燥して製品を得る。 Example 2: Pretreatment: An etching foil for low pressure is placed in a mixed solution of 15 wt% γ-butyrolactone and 1 wt% maleic acid, and immersed at a temperature of 50 ° C for 3 minutes. The pre-treated aluminum foil was oxidized with a 10 wt% ammonium adipate and 0.1 wt% maleic acid solution at a temperature of 60 ° C., a current density of 50 mA / cm 2 , a voltage of 10 v, and the anode was oxidized for 7 min to form a first formed foil. To get The first formed foil was placed in a 10 wt% ammonium adipate and 0.1 wt% maleic acid solution, the temperature was 60 ° C., the current density was 50 mA / cm 2 , the voltage was 20 v, and the anode was oxidized for 7 min to form the second formed foil. To get The second formed foil was placed in a 10 wt% ammonium adipate and 0.1 wt% maleic acid solution, the temperature was 60 ° C., the current density was 50 mA / cm 2 , the voltage was 30 v, and the anode was oxidized for 7 min. To get The third chemical conversion foil was put into a 10 wt% ammonium adipate and 0.01 wt% maleic acid solution, and the temperature was 60 ° C., the current density was 50 mA / cm 2 , the voltage was 40 v, and the anode was oxidized for 7 min to form the fourth chemical conversion foil. To get The fourth chemical conversion foil was placed in a 10 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 60 ° C., the current density was 50 mA / cm 2 , the voltage was 50 v, and the anode was oxidized for 20 min to form the fifth chemical conversion foil. Obtain, take out and wash with water. Depolarization treatment: The fifth chemical conversion foil is put into a 3 wt% phosphoric acid aqueous solution, immersed at 70 ° C. for 5 minutes, taken out, and washed with water. Chemical conversion for primary repair: The aluminum foil after the depolarization treatment was placed in a 0.3% diammonium hydrogen phosphate solution, and chemical conversion was performed for 7 minutes at 85 ° C. and a voltage of 50 v to obtain a repaired chemical foil. Remove and wash with water. Intermediate treatment: The restored chemical conversion foil is put into a rare earth inorganic salt solution having a crystal grain refining effect, and subjected to immersion treatment at a concentration of 3 wt% and a temperature of 70 ° C. for 3 minutes to obtain an intermediate treatment foil. Here, rare earth inorganic salt La (NO 3) 3, Sc (NO 3) 3, Ce (NO 3) 3, Pr (NO 3) 3, Nd (NO 3) 3, Eu (NO 3) 3 , etc. One or more of these. Heat treatment: The intermediate treated foil is placed in an oven at 480 ° C. and treated for 2 minutes to obtain a heat treated foil. Chemical conversion for secondary repair: Put the heat-treated foil in a 0.3% diammonium hydrogen phosphate solution, perform chemical conversion for repair for 7 minutes at 85 ° C and 50v voltage, take out, wash with water and dry to obtain the product. .
実施例３：前処理：低圧用エッチング箔を３０ｗｔ％γ−ブチロラクトンと２ｗｔ％マレイン酸混合水溶液に入れ、温度が６０℃で１ｍｉｎ浸漬処理する。前処理されたアルミ箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が２０ｖで、陽極を１０ｍｉｎ酸化して第一の化成箔を得る。第一の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が４０ｖで、陽極を１０ｍｉｎ酸化して第二の化成箔を得る。第二の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が６０ｖで、陽極を１０ｍｉｎ酸化して第三の化成箔を得る。第三の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が８０ｖで、陽極を１０ｍｉｎ酸化して第四の化成箔を得る。第四の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が１００ｖで、陽極を３０ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗する。脱分極処理：第五の化成箔を５ｗｔ％りん酸水溶液に入れ、５５℃で２ｍｉｎ浸漬し、取り出して水洗する。一次修復のための化成：脱分極処理後のアルミ箔を０．６％リン酸水素ニアンモニウム溶液に入れ、９０℃、１００ｖ電圧で１０ｍｉｎ、修復のために化成して、修復された化成箔を得て、取り出して水洗する。中間処理：修復された化成箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が５ｗｔ％で温度が９０℃で０．５ｍｉｎ浸漬処理して、中間処理箔を得る。ここで、希土無機塩はＬａ（ＮＯ３）３、Ｓｃ（ＮＯ３）３、Ｃｅ（ＮＯ３）３、Ｐｒ（ＮＯ３）３、Ｎｄ（ＮＯ３）３、Ｅｕ（ＮＯ３）３等のうちの一つ又は複数である。熱処理：中間処理箔を５５０℃のオーブンに入れ、１ｍｉｎ処理して、熱処理箔を得る。二次修復のための化成：熱処理箔を０．６％リン酸水素ニアンモニウム溶液に入れ、９０℃、１００ｖ電圧で１０ｍｉｎ、修復のために化成して、取り出して水洗し、乾燥して製品を得る。 Example 3: Pretreatment: A low-pressure etching foil is put in a mixed aqueous solution of 30 wt% γ-butyrolactone and 2 wt% maleic acid, and immersed at a temperature of 60 ° C for 1 min. The pretreated aluminum foil was placed in a 15 wt% ammonium adipate and 0.5 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 20 v, and the anode was oxidized for 10 min to perform the first chemical conversion. Get the foil. The first formed foil was placed in a 15 wt% ammonium adipate and 0.5 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 40 v, and the anode was oxidized for 10 min to form the second formed foil. To get The second formed foil was placed in a solution of 15 wt% ammonium adipate and 0.5 wt% maleic acid, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 60 v, and the anode was oxidized for 10 min. To get The third chemical conversion foil was placed in a 15 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 80 v, and the anode was oxidized for 10 min to form the fourth chemical conversion foil. To get The fourth chemical conversion foil was put in a 15 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 100 v, and the anode was oxidized for 30 minutes to obtain the fifth chemical conversion foil. Obtain, take out and wash with water. Depolarization treatment: The fifth chemical conversion foil is put in a 5 wt% phosphoric acid aqueous solution, immersed at 55 ° C. for 2 minutes, taken out, and washed with water. Chemical formation for primary repair: The aluminum foil after depolarization treatment was placed in a 0.6% diammonium hydrogen phosphate solution and subjected to chemical formation for repair for 10 minutes at 90 ° C. and 100 v voltage to give the repaired chemical foil. Obtained, taken out and washed with water. Intermediate treatment: The restored chemical conversion foil is put into a rare earth inorganic salt solution having a crystal grain refining effect, and subjected to immersion treatment at a concentration of 5 wt% and a temperature of 90 ° C. for 0.5 min to obtain an intermediate treatment foil. Here, rare earth inorganic salt La (NO 3) 3, Sc (NO 3) 3, Ce (NO 3) 3, Pr (NO 3) 3, Nd (NO 3) 3, Eu (NO 3) 3 , etc. One or more of these. Heat treatment: The intermediate treated foil is placed in an oven at 550 ° C. and treated for 1 min to obtain a heat treated foil. Chemical conversion for secondary repair: Put the heat-treated foil in 0.6% diammonium hydrogen phosphate solution, perform chemical conversion for repair for 10 min at 90 ° C and 100v voltage, take out, wash with water, and dry the product. obtain.
実施例４：前処理：低圧用エッチング箔を３ｗｔ％γ−ブチロラクトンと０．１ｗｔ％マレイン酸混合水溶液に入れ、温度が４０℃で５ｍｉｎ浸漬処理する。前処理されたアルミ箔を７ｗｔ％アジピン酸アンモニウムと０．０５ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が５ｖで、陽極を５ｍｉｎ酸化して第一の化成箔を得る。第一の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０５ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２、電圧が１０ｖで、陽極を５ｍｉｎ酸化して第二の化成箔を得る。第二の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０５ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が１５ｖで、陽極を５ｍｉｎ酸化して第三の化成箔を得る。第三の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が２０ｖで、陽極を５ｍｉｎ酸化して第四の化成箔を得る。第四の化成箔を７ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度７０℃、電流密度２０ｍＡ／ｃｍ２で、電圧が２５ｖで、陽極を１５ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗する。脱分極処理：第五の化成箔を６ｗｔ％りん酸水溶液に入れ、４０℃で３ｍｉｎ浸漬して、取り出して水洗する。一次修復のための化成：脱分極処理後のアルミ箔を０．１％リン酸水素ニアンモニウム溶液に入れ、８０℃、２５ｖ電圧で５ｍｉｎ、修復のために化成して、修復された化成箔を得て、取り出して水洗する。中間処理：修復された化成箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が０．１ｗｔ％で温度が５０℃で６ｍｉｎ浸漬処理して、中間処理箔を得る。ここで、希土無機塩はＬａ（ＮＯ３）３、Ｓｃ（ＮＯ３）３、Ｃｅ（ＮＯ３）３、Ｐｒ（ＮＯ３）３、Ｎｄ（ＮＯ３）３、Ｅｕ（ＮＯ３）３等のうちの一つ又は複数である。熱処理：中間処理箔を４００℃のオーブンに入れ、３ｍｉｎ処理して、熱処理箔を得る。二次修復のための化成：熱処理箔を０．１％リン酸水素ニアンモニウム溶液に入れ、８０℃、２５ｖ電圧で５ｍｉｎ、修復のために化成する。取り出して水洗し、乾燥して製品を得る。 Example 4: Pretreatment: A low-pressure etching foil is placed in a mixed aqueous solution of 3 wt% γ-butyrolactone and 0.1 wt% maleic acid, and immersed at a temperature of 40 ° C for 5 minutes. The pretreated aluminum foil was placed in a 7 wt% ammonium adipate and 0.05 wt% maleic acid solution, the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 5 v, and the anode was oxidized for 5 min to perform the first chemical conversion. Get the foil. The first formed foil was placed in a 7 wt% ammonium adipate and 0.05 wt% maleic acid solution, and the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 10 v, and the anode was oxidized for 5 min to form the second formed foil. obtain. The second formed foil was placed in a 7 wt% ammonium adipate and 0.05 wt% maleic acid solution, and the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 15 v, and the anode was oxidized for 5 min. To get The third chemical conversion foil was placed in a 7 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 20 v, and the anode was oxidized for 5 min to obtain the fourth chemical conversion foil. To get The fourth chemical conversion foil was placed in a 7 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 70 ° C., the current density was 20 mA / cm 2 , the voltage was 25 v, and the anode was oxidized for 15 min to form the fifth chemical conversion foil. Obtain, take out and wash with water. Depolarization treatment: The fifth chemical conversion foil is put in a 6 wt% phosphoric acid aqueous solution, immersed at 40 ° C. for 3 minutes, taken out, and washed with water. Chemical formation for primary repair: The aluminum foil after the depolarization treatment was placed in a 0.1% diammonium hydrogen phosphate solution and subjected to chemical formation for repair at 80 ° C. and 25v voltage for 5 min to give the repaired chemical foil. Obtained, taken out and washed with water. Intermediate treatment: The restored chemical conversion foil is put into a rare earth inorganic salt solution having a crystal grain refining effect, and subjected to immersion treatment at a concentration of 0.1 wt% at a temperature of 50 ° C. for 6 minutes to obtain an intermediate treatment foil. Here, rare earth inorganic salt La (NO 3) 3, Sc (NO 3) 3, Ce (NO 3) 3, Pr (NO 3) 3, Nd (NO 3) 3, Eu (NO 3) 3 , etc. One or more of these. Heat treatment: The intermediate treated foil is placed in an oven at 400 ° C. and treated for 3 minutes to obtain a heat treated foil. Chemical formation for secondary repair: The heat-treated foil is put in a 0.1% diammonium hydrogen phosphate solution and subjected to chemical formation for repair at 80 ° C. and 25 V voltage for 5 minutes. It is taken out, washed with water and dried to obtain the product.
実施例５：前処理：低圧用エッチング箔を１０ｗｔ％γ−ブチロラクトンと０．６ｗｔ％マレイン酸混合水溶液に入れ、温度が７０℃で１ｍｉｎ浸漬処理する。前処理されたアルミ箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が２０ｖで、陽極を１０ｍｉｎ酸化して第一の化成箔を得る。第一の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が４０ｖで、陽極を１０ｍｉｎ酸化して第二の化成箔を得る。第二の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が６０ｖで、陽極を１０ｍｉｎ酸化して第三の化成箔を得る。第三の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が８０ｖで、陽極を１０ｍｉｎ酸化して第四の化成箔を得る。第四の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が１００ｖで、陽極を３０ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗する。脱分極処理：第五の化成箔を５ｗｔ％りん酸水溶液に入れ、５５℃で２ｍｉｎ浸漬し、取り出して水洗する。一次修復のための化成：脱分極処理後のアルミ箔を０．６％リン酸水素ニアンモニウム溶液に入れ、９０℃、１００ｖ電圧で１０ｍｉｎ、修復のために化成して、修復された化成箔を得て、取り出して水洗する。中間処理：修復された化成箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が５ｗｔ％で温度が９０℃で０．５ｍｉｎ浸漬処理し、中間処理箔を得る。ここで、希土無機塩はＬａ（ＮＯ３）３、Ｓｃ（ＮＯ３）３、Ｃｅ（ＮＯ３）３、Ｐｒ（ＮＯ３）３、Ｎｄ（ＮＯ３）３、Ｅｕ（ＮＯ３）３等のうちの一つ又は複数である。熱処理：中間処理箔を５５０℃のオーブンに入れ、１ｍｉｎ処理して、熱処理箔を得る。二次修復のための化成：熱処理箔を０．６％リン酸水素ニアンモニウム溶液に入れ、９０℃、１００ｖ電圧で１０ｍｉｎ、修復のために化成して、取り出して水洗し、乾燥して製品を得る。 Example 5: Pretreatment: A low-pressure etching foil is placed in a mixed aqueous solution of 10 wt% γ-butyrolactone and 0.6 wt% maleic acid, and immersed at 70 ° C. for 1 min. The pretreated aluminum foil was placed in a 15 wt% ammonium adipate and 0.5 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 20 v, and the anode was oxidized for 10 min to perform the first chemical conversion. Get the foil. The first formed foil was placed in a 15 wt% ammonium adipate and 0.5 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 40 v, and the anode was oxidized for 10 min to form the second formed foil. To get The second formed foil was placed in a solution of 15 wt% ammonium adipate and 0.5 wt% maleic acid, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 60 v, and the anode was oxidized for 10 min. To get The third chemical conversion foil was placed in a 15 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 80 v, and the anode was oxidized for 10 min to form the fourth chemical conversion foil. To get The fourth chemical conversion foil was put in a 15 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 100 v, and the anode was oxidized for 30 minutes to obtain the fifth chemical conversion foil. Obtain, take out and wash with water. Depolarization treatment: The fifth chemical conversion foil is put in a 5 wt% phosphoric acid aqueous solution, immersed at 55 ° C. for 2 minutes, taken out, and washed with water. Chemical formation for primary repair: The aluminum foil after depolarization treatment was placed in a 0.6% diammonium hydrogen phosphate solution and subjected to chemical formation for repair for 10 minutes at 90 ° C. and 100 v voltage to give the repaired chemical foil. Obtained, taken out and washed with water. Intermediate treatment: The restored chemical conversion foil is put into a rare earth inorganic salt solution having a crystal grain refining effect, and subjected to immersion treatment at a concentration of 5 wt% and a temperature of 90 ° C. for 0.5 min to obtain an intermediate treatment foil. Here, rare earth inorganic salt La (NO 3) 3, Sc (NO 3) 3, Ce (NO 3) 3, Pr (NO 3) 3, Nd (NO 3) 3, Eu (NO 3) 3 , etc. One or more of these. Heat treatment: The intermediate treated foil is placed in an oven at 550 ° C. and treated for 1 min to obtain a heat treated foil. Chemical conversion for secondary repair: Put the heat-treated foil in 0.6% diammonium hydrogen phosphate solution, perform chemical conversion for repair for 10 min at 90 ° C and 100v voltage, take out, wash with water, and dry the product. obtain.
実施例６：前処理：低圧用エッチング箔を３０ｗｔ％γ−ブチロラクトンと１ｗｔ％マレイン酸混合水溶液に入れ、温度が６０℃で１ｍｉｎ浸漬処理する。前処理されたアルミ箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が２０ｖで、陽極を１０ｍｉｎ酸化して第一の化成箔を得る。第一の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が４０ｖで、陽極を１０ｍｉｎ酸化して第二の化成箔を得る。第二の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．５ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が６０ｖで、陽極を１０ｍｉｎ酸化して第三の化成箔を得る。第三の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が８０ｖで、陽極を１０ｍｉｎ酸化して第四の化成箔を得る。第四の化成箔を１５ｗｔ％アジピン酸アンモニウムと０．０１ｗｔ％マレイン酸溶液に入れ、温度８０℃、電流密度１００ｍＡ／ｃｍ２で、電圧が１００ｖで、陽極を３０ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗する。脱分極処理：第五の化成箔を５ｗｔ％りん酸水溶液に入れ、５５℃で２ｍｉｎ浸漬して、取り出して水洗する。一次修復のための化成：脱分極処理後のアルミ箔を０．６％リン酸水素ニアンモニウム溶液に入れ、９０℃、１００ｖ電圧で１０ｍｉｎ、修復のために化成して、修復された化成箔を得て、取り出して水洗する。中間処理：修復された化成箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が５ｗｔ％で温度が９０℃で０．５ｍｉｎ浸漬処理して、中間処理箔を得る。ここで、希土無機塩はＬａ（ＮＯ３）３、Ｓｃ（ＮＯ３）３、Ｃｅ（ＮＯ３）３、Ｐｒ（ＮＯ３）３、Ｎｄ（ＮＯ３）３、Ｅｕ（ＮＯ３）３等のうちの一つ又は複数である。熱処理：中間処理箔を５５０℃のオーブンに入れ、１ｍｉｎ処理して、熱処理箔を得る。二次修復化成：熱処理箔を０．６％リン酸水素ニアンモニウム溶液に入れ、９０℃、１００ｖ電圧で１０ｍｉｎ修復化成して、取り出して水洗し、乾燥して製品を得る。 Example 6: Pretreatment: An etching foil for low pressure is placed in a mixed aqueous solution of 30 wt% γ-butyrolactone and 1 wt% maleic acid, and immersed at a temperature of 60 ° C for 1 min. The pretreated aluminum foil was placed in a 15 wt% ammonium adipate and 0.5 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 20 v, and the anode was oxidized for 10 min to perform the first chemical conversion. Get the foil. The first formed foil was placed in a 15 wt% ammonium adipate and 0.5 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 40 v, and the anode was oxidized for 10 min to form the second formed foil. To get The second formed foil was placed in a solution of 15 wt% ammonium adipate and 0.5 wt% maleic acid, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 60 v, and the anode was oxidized for 10 min. To get The third chemical conversion foil was placed in a 15 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 80 v, and the anode was oxidized for 10 min to form the fourth chemical conversion foil. To get The fourth chemical conversion foil was placed in a 15 wt% ammonium adipate and 0.01 wt% maleic acid solution, the temperature was 80 ° C., the current density was 100 mA / cm 2 , the voltage was 100 v, and the anode was oxidized for 30 min to form the fifth chemical conversion foil. Obtain, take out and wash with water. Depolarization treatment: The fifth chemical conversion foil is put in a 5 wt% phosphoric acid aqueous solution, immersed at 55 ° C. for 2 minutes, taken out, and washed with water. Chemical conversion for primary repair: The aluminum foil after the depolarization treatment was placed in a 0.6% diammonium hydrogen phosphate solution, and chemical conversion was performed for 10 minutes at 90 ° C. and a voltage of 100 v for 10 minutes to recover the recovered chemical foil. Obtained, taken out and washed with water. Intermediate treatment: The restored chemical conversion foil is put in a rare earth inorganic salt solution having a crystal grain refining effect, and subjected to immersion treatment at a concentration of 5 wt% and a temperature of 90 ° C. for 0.5 min to obtain an intermediate treatment foil. Here, the rare earth inorganic salt is La (NO 3 ) 3 , Sc (NO 3 ) 3 , Ce (NO 3 ) 3 , Pr (NO 3 ) 3 , Nd (NO 3 ) 3 , Eu (NO 3 ) 3, etc. One or more of these. Heat treatment: The intermediate treated foil is placed in an oven at 550 ° C. and treated for 1 min to obtain a heat treated foil. Secondary restoration formation: The heat-treated foil is placed in a 0.6% diammonium hydrogen phosphate solution, subjected to restoration formation at 90 ° C. and a voltage of 100 v for 10 minutes, taken out, washed with water, and dried to obtain a product.
表１は、実施例１−６による化成箔の全幅５点における嵩密度ばらつき表である。
Table 1 is a bulk density variation table of the chemical conversion foil according to Example 1-6 at 5 points in total width.
Claims (8)
前記前処理の工程は、γ−ブチロラクトンとマレイン酸の混合水溶液で浸漬処理を行い、具体的には、低圧用エッチング箔を０．１〜３０ｗｔ％γ−ブチロラクトンと０．１〜２ｗｔ％マレイン酸の混合水溶液に入れ、温度が４０〜６０℃で０．５〜５ｍｉｎ浸漬処理することであり、
前処理されたアルミ箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸溶液で、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ ２ で、電圧が２０〜１７０Ｖである印加電圧の２０％の状態で、陽極が５〜１０ｍｉｎ酸化して第一の化成箔を得て、
前記五段階化成処理は、第一の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸の溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ ２ で、電圧が印加電圧の４０％の状態で、陽極を５〜１０ｍｉｎ酸化して第二の化成箔を得て、
第二の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸の溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ ２ で、電圧が印加電圧の６０％の状態で、陽極を５〜１０ｍｉｎ酸化して第三の化成箔を得て、
第三の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸の溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ ２ で、電圧が印加電圧の８０％の状態で、陽極を５〜１０ｍｉｎ酸化して第四の化成箔を得て、
第四の化成箔を３〜１５ｗｔ％アジピン酸アンモニウムと０．０１〜０．５ｗｔ％マレイン酸の溶液に入れ、温度６０〜８０℃で、電流密度１０〜１００ｍＡ／ｃｍ ２ で、電圧が印加電圧の１００％の状態で、陽極を５〜１０ｍｉｎ酸化して第五の化成箔を得て、取り出して水洗することであり、
前記脱分極処理は、第五の化成箔を３〜６ｗｔ％りん酸水溶液に入れ、４０〜７０℃で２〜５ｍｉｎ浸漬し、取り出して水洗することであり、
前記一次修復のための化成は、脱分極処理後のアルミ箔を０．１〜０．６％リン酸水素ニアンモニウム溶液に入れ、７５〜９０℃、１００％印加電圧で５〜１０ｍｉｎ、修復のために化成し、修復された化成箔を得て、取り出して水洗することであり、
前記中間処理工程は、一次修復のための化成処理後のアルミ箔を結晶粒子の微細化作用を有する希土無機塩溶液に入れ、濃度が０．１〜５ｗｔ％で、温度が５０〜９０℃で、０．５〜６ｍｉｎ浸漬処理することであり、
前記熱処理は中間処理箔を４００〜５５０℃のオーブンに入れ、１〜３ｍｉｎ処理し、熱処理箔を得ることであり、
前記二次修復のための化成は、熱処理箔を０．１〜０．６％リン酸水素ニアンモニウム溶液に入れ、７５〜９０℃、１００％印加電圧で５〜１０ｍｉｎ修復化成し、取り出して水洗し、乾燥して製品を得ることである、低圧用化成箔のアンジュレーションを減軽する化成方法。 For low pressure where the process flow is pretreatment, five-step chemical conversion treatment, water washing, depolarization treatment, water washing, chemical conversion treatment for primary restoration, water washing, intermediate treatment, heat treatment, chemical conversion treatment and drying treatment for secondary restoration A chemical conversion method for reducing the undulation of the chemical conversion foil,
In the pretreatment step, a dipping treatment is performed with a mixed aqueous solution of γ-butyrolactone and maleic acid. Specifically, the etching foil for low pressure is 0.1 to 30 wt% γ-butyrolactone and 0.1 to 2 wt% maleic acid. Is placed in a mixed aqueous solution of and is subjected to immersion treatment at a temperature of 40 to 60 ° C. for 0.5 to 5 minutes,
The pretreated aluminum foil was treated with 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid solution at a temperature of 60 to 80 ° C., a current density of 10 to 100 mA / cm 2 , and a voltage of 20 to 170 V. With the applied voltage being 20%, the anode is oxidized for 5 to 10 minutes to obtain the first chemical conversion foil,
In the five-step chemical conversion treatment, the first chemical conversion foil was put in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, and the temperature was 60 to 80 ° C. and the current density was 10 to 100 mA / cm 2. In 2 , the voltage is 40% of the applied voltage, the anode is oxidized for 5 to 10 minutes to obtain a second chemical conversion foil,
The second chemical conversion foil is placed in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, the temperature is 60 to 80 ° C., the current density is 10 to 100 mA / cm 2 , and the voltage is the applied voltage. In the state of 60% of the above, the anode is oxidized for 5 to 10 minutes to obtain a third chemical conversion foil,
The third chemical conversion foil is placed in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, the temperature is 60 to 80 ° C., the current density is 10 to 100 mA / cm 2 , and the voltage is the applied voltage. In the state of 80% of the above, the anode is oxidized for 5 to 10 minutes to obtain a fourth chemical conversion foil,
The fourth chemical conversion foil is placed in a solution of 3 to 15 wt% ammonium adipate and 0.01 to 0.5 wt% maleic acid, the temperature is 60 to 80 ° C., the current density is 10 to 100 mA / cm 2 , and the voltage is the applied voltage. In the state of 100% of the above, the anode is oxidized for 5 to 10 minutes to obtain a fifth chemical conversion foil, which is taken out and washed with water.
The depolarization treatment is to put the fifth chemical conversion foil in a 3 to 6 wt% phosphoric acid aqueous solution, immerse it at 40 to 70 ° C. for 2 to 5 minutes, take it out and wash it with water.
The formation for the primary repair is carried out by putting the aluminum foil after the depolarization treatment in a 0.1-0.6% diammonium hydrogen phosphate solution, and performing the repair for 5-10 min at 75-90 ° C. and 100% applied voltage. In order to obtain a restored formed foil, it is taken out and washed with water.
In the intermediate treatment step, the aluminum foil after the chemical conversion treatment for the primary restoration is put into a rare earth inorganic salt solution having a crystal grain refining effect, the concentration is 0.1 to 5 wt% and the temperature is 50 to 90 ° C. Then, it is a dipping treatment for 0.5 to 6 minutes,
The heat treatment is to put the intermediate treated foil in an oven at 400 to 550 ° C. and treat it for 1 to 3 minutes to obtain a heat treated foil,
For the chemical conversion for the secondary restoration, the heat-treated foil is put in a 0.1-0.6% diammonium hydrogen phosphate solution, subjected to a restoration chemical formation at 75-90 ° C and 100% applied voltage for 5-10 minutes, taken out and washed with water. The chemical conversion method is to reduce the undulation of the low-pressure chemical foil , which is to obtain a product by drying .
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