JPS63206499A - White color treatment of aluminum or aluminum alloy - Google Patents
White color treatment of aluminum or aluminum alloyInfo
- Publication number
- JPS63206499A JPS63206499A JP3961887A JP3961887A JPS63206499A JP S63206499 A JPS63206499 A JP S63206499A JP 3961887 A JP3961887 A JP 3961887A JP 3961887 A JP3961887 A JP 3961887A JP S63206499 A JPS63206499 A JP S63206499A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- aluminum
- film
- oxide film
- voltage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 30
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 28
- 238000011282 treatment Methods 0.000 title abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 239000013522 chelant Substances 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 43
- 239000010407 anodic oxide Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 230000002087 whitening effect Effects 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- -1 amino compound Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 abstract description 19
- 150000003839 salts Chemical class 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract 2
- 239000000956 alloy Substances 0.000 abstract 2
- 238000004040 coloring Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 240000000018 Gnetum gnemon Species 0.000 description 1
- 241000343235 Maso Species 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Classifications
-
- 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
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
《産業上の利用分野》
本発明は、アルミニウム又はアルミニウム合金製品、例
えばアルミニウムサツシ、引戸、玄関等の建築製品、シ
ョーケース、日用品、脚立、梯子、装飾用品、鋳物、ダ
イカスト、Ｉｆｉ輌又は船舶等の部品に使用されるアル
ミニウム又はアルミニウム合金の白色処理方法に関する
。[Detailed Description of the Invention] <<Industrial Application Field>> The present invention is applicable to aluminum or aluminum alloy products, such as architectural products such as aluminum sashes, sliding doors, entrances, showcases, daily necessities, stepladders, ladders, decorative items, castings, This invention relates to a method for whitening aluminum or aluminum alloys used in parts for die casting, Ifi vehicles, ships, etc.
（従来の技術）
近来の消費生活、需要嗜好の多様化に伴い、アルミニウ
ム又はアルミニウム合金製品についても種々の色に着色
することが要求されるようになっている。特に従来のア
ルミニウム又はアルミニウム合金に施された着色皮膜の
色調は、ゴールド又はシルバー等の金属色を基調とした
冷たい印象を与える色合いであるため、白色を基調とし
た温かい感じを与える着色皮膜の′：Ｊ要が高まってい
る。(Prior Art) With the recent diversification of consumer lifestyles and demand preferences, there is a growing demand for aluminum or aluminum alloy products to be colored in various colors. In particular, the color tone of conventional colored films applied to aluminum or aluminum alloys is based on metallic colors such as gold or silver, giving a cold impression. :J The importance is increasing.
そしてその様な着色皮膜を得るために、従来幾つかの不
透明白色処理が提案されてきた。In order to obtain such a colored film, several opaque white treatments have been proposed.
（発明が解決しようとする問題点）
ところが従来の白色処理方法では、使用される薬品が有
害物質であるために公害防止手段を講じなければならず
、又得られる不透明白色皮膜の程度によっては実用上不
適当な場合もある。従って現状では塗装法などで対処さ
れている。(Problems to be solved by the invention) However, in the conventional white treatment method, since the chemicals used are harmful substances, measures must be taken to prevent pollution, and depending on the degree of the opaque white film obtained, it may not be practical. There are cases where it is inappropriate. Therefore, at present, this problem is dealt with by painting methods.
又この様な問題点を解決するために特開昭６０−１９７
８９７号公報において、以下の方法が提案されている。In addition, in order to solve such problems, Japanese Patent Application Laid-Open No. 60-197
In Japanese Patent No. 897, the following method is proposed.
即もアルミニウム又はアルミニウム合金の陽極酸化皮膜
を白色にする手段として、陽極酸化皮膜孔中に白色ない
し灰白色の物質を生成せしめる方法である。Specifically, as a means of making the anodic oxide film of aluminum or aluminum alloy white, it is a method of producing a white to gray-white substance in the pores of the anodic oxide film.
ところがその方法では、２次電解着色の段階で白色化合
物に該金属を反応させて白色化合物を生成する際に、析
出むらが生じていることを発見してｂ１既に金属が析出
されているので上記析出むらを修正することができず、
着色むらが生じるという不具合が生じる。However, with that method, it was discovered that uneven precipitation occurred when the metal was reacted with the white compound at the stage of secondary electrolytic coloring to produce a white compound. It is not possible to correct uneven precipitation,
A problem arises in that uneven coloring occurs.
又他方１１２極酸化皮膜の孔を拡大せずに、白色の酸化
物を孔に析出６Ｕることは出来ず、鍋形状のアルミニウ
ム製製品や、コの字形の製品を着色処理する際に、１次
電解着色の段階で陽極酸化皮膜の孔中に白色の基礎とな
る金属を析出さＵる時に析出むらが生じやすいという不
具合が生じる。しかも上述した理由により、処Ｉ！！製
品の表面に生じた析出むらを修正することができず、着
色むらを解消することができないという不具合が生じる
。On the other hand, it is not possible to deposit 6U of white oxide into the pores of the 112 electrode oxide film without enlarging the pores, so when coloring pot-shaped aluminum products or U-shaped products, 1. When the white basic metal is deposited into the pores of the anodic oxide film in the subsequent electrolytic coloring step, a problem arises in that uneven deposition tends to occur. Moreover, for the reasons mentioned above, the treatment I! ! A problem arises in that it is not possible to correct the uneven precipitation that occurs on the surface of the product, and it is not possible to eliminate the uneven coloring.
そこで本件出願人は、以下の発明を提案している。即ち
アルミニウム又はアルミニウム合金に陽極酸化皮膜を形
成し、次に上記陽極酸化皮膜の孔径をリン酸、ｉ酸等の
無機酸又はスルホサリチル酸、シュウｗＪ等のｈａｍ、
あるいは水酸化ナトリウム、水酸化カリウム等のアルカ
リ性溶液を用いて拡大した後、Ｃａ、Ｂａ、Ｔ ｉ 、
ＺｎｌＭＱ、ＡＩ等の酸化物が白色である金属の水溶液
中で再陽極酸化処理を行い、更に同浴中で電解着色処理
を行うことを特徴とするアルミニウム又はアルミニウム
合金の白色処理方法である。Therefore, the applicant has proposed the following invention. That is, an anodic oxide film is formed on aluminum or an aluminum alloy, and then the pore size of the anodic oxide film is adjusted by adjusting the pore size of the anodic oxide film using an inorganic acid such as phosphoric acid, ionic acid, sulfosalicylic acid, ham, etc.
Alternatively, after expanding using an alkaline solution such as sodium hydroxide or potassium hydroxide, Ca, Ba, Ti,
This is a method for whitening aluminum or aluminum alloy, which is characterized by performing re-anodizing treatment in an aqueous solution of a metal whose oxide is white, such as ZnlMQ, AI, etc., and further performing electrolytic coloring treatment in the same bath.
［記処理方法を採用り゛ることにより、均一で暖かな色
調の白色皮膜が生成される。ところがそのＩＪ法では、
着色処理後の封孔処理において脱色が生じるおそれがあ
る。その様な不具合を解決するために、電解着色模、別
の工程として有機系極性溶媒又は４゛レ一ト化合物ある
いは有機系極性溶媒及びキレート化合物を含む浴中で浸
漬又は電解処理を施すことも考えられる。しかしその方
法では、工程が多くなり、生産性の低下を回避できない
。[By employing the treatment method described above, a uniform, warm-toned white film is produced. However, in the IJ method,
There is a possibility that decolorization may occur during the sealing treatment after the coloring treatment. In order to solve such problems, the electrolytically colored model may be immersed or electrolytically treated in a bath containing an organic polar solvent or a chelate compound or an organic polar solvent and a chelate compound as a separate process. Conceivable. However, this method requires a large number of steps and cannot avoid a decrease in productivity.
本発明は、アルミニウム又はアルミニウム合金の表面に
、均一な白色皮膜を生成し、ざらに封孔処理を施しても
脱色することのない白色皮膜を（１することのできる白
色皮膜処理方法を提供することを目的としている。The present invention provides a white film treatment method that can generate a uniform white film on the surface of aluminum or aluminum alloy, and that does not discolor even after rough pore sealing treatment. The purpose is to
（問題点を解決するための手段）
本発明者はアルミニウム又はアルミニウム合金を白色に
着色する場合において上記問題点を解決する方法を研究
した結果、少なくと６１種の金属塩と、有機酸系極性溶
媒又はキレート化合物あるいは有機酸系極性２ｍ媒及び
キレート化合物とを含む水溶液中で、該陽極酸化皮膜を
陽極とし゛（直流電圧を印加した後、同浴中で陰極とし
て０流電圧を印加するか又は交流電圧を印加して該１ｌ
ｌｉ極酸化皮膜の孔の中に白色化合物を析出させること
が極めて有効であることを見出し、本発明を完成さゼる
に至った。(Means for Solving the Problems) As a result of research into methods for solving the above problems when coloring aluminum or aluminum alloys white, the present inventor found that at least 61 types of metal salts and organic acid-based polar In an aqueous solution containing a solvent or a chelate compound or an organic acid-based polar 2m medium and a chelate compound, use the anodic oxide film as an anode (after applying a DC voltage, apply a zero current voltage as a cathode in the same bath, or Apply AC voltage to the 1l
We have discovered that it is extremely effective to precipitate a white compound into the pores of the Li polar oxide film, and have completed the present invention.
即ち本発明は、アルミニウム又はアルミニウム合金に陽
極酸化皮膜を形成し、上記陽極酸化皮膜に硫酸、リン酸
、シ１つ酸等の酸性溶液及び水醒化ナトリウム、リン酸
三ナトリウム、炭酸プトリウム等のアルカリ性溶液中ぐ
再陽極酸化を行なって上記陽極酸化皮膜の孔径を拡大し
た後、Ｔｉ１ｚ ｎ、Ｃａ１Ｌ３ａ、Ｓｔ’、ｆｌ／Ｈ
１、ＡＩの塩の少なくとも１種の金属塩と、有機酸系極
性溶媒又はキレート化合物あるいは有ＩＩＩＭ′Ａ極性
溶媒及びキレ−１−化合物とを含む水溶液中で、該陽極
酸化皮膜を陽極として直流電圧を印加した後、同浴中で
陰極として直流電圧を印加するか又は交流電圧を印加し
て該陽極酸化皮膜の孔の中に白色化合物を析出させ、均
一な白色陽４４１Ｍ化皮膜を得ることを特徴とするアル
ミニウム又はアルミニウム合金の白色処理方法である。That is, in the present invention, an anodic oxide film is formed on aluminum or an aluminum alloy, and an acidic solution such as sulfuric acid, phosphoric acid, or silicic acid, and an aqueous solution of sodium hydrate, trisodium phosphate, putrium carbonate, etc. After enlarging the pore size of the anodic oxide film by re-anodizing in an alkaline solution, Ti1z n, Ca1L3a, St', fl/H
1. In an aqueous solution containing at least one metal salt of AI, an organic acid polar solvent, a chelate compound, or a IIIM'A polar solvent and a chelate compound, direct current is applied using the anodic oxide film as an anode. After applying the voltage, apply a DC voltage or apply an AC voltage as a cathode in the same bath to precipitate a white compound in the pores of the anodic oxide film to obtain a uniform white anodic 441M coating. This is a method for whitening aluminum or aluminum alloy, which is characterized by:
上記陽極酸化皮膜を形成するには、通常の陽極酸化法が
採用される。例えばＩｉ１酸、リン酸、クロム酸等から
なる無機酸、シュウ酸、スルホサリチル酸、マロン酸等
からなる０機酸、又は水酸化ナトリウム、リン酸三ナト
リウム等からなるアルカリ性の水溶液中で、直流、交流
、パルス、Ｐ Ｒ波、又は交直重畳法による電解によっ
て形成される。A normal anodic oxidation method is employed to form the anodic oxide film. For example, direct current, It is formed by electrolysis using alternating current, pulse, PR wave, or AC/DC superposition method.
これにより、孔を備えたｇ！極酸酸化皮膜断面模式図で
ある第１図に示すような陽極酸化皮膜１が得られる。尚
第１図〜第３図中、４はＢＪ月、５はバリヤ一層である
。This allows g! An anodic oxide film 1 as shown in FIG. 1, which is a schematic cross-sectional view of the anodic oxide film, is obtained. In FIGS. 1 to 3, 4 is the BJ month and 5 is the barrier layer.
、Ｆ記孔径を拡大する方法としては、例えば酸性？８ｗ
ｌあるいはアルカリ性溶液中で試料を陽極とし、直流若
しくはパルスあるいは交流を印加する方法を用いる。こ
れにより第２図に示すような拡大された孔２を冑ること
ができる。首孔２の直径ａは、約２００オンゲストＯ−
ム以−Ｆに拡大することが好ましい。上記方法によりｍ
３図に示すように、白色酸化物３が拡大された孔２の中
に析出し、白色皮膜を得ることが可能となる。, As a method of enlarging the F pore diameter, for example, acidic ? 8w
A method is used in which a sample is used as an anode in an alkaline solution or a direct current, a pulse, or an alternating current is applied. This allows the enlarged hole 2 as shown in FIG. 2 to be drilled. The diameter a of the neck hole 2 is approximately 200 mm
It is preferable to expand from M to F. m by the above method
As shown in FIG. 3, white oxide 3 is deposited in the enlarged pores 2, making it possible to obtain a white film.
上記キレート化合物の具体的な代表例としては、エチレ
ンジアミン四酢酸やそのナトリウム塩、トランス−１，
２−シクロヘキサンジアミン四酢酸、ジエチレントリア
ミン五酢酸、エチレジアミンニ酢酸、３，６−シオキサ
ー１．８−オクタンジアミン四酢酸、Ｎ−（２−ヒト［
１キシエチル）イミノニ酢酸、トリエチレンテトラミン
六酢酸等のポリアミノカルボン酸類、エチレンジアミン
等のジアミン類、トリエタノールアミン、トリ］チレン
テトラミン等の一分子中に２以上のアミン基を有するア
ミン化合物、アセト酢酸エチル、ニトリ〇三酢酸、ホル
マリン、修酸、マレイン酸、酒石酸、リンゴ酸、クエン
酸、コハク酸、グルコン酸又はグリシン等の多塩基酸及
びこれらの可溶性金属塩が挙げられる。Specific representative examples of the above chelate compounds include ethylenediaminetetraacetic acid and its sodium salt, trans-1,
2-Cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminediacetic acid, 3,6-thioxal 1,8-octanediaminetetraacetic acid, N-(2-human[
Polyaminocarboxylic acids such as (1xethyl)iminodiacetic acid, triethylenetetraminehexaacetic acid, diamines such as ethylenediamine, amine compounds having two or more amine groups in one molecule such as triethanolamine, tri]ethylenetetramine, ethyl acetoacetate , nitric triacetic acid, formalin, oxalic acid, maleic acid, tartaric acid, malic acid, citric acid, succinic acid, gluconic acid, or glycine, and their soluble metal salts.
（作用）
金属塩に有機系極性ｗ１媒又はキレート化合物あるいは
有機系極性２８媒及びキレート化合物の添加された浴中
で電解着色処理を行なうことにより、着色反応によって
１ＩｉＪｋ酸化皮膜の孔の中に生成した白色化合物と強
固な不溶性化合物を形成し、孔の中にその白色生成物が
固着する。(Function) By electrolytically coloring the metal salt in a bath to which an organic polar W1 medium or a chelate compound or an organic polar 28 medium and a chelate compound are added, coloring reaction occurs in the pores of the 1IiJk oxide film. A strong insoluble compound is formed with the white compound, and the white product is fixed in the pores.
（発明の効果）
（１）本発明によると、陽極酸化皮膜の孔径を拡大させ
た後、Ｔ ｉ 、Ｚｎ、Ｃａ、８ａ、ＳｒｌＭｕ、ＡＮ
の塩の少なくとも１種の金ｊＩ！塩と、有機酸系極性溶
媒又はキレート化合物あるいは有機酸系極性溶媒及びキ
レート化合物とを含む水溶液中で、該陽極酸化皮膜を陽
極として直流電圧を印加した後、同浴中で陰極として直
流電圧を印加するか又は交流電圧を印加して該陽極酸化
皮膜の孔の中に白色化合物を析出させ、均一な白色ｆｉ
ｌ極酸化皮膜を得ることを特徴としているので、白色生
成物が孔の中に固着し、封孔処理を１Ｍ１ノだ後も脱色
することはない。又本発明は１つの浴で着色処理を行な
うので、他の浴で浸漬又は電解処理を行なうことにより
、白色生成物を孔の中に固着させる方法に比べて処理工
程が少なく、生産性が高いという利点がある。(Effects of the Invention) (1) According to the present invention, after expanding the pore size of the anodic oxide film, Ti, Zn, Ca, 8a, SrlMu, AN
At least one kind of gold jI in the salt of! In an aqueous solution containing a salt and an organic acid-based polar solvent or a chelate compound, or an organic acid-based polar solvent and a chelate compound, a DC voltage is applied using the anodic oxide film as an anode, and then a DC voltage is applied as a cathode in the same bath. A white compound is precipitated into the pores of the anodic oxide film by applying an alternating voltage or an alternating current voltage to produce a uniform white fi.
Since it is characterized by the formation of a polar oxide film, the white product is fixed in the pores and does not decolor even after the pore sealing treatment is performed at 1M1. In addition, since the present invention performs coloring treatment in one bath, there are fewer treatment steps and higher productivity compared to a method in which a white product is fixed in the pores by immersion or electrolytic treatment in another bath. There is an advantage.
（２）白色をＭｌｌとした暖かな色合いの白色皮膜をア
ルミニウムやアルミニウム合金の表面に生成することが
でき、多用な市場のニーズに応じることができる。又陽
極酸化皮膜の孔径を拡大させることにより、従来孔中に
析出できなかった白色酸化物を直接析出させることがで
きる。さらに本発明によると、電流の電流密磨に比例し
た厚さのバリｔ−−ｆｌを得ることができる。従っで処
１１！製品の形状が複雑なために、電流密度が局部的に
増減している場合でも、ｆｆｉ！密度に比例配分したバ
リヤ一層を得ることができるので、本発明を形状の複雑
な鋼状の製品に採用した場合でも、従来の方法では困難
であった着色むらを容易に防Ｉｔケることができる。(2) A warm-colored white film with a white color of Mll can be produced on the surface of aluminum or aluminum alloy, and can meet the needs of various markets. Furthermore, by enlarging the pore diameter of the anodic oxide film, white oxides that could not be deposited in the pores can be directly deposited. Furthermore, according to the present invention, it is possible to obtain a burr t--fl whose thickness is proportional to the current densification of the current. Follow me 11! Even if the current density locally increases or decreases due to the complex shape of the product, ffi! Since it is possible to obtain a barrier layer proportional to the density, even when the present invention is applied to steel-like products with complex shapes, uneven coloring, which is difficult with conventional methods, can be easily prevented. can.
（実施例）
以下に説明する実施例は、アルミニウム合金について行
なわれたものであるが、アルミニウム材についても同様
に採用することができることはいうまでもない。(Example) Although the example described below was carried out using an aluminum alloy, it goes without saying that the same can be applied to an aluminum material as well.
第４図及び第５図に示すように、平板状のアルミニウム
合金（Ａ６０６３Ｓ−Ｔ５材）処理材１０を電ｗＩ枠１
２の電解棒１４に吊った。これを１７００／ｊのＨ２Ｓ
Ｏ４浴中で陽極酸化処理を行ない、皮膜厚９μｍのｗＡ
権酸酸化皮膜得た。その俊該陽極酸化皮膜をカーボンを
対極としてリン酸１０００／ｊ （２０℃）中で再１
１４！酸化処理（直流型ｒｆ１６Ｖｘ１０分）を行なっ
て、陽極酸化皮膜の孔径の拡大処理を行った。As shown in FIGS. 4 and 5, a flat aluminum alloy (A6063S-T5 material) treated material 10 is placed in an electric wI frame 1.
It was hung from the electrolytic rod 14 of No. 2. This is 1700/j H2S
Anodic oxidation treatment was performed in an O4 bath to give a film thickness of 9μm wA.
An acid oxide film was obtained. The anodic oxide film was then re-immersed in phosphoric acid 1000/j (20°C) with carbon as the counter electrode.
14! Oxidation treatment (DC type rf16V x 10 minutes) was performed to enlarge the pore diameter of the anodic oxide film.
次に白色皮膜の電解着色を以下に示す第１実施例〜第５
実施例の通り行なった。Next, the electrolytic coloring of the white film is shown in Examples 1 to 5 below.
It was carried out as in the example.
［第１実施例１
１０ａ／ｊのＭａＳＯ，５％のメタノールの雷解着色浴
中で、第６図（示すように、直流のｆｆｉ圧Ｅ−２４ボ
ルト、交流の電圧Ｖ−２０ボルト、直流の電Ｊ）、Ｉ：
の昇圧時間ｔ１−２０秒、保持時開ｔ −２秒、交流
の電圧Ｖの昇圧時間ｔ３−５秒、保持時＋ｆｆ１ｔ４−
３００秒として通電した結果、処理材１０の中央部１０
ａ、端部１０ｂ（第４図、第５図）とも均一な白色度１
１！Ｊ（ハンタ一方式による白色度−９２，５％）を得
ることができた。[Example 1] In a lightning coloring bath of 10 a/j MaSO, 5% methanol, as shown in Figure 6 (DC ffi pressure E - 24 volts, AC voltage V - 20 volts, DC den J), I:
Boosting time t1-20 seconds, open t-2 seconds when holding, boosting time t3-5 seconds of AC voltage V, holding +ff1t4-
As a result of energizing for 300 seconds, the center part 10 of the treated material 10
Uniform whiteness of 1 for both a and end portion 10b (Figs. 4 and 5)
1! It was possible to obtain a whiteness of -92.5% by Hunter's method.
さらに封孔処理として、シーリングソルトＡｓ（サンド
社製封孔助剤）７０＃ｌ浴中９０℃×２０分を行なった
が、処理材１０の中央７！ｌＳｉ ｏａ、端部１０ｂ（
第４図、第５図）いずれも全く脱色しなかった。Furthermore, as a sealing treatment, sealing salt As (sealing aid manufactured by Sandoz Co., Ltd.) was carried out in a 70 #l bath at 90°C for 20 minutes, but the center 7 of the treated material 10 was sealed. lSi oa, end 10b (
(Figures 4 and 5) No bleaching occurred at all.
【第２実施例］
５ｇ／ｊのＢａＧＯ，１％のアセトンの電解者色浴中で
、第７図に示すように、正の極性の電圧Ｅ１−２０，１
ルト、負の極性ノｒＩＩＥ［Ｅ２＝−１８ホルト、正の
極性の電圧Ｅ１の昇圧時ｍｔ、−ｉｓ秒、保持時ｒｍｔ
−ｉ秒、負の極性の電圧［２の昇ｒｒｕｎ ｔ ３
− ａ ｏ秒、保持ｌｉ固ｔ４−１８０秒として通電し
た結果、処１１ＩＩ４１０の中央部１０ａ１端部１０ｂ
（第４図、第５図）とも均一な白色皮膜（ハンタ一方式
による白色＊−８９，２％″）を得ることができた。[Second Example] In an electrolyzer color bath of 5 g/j BaGO and 1% acetone, a positive polarity voltage E1-20,1 was applied as shown in FIG.
default, negative polarity nor rIIE [E2 = -18 halt, positive polarity voltage E1 when boosting mt, -is seconds, holding when rmt
−i seconds, negative polarity voltage [2 rise rrun t 3
- As a result of energizing for ao seconds and holding li for 4-180 seconds, the center part 10a1 end part 10b of the part 11II410
In both cases (FIGS. 4 and 5), a uniform white film (white color by Hunter one method *-89.2%) could be obtained.
ざらに封孔処理として、シーリングソルトＡｓ（サンド
社製封孔助剤）７ｏ／ｊ浴中９０℃×２０分を行なった
が、処３１１！＠１０の中央部１０ａ１端部１０ｂ（第
４図、第５図）いずれも全く脱色しなかった。As a rough sealing treatment, sealing salt As (sealing aid manufactured by Sandoz Co., Ltd.) was carried out at 90°C for 20 minutes in a 7o/j bath, but the result was 311! Neither the central portion 10a1 nor the end portion 10b (FIGS. 4 and 5) of @10 was bleached at all.
［第３実施例］
２ Ｑ／ＩのＺｎ （Ｎｏ ） 、１０ｏ／ｊの八
ｊ （Ｓｏ ） 、２ａ／磨のＥＤＴへの電解
者色浴中で、第８図に示すように、正の極性の電圧Ｅ
−１８ボルト、負の極性の電圧Ｅ２−１８ボル
ト
秒、保持時間ｔ２−２秒、負の極性の電圧Ｅ２の昇圧時
間ｔ３−１０秒、保持時間ｔ４−５秒、体止時ｒｌＪｔ
５＝１秒として反復回数ｎ・・３０同で通電した結果、
処理材１０の中央部１０ａ，端部１０ｂ（第４図、第５
図）とも均・な白色皮膜（ハンタ一方式による白色度−
９１．５％）を得ることができた。[Third Example] Zn (No) of 2Q/I, 8j (So) of 10o/j, in an electrolyzer color bath to EDT of 2a/polish, as shown in FIG. Polarity voltage E
-18 volts, negative polarity voltage E2-18 volt seconds, hold time t2-2 seconds, negative polarity voltage E2 boost time t3-10 seconds, hold time t4-5 seconds, body stop rlJt
Assuming 5=1 second, the number of repetitions n...30 times, the result is
The center portion 10a and end portions 10b of the treated material 10 (Figs. 4 and 5)
(Fig.) A uniform white film (whiteness by Hunter method -
91.5%).
ざらに封孔処理として、シーリングソルトＡｓ（サンド
社製封孔助剤）ｌ／ｊ浴中９０り×２０分を行なったが
、処１１材１０の中火部１０ａ，端部１０ｂ（第４図、
第５図）いずれも仝く１脱色しなかった。As a rough sealing treatment, 90 ml of sealing salt As (sealing aid manufactured by Sandoz Co., Ltd.) l/j bath was carried out for 20 minutes. figure,
(Fig. 5) None of them were completely bleached.
［第４実施例］
１００／ｊのＴｉＯＳｏ 、５％のジメチルホルムア
ミド、５ ａ／ｊのグリシンの電解着色浴中で、第９図
に示すように、直流の電圧Ｅ−２６ボルト、交流の電圧
ｖ−２０ボルト、直流の電圧［の弁圧時間ｔ，ー１５秒
、保持時間ｔ２−２秒、交流の電ＪＩＶ（７）ｌＪＩ＆
？ｆｌｌ ｔ ３− １ ０秒、ｓ 持ｕｓ ｒｍ ｔ
４−３００秒として通電した結果、処理材１０の中央
部１０ａ、端部１０ｂ（第４図、第５図）とも均−な白
色皮膜（ハンタ一方式による白色度−９２，３％）を得
ることができた。[Fourth Example] In an electrolytic coloring bath of 100/j TiOSo, 5% dimethylformamide, 5 a/j glycine, as shown in FIG. V-20 volts, DC voltage [valve pressure time t, -15 seconds, holding time t2-2 seconds, AC voltage JIV (7) lJI &
? full t 3-10 seconds, s hold us rm t
As a result of energizing for 4-300 seconds, a uniform white film (whiteness of -92.3% by Hunter one-way method) was obtained on both the center portion 10a and end portions 10b (Figures 4 and 5) of the treated material 10. I was able to do that.
さらに封孔処理として、シーリングソルトＡｓ（サンド
社製封孔助剤’）７ａ／Ｉ浴中９０℃Ｘ２０分を行なっ
たが、処理材１０の中央部１０ａ、端部１０ｂ（第４図
、第５図）いずれも全く脱色しなかった。Further, as a sealing treatment, sealing salt As (sealing aid manufactured by Sandoz) 7a/I bath at 90°C for 20 minutes was carried out at 90°C for 20 minutes. Figure 5) No bleaching occurred at all.
［第５実施例１
１０ｇ／ｊのＡｌ （ＳＯ） 、２ａ／ｌのＣａＳＯ
，１％のグルコン酸の電解着色浴中で、第１０図に示す
ように、正の極性の電圧Ｅ。[Fifth Example 1 10 g/j Al (SO), 2 a/l CaSO
, in an electrolytic coloring bath of 1% gluconic acid, at a voltage E of positive polarity, as shown in FIG.
−１８ボルト、負め極性の電圧Ｅ、２−１８ボルト、正
の極性の電圧Ｅ１のシー正時間ｔ１−１０秒、保持時間
ｔ２＝１秒、負の極性の電圧Ｅ２の昇圧時間ｔ３−ａｏ
秒、保持時間ｔ４−１８０秒として通電した結果、処理
材１０の中央Ｎ １０ ａ 、端部１０ｂ（第４図、第
５図）とも均一な白色皮膜（ハンタ一方式による白色度
−９０，７％）を得ることができた。-18 volts, voltage E with negative polarity, 2-18 volts, voltage E1 with positive polarity, positive time t1-10 seconds, holding time t2 = 1 second, boost time t3-ao of voltage E2 with negative polarity
As a result of energizing with a holding time of t4-180 seconds, a uniform white film was formed on both the center N 10 a and the end portions 10b (Figs. 4 and 5) of the treated material 10 (whiteness by Hunter method -90,7). %).
ざらに封孔処理として、シーリングソルトＡＳ（ＩＪ′
ンド社製封孔助剤）ｌ／ｊ浴中９０り×２０分を行＜ｋ
つだが、処理材１０の中央部１０ａ１端部１０ｂ（第４
図、第５１ｊ！４）いずれも全く脱色しなかった。As a rough sealing treatment, sealing salt AS (IJ'
Sealing aid manufactured by Ndo Co., Ltd.) 90 ml x 20 minutes in l/j bath <k
However, the center part 10a1 end part 10b (fourth
Figure, No. 51j! 4) None of them were bleached at all.
本発明の実施例を示す第１図〜第１０図において、第１
図は孔を備えた陽極酸化皮膜の断面模式図、第２図はｗ
Ａ権酸酸化皮膜孔径を拡大した状態を示す陽極酸化皮膜
の断面模式図、第３図は拡大した陽１４ｇＦｉｆｉ化皮
膜の孔の中に白色酸化物を析出した状態を示すｌ！ｇ極
酸化皮膜の断面模式図、第４図は第１〜第５実施例に用
いたｔｌｌり具の１１石略図、第５図は第１〜第５実施
例に用いた吊り具の側面略図、第６図は第１実施例の電
圧印加方法を示Ｊグラフ、第７図は第２実施例の電圧印
加方法を示すグラフ、第８図は第３実施例の電圧印加方
法を示すグラフ、第９図は第４実施例の電圧印加方法を
示タグラフ、第１０図は第５実施例の電圧印加方法を示
すグラフである。
第４図 第５図
第６図
７サイクル
手続補正書（自発）
昭和６３年２月２１１＝１
詩許庁長官 殿
１ｖ司−件の表示
昭和６２年 特 許 願 第３９６１８号２ 発明の名
称
アルミニウム又はアルミニウム合金の白色゛処理方法
３、補正をする者
事件との関係 特許出願人
住 所 大阪市東区農人橋詰町２３番地名 称 藤田商
事株式会社
代表者 代表取締役 ａ ｍ 安彦
４、代理人
住 所 大阪市北区東天満２丁目９番４ｆ−５千代川
ピル東館７Ｍ（・５３０）
５、補正命令の日付 （発送日）昭和 年 月 日（１
） 特許請求の範囲を別紙の通り補正する。
絶・
陽極酸化皮膜に陽極電解処理をしだ後」と補正する。
（３） 同７頁７〜８行の［該陽極酸化皮膜を陽極とし
て直流電圧を印加した後」を［該陽極酸化皮膜に陽極電
解処理をしだ後］と補正する。
（４） 同９′ｆｉ８行と９行の間に次の説明を加える
。
「 上記陽極電解処理としては、例えば試料を陽極とす
る直流またはパルスを印加する方法が用いられる。」
（５） 同１０頁２〜３行の［該陽極酸化皮膜を１１１
ｉ１４ｉとして直流電圧を印加した後」を「該陽極酸ヒ
皮膜に陽極電解処理をしだ後」と補正する。
（６） 同１０頁１２行の「利点がある。」の次に以下
の説明を加える。
「このｇｉｌｆ！電解処理は、形状の複雑な処理物品の
１面に均一に着色処理を行なう上で特に重要である。す
なわち仮にこの陽極電解処理を行わないと、処理物品の
対極に近い部所に電流が集中し、よく着色されるが、遠
い箇所は電流が流れにクク着色しにくい。従って色調が
不均一になってしまう。
使方本発明においては、陽極電解処理を行なっているの
で、電流密度に比例した厚さのバリヤー履を１９ること
ができ、形状の複雑な処理物品の着色に際しても着色む
らは生じないのである。」（７） 同１６頁４行と５行
の間に以下の説明を加える。
「［第１〜第５実施例の効果］
以上説明した第１〜第５実施例によって上述した本発明
の効果を得ることができる。すなわち第１〜第５実施例
によるとＴ ＋、ｚｎ、ｃａ１ｓａ。
Ｓｒ、Ｍｇ、Ａｌｌの塩の少なくとも１種の金属塩と、
有機酸系極性溶媒又はキレート化合物あるいは有機酸系
極性溶媒及びキレート化合物とを含む水溶液中で、該陽
極酸化皮膜に陽極電解処理を施しているので、電流密度
に比例した厚さのバリヤーｌｉｄを得ることができ、コ
の字形の処理物品の着色に際しても着色むらは生じない
のである。
他方仮にこの陽極電解処理を行なわないと、断面がコの
字形の処理物品の着色に際し、対極に近い外周面に電流
が集中し、内周面には電流が流れにくくなるため、着色
むらが生じやすくなる。しかし第１〜第５実施例におい
ては、上記陽極電解処理を採用しているので、断面がコ
の字形処理物品についてもより一層確実に均一な着色皮
膜を得ることができる。
なお第１〜第５実施例においては、上記陽極電解処理と
して、第６図、第７図、第８図、第９図、第１０図の１
１で示すように、電圧を印加開始時点から目標の電圧値
にまで比例的に昇圧し、その間の昇圧時間を５〜２０秒
とする方法を採用している。」
８、添附書類の目録
（１） 特許請求の範囲・・・ １ 通以
上
特許請求の範囲
（１）アルミニウム又はアルミニウム合金に陽極酸化皮
膜を形成し、上記ｖＪ極酸酸化皮膜硫酸、リン酸、シュ
ウＭ＠の酸性溶液及び水酸化ナトリウム、リン酸三ナト
リウム、炭酸ナトリウム等のアルカリ性溶液中で再陽極
酸化を行なって上記陽極酸化皮膜の孔径を拡大した棲、
Ｔｉ、Ｚｎ、Ｃａ、Ｂａ、Ｓｒ、ＭＱ、ＡＪの塩の少な
くとも１種の金属塩と、有機酸系極性溶媒又はキレート
化合物あるいは有！ａ酸系極性ｍｔｓ及びキレート化合
物とを含む水溶液中で、 に陽極′解処理
をした後、同浴中で陰極として直流電圧を印加するか又
は交流電圧を印加して該陽極酸化皮膜の孔の中に白色化
合物を析出させ、均一な白色ｌ！極酸酸化皮膜得ること
を特徴とするアルミニウム又はアルミニウム合金の白色
処理方法。
（２）上記酸性溶液が、リン酸、Ｔｍ酸等の無機酸又は
スルホサリチル酸、シュウ酸箸の有機酸である特許請求
の範囲第１項記載のアルミニウム又はアルミニウム合金
の白色処理方法。
（３）上記孔径を拡大する方法として、酸性溶液あるい
はアルカリ性溶液中で試料を陽極とし、直流若しくはパ
ルスあるいは交流を印加する方法を用いた特許請求の範
囲第１項記載のアルミニウム又−はアルミニウム合金の
白色処理方法。
（４）上記キレート化合物が、ポリアミノカルボン酸類
、多塩基酸類又は１分子中に２以上のアミン ′基
を有するアミノ化合物である特許請求の範囲第１項記載
のアルミニウム又はアルミニウム合金の白色処理方法。
（５）ｒ 処理として を とする直流
又はパルスを印加する特許請求の範囲第１項記載のアル
ミニウム又はアルミニウム合金の白色処理方法。In FIGS. 1 to 10 showing embodiments of the present invention, the first
The figure is a schematic cross-sectional view of an anodic oxide film with holes, and Figure 2 is w.
A schematic cross-sectional view of the anodic oxide film showing the enlarged pore diameter of the anodic oxide film, and Figure 3 shows the state in which white oxide has been precipitated into the enlarged pores of the anodic oxide film. g A schematic cross-sectional view of the polar oxide film, Figure 4 is a schematic diagram of the tll lifting tool used in the first to fifth examples, and Figure 5 is a side schematic diagram of the hanging tool used in the first to fifth examples. , FIG. 6 is a graph showing the voltage application method of the first embodiment, FIG. 7 is a graph showing the voltage application method of the second embodiment, and FIG. 8 is a graph showing the voltage application method of the third embodiment. FIG. 9 is a graph showing the voltage application method of the fourth embodiment, and FIG. 10 is a graph showing the voltage application method of the fifth embodiment. Fig. 4 Fig. 5 Fig. 6 Fig. 7 Cycle procedure amendment (voluntary) February 1988 211 = 1 Director General of the Publications Office 1 v. Indication of the matter 1988 Patent Application No. 39618 2 Name of the invention Aluminum or white color treatment method for aluminum alloy 3, relationship with the case of the person making the amendment Patent applicant address 23 Nonin Hashizume-cho, Higashi-ku, Osaka Name Fujita Shoji Co., Ltd. Representative Director A.M. Yasuhiko 4, Agent address 7M Chiyogawa Pill Higashikan 2-9-4F-5 Higashitenma, Kita-ku, Osaka (・530) 5. Date of amendment order (shipment date) Showa year, month, day (1)
) Amend the claims as shown in the attached sheet. After the anodic electrolytic treatment is applied to the anodic oxide film.'' (3) On page 7, lines 7-8, "after applying a DC voltage using the anodic oxide film as an anode" is corrected to "after the anodic electrolytic treatment is applied to the anodic oxide film". (4) Add the following explanation between lines 8 and 9 of 9'fi. "For the above anodic electrolytic treatment, for example, a method of applying a direct current or a pulse using the sample as an anode is used." (5) "The anodic oxide film is
``After applying a DC voltage as i14i'' is corrected to ``After the anodic electrolytic treatment is applied to the anodic arsenic film''. (6) Add the following explanation after "There are advantages." on page 10, line 12. ``This gilf! electrolytic treatment is particularly important for uniformly coloring one side of a processed article with a complex shape.In other words, if this anodic electrolytic treatment is not performed, the parts of the treated article near the opposite electrode The current concentrates on the area, resulting in good coloring, but it is difficult to color the area where the current flows, resulting in uneven color tone. It is possible to create barrier footwear with a thickness proportional to the current density, and uneven coloring does not occur even when coloring objects with complex shapes.'' (7) Between lines 4 and 5, page 16. Add the following explanation. [Effects of the first to fifth embodiments] The above-described effects of the present invention can be obtained by the first to fifth embodiments described above. That is, according to the first to fifth embodiments, T +, zn, ca1sa. At least one metal salt of Sr, Mg, and All salt;
Since the anodic oxide film is subjected to anodic electrolysis treatment in an aqueous solution containing an organic acid-based polar solvent or a chelate compound, or an organic acid-based polar solvent and a chelate compound, a barrier lid having a thickness proportional to the current density is obtained. Therefore, even when coloring a U-shaped processed article, uneven coloring does not occur. On the other hand, if this anodic electrolytic treatment is not performed, when coloring a treated article with a U-shaped cross section, the current will concentrate on the outer peripheral surface near the counter electrode, and it will be difficult for the current to flow to the inner peripheral surface, resulting in uneven coloring. It becomes easier. However, in the first to fifth embodiments, since the anodic electrolytic treatment described above is employed, it is possible to more reliably obtain a uniform colored film even for treated articles having a U-shaped cross section. In the first to fifth embodiments, as the anodic electrolytic treatment, 1 in FIGS. 6, 7, 8, 9, and 10 is used.
As shown in No. 1, a method is adopted in which the voltage is increased proportionally from the start of application to a target voltage value, and the voltage increase time during that time is 5 to 20 seconds. 8. List of attached documents (1) Claims... 1 or more copies Claims (1) An anodic oxide film is formed on aluminum or an aluminum alloy, and the vJ polar acid oxide film is coated with sulfuric acid or phosphoric acid. , anodized film in which the pore size of the anodic oxide film was enlarged by re-anodizing in an acidic solution of Shu M@ and an alkaline solution of sodium hydroxide, trisodium phosphate, sodium carbonate, etc.,
At least one metal salt selected from salts of Ti, Zn, Ca, Ba, Sr, MQ, and AJ, and an organic acid-based polar solvent or chelate compound or! After anodic decomposition treatment in an aqueous solution containing an acid-based polar mTS and a chelate compound, a DC voltage is applied as a cathode in the same bath, or an AC voltage is applied to close the pores of the anodic oxide film. A white compound is precipitated inside, giving a uniform white color! A method for whitening aluminum or aluminum alloy, characterized by obtaining a polar acid oxide film. (2) The method for whitening aluminum or aluminum alloy according to claim 1, wherein the acidic solution is an inorganic acid such as phosphoric acid or Tm acid, or an organic acid such as sulfosalicylic acid or oxalic acid. (3) The aluminum or aluminum alloy according to claim 1, wherein the pore diameter is expanded by using a method of applying direct current, pulses, or alternating current to the sample as an anode in an acidic or alkaline solution. White processing method. (4) The method for whitening aluminum or aluminum alloy according to claim 1, wherein the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amino compound having two or more amine groups in one molecule. (5) The white treatment method for aluminum or aluminum alloy according to claim 1, wherein a direct current or a pulse is applied as the r treatment.
Claims (4)
膜を形成し、上記陽極酸化皮膜に硫酸、リン酸、シユウ
酸等の酸性溶液及び水酸化ナトリウム、リン酸三ナトリ
ウム、炭酸ナトリウム等のアルカリ性溶液中で再陽極酸
化を行なって上記陽極酸化皮膜の孔径を拡大した後、Ｔ
ｉ、Ｚｎ、Ｃａ、Ｂａ、Ｓｒ、Ｍｇ、Ａｌの塩の少なく
とも１種の金属塩と、有機酸系極性溶媒又はキレート化
合物あるいは有機酸系極性溶媒及びキレート化合物とを
含む水溶液中で、該陽極酸化皮膜を陽極として直流電圧
を印加した後、同浴中で陰極として直流電圧を印加する
か又は交流電圧を印加して該陽極酸化皮膜の孔の中に白
色化合物を析出させ、均一な白色陽極酸化皮膜を得るこ
とを特徴とするアルミニウム又はアルミニウム合金の白
色処理方法。(1) Form an anodic oxide film on aluminum or aluminum alloy, and reprocess the anodic oxide film in an acidic solution such as sulfuric acid, phosphoric acid, or oxalic acid, or an alkaline solution such as sodium hydroxide, trisodium phosphate, or sodium carbonate. After enlarging the pore size of the anodic oxide film by anodic oxidation, T
i, Zn, Ca, Ba, Sr, Mg, Al, and an organic acid-based polar solvent or a chelate compound, or an organic acid-based polar solvent and a chelate compound. After applying a DC voltage using the oxide film as an anode, a white compound is precipitated in the pores of the anodic oxide film by applying DC voltage or AC voltage as a cathode in the same bath, thereby forming a uniform white anode. A method for whitening aluminum or aluminum alloy, characterized by obtaining an oxide film.
ルホサリチル酸、シユウ酸等の有機酸である特許請求の
範囲第１項記載のアルミニウム又はアルミニウム合金の
白色処理方法。(2) The method for whitening aluminum or aluminum alloy according to claim 1, wherein the acidic solution is an inorganic acid such as phosphoric acid or sulfuric acid or an organic acid such as sulfosalicylic acid or oxalic acid.
はアルカリ性溶液中で試料を陽極とし、直流若しくはパ
ルスあるいは交流を印加する方法を用いた特許請求の範
囲第１項記載のアルミニウム又はアルミニウム合金の白
色処理方法。(3) The white color of the aluminum or aluminum alloy according to claim 1, which uses a method of enlarging the pore size by applying direct current, pulses, or alternating current to the sample as an anode in an acidic or alkaline solution. Processing method.
、多塩基酸類又は１分子中に２以上のアミン基を有する
アミノ化合物である特許請求の範囲第１項記載のアルミ
ニウム又はアルミニウム合金の白色処理方法。(4) The method for whitening aluminum or aluminum alloy according to claim 1, wherein the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amino compound having two or more amine groups in one molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62039618A JPH0633504B2 (en) | 1987-02-23 | 1987-02-23 | White treatment method for aluminum or aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62039618A JPH0633504B2 (en) | 1987-02-23 | 1987-02-23 | White treatment method for aluminum or aluminum alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63206499A true JPS63206499A (en) | 1988-08-25 |
| JPH0633504B2 JPH0633504B2 (en) | 1994-05-02 |
Family
ID=12558096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62039618A Expired - Lifetime JPH0633504B2 (en) | 1987-02-23 | 1987-02-23 | White treatment method for aluminum or aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0633504B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103080386A (en) * | 2010-08-25 | 2013-05-01 | 丰田自动车株式会社 | Internal combustion engine and method of producing same |
| JP2017020114A (en) * | 2012-06-22 | 2017-01-26 | アップル インコーポレイテッド | White-appearing anodized films, and methods for forming the same |
| US9839974B2 (en) | 2013-11-13 | 2017-12-12 | Apple Inc. | Forming white metal oxide films by oxide structure modification or subsurface cracking |
| US10017872B2 (en) | 2013-10-30 | 2018-07-10 | Apple Inc. | Metal oxide films with reflective particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792194A (en) * | 1980-12-01 | 1982-06-08 | Nippon Light Metal Co Ltd | Formation of opaque white film on aluminum |
-
1987
- 1987-02-23 JP JP62039618A patent/JPH0633504B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792194A (en) * | 1980-12-01 | 1982-06-08 | Nippon Light Metal Co Ltd | Formation of opaque white film on aluminum |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103080386A (en) * | 2010-08-25 | 2013-05-01 | 丰田自动车株式会社 | Internal combustion engine and method of producing same |
| US8893693B2 (en) | 2010-08-25 | 2014-11-25 | Toyota Jidosha Kabushiki Kaisha | Internal combustion engine and method of producing same |
| JP2017020114A (en) * | 2012-06-22 | 2017-01-26 | アップル インコーポレイテッド | White-appearing anodized films, and methods for forming the same |
| US10184190B2 (en) | 2012-06-22 | 2019-01-22 | Apple Inc. | White appearing anodized films |
| US10941503B2 (en) | 2012-06-22 | 2021-03-09 | Apple Inc. | White appearing anodized films |
| US10017872B2 (en) | 2013-10-30 | 2018-07-10 | Apple Inc. | Metal oxide films with reflective particles |
| US9839974B2 (en) | 2013-11-13 | 2017-12-12 | Apple Inc. | Forming white metal oxide films by oxide structure modification or subsurface cracking |
| US10434602B2 (en) | 2013-11-13 | 2019-10-08 | Apple Inc. | Forming white metal oxide films by oxide structure modification or subsurface cracking |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0633504B2 (en) | 1994-05-02 |
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