JPH052751B2 - - Google Patents
Info
- Publication number
- JPH052751B2 JPH052751B2 JP3765788A JP3765788A JPH052751B2 JP H052751 B2 JPH052751 B2 JP H052751B2 JP 3765788 A JP3765788 A JP 3765788A JP 3765788 A JP3765788 A JP 3765788A JP H052751 B2 JPH052751 B2 JP H052751B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- aluminum alloy
- treatment
- achromatic
- coloring
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 claims description 84
- 238000011282 treatment Methods 0.000 claims description 81
- 229910000838 Al alloy Inorganic materials 0.000 claims description 46
- 230000032683 aging Effects 0.000 claims description 31
- 238000011084 recovery Methods 0.000 claims description 29
- 238000007743 anodising Methods 0.000 claims description 20
- 230000035882 stress Effects 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 3
- 238000004040 coloring Methods 0.000 description 46
- 230000003750 conditioning effect Effects 0.000 description 22
- 238000011161 development Methods 0.000 description 21
- 230000018109 developmental process Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 8
- 239000010407 anodic oxide Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000003483 aging Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005422 blasting Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011701 zinc Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005270 abrasive blasting Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 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
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アルミニウム合金の不透明無彩色皮
膜の形成方法に関し、さらに詳しくは、短時間に
生産性よく、耐食性等の被膜性能に優れた無彩色
系の着色皮膜を形成する方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for forming an opaque achromatic film on an aluminum alloy, and more specifically, a method for forming an opaque achromatic film on an aluminum alloy, and more specifically, a method for forming an opaque achromatic film on an aluminum alloy, and more specifically, a method for forming an opaque, achromatic film on an aluminum alloy. The present invention relates to a method of forming a colored film.
一般にアルミニウム合金は加工性、耐食性等が
優れていることからサツシやカーテンウオール
等、建材として広く利用されており、通常シルバ
ー系、ブロンズ系、ゴールド系の着色皮膜が形成
されている。しかし、近年、建築業界でのニーズ
の多様化により、不透明色（パステル調）、特に
不透明灰色系のアルミニウム形材への要望が強ま
つている。
In general, aluminum alloys have excellent workability and corrosion resistance, so they are widely used as building materials such as sash and curtain walls, and usually have a silver, bronze, or gold colored film formed on them. However, in recent years, with the diversification of needs in the construction industry, there has been an increasing demand for aluminum shapes in opaque colors (pastel tones), especially opaque gray shades.
アルミニウム合金表面に不透明灰色系の着色皮
膜を形成する方法としては、従来、前処理法、電
解着色法、電流回復法、合金法、時効処理を伴う
方法などが知られている。 Conventionally known methods for forming an opaque gray colored film on the surface of an aluminum alloy include a pretreatment method, an electrolytic coloring method, a current recovery method, an alloy method, and a method involving aging treatment.
前処理法としては、例えば、特公昭49−24330
号公報に記載されているように、アルミニウム形
材をCl-イオン含有液中にて腐食させ、表面を粗
面化し、その後陽極酸化処理によりアルミニウム
形材の表面を灰色に着色する方法が知られてい
る。しかし、このような腐食法の場合、陽極酸化
処理後に皮膜上部に凹凸成分が残り、これにより
灰色に見えるため、粉吹き状になり、その後の塗
膜密着性が悪くなるという欠点がある。 As a pretreatment method, for example, Japanese Patent Publication No. 49-24330
As described in the publication, a method is known in which an aluminum profile is corroded in a solution containing Cl - ions to roughen the surface, and then the surface of the aluminum profile is colored gray by anodizing. ing. However, such corrosion methods have the drawback that uneven components remain on the upper part of the film after the anodizing treatment, which makes it look gray, resulting in a powdery appearance, and subsequent adhesion of the film becomes poor.
一方、電解着色法としては、例えば特開昭61−
143593号公報には、陽極酸化皮膜生成後、Ni塩
及びZn塩中にて２次電解着色を行ない、灰色に
する方法が記載されている。しかし、この方法で
は、Znを着色物質として使用するため、耐候性
が極端に悪くなり、また付廻り性も悪いという難
点があり、さらにはエツチング槽にこの亜鉛が入
ると荒れの原因にもなる。 On the other hand, as an electrolytic coloring method, for example,
Publication No. 143593 describes a method of performing secondary electrolytic coloring in Ni salt and Zn salt after forming an anodic oxide film to make it gray. However, this method uses Zn as a coloring substance, which has the drawbacks of extremely poor weather resistance and poor adhesion.Furthermore, if this zinc gets into the etching bath, it can cause roughness. .
電流回復法は、例えば特開昭50−148247号公報
に記載されているように、陽極酸化皮膜生成後、
その印加電圧よりも低い電圧で電流回復処理を行
ない、グレー発色させる方法である。しかし、こ
の方法の場合、グレーの着色酸化皮膜とするため
には、電流回復処理に30分以上を必要として、そ
のため、弱酸性の電解液中での浸漬時間が長いた
め皮膜性能が悪くなるという問題があり、また電
解濃度を上げたり、温度を上げたり、あるいは波
形をコントロールしたりすることにより発色時間
を短縮しようとすると、有彩色になり、無彩色の
灰黒色が得られ難いという問題がある。 The current recovery method is, for example, as described in Japanese Patent Application Laid-Open No. 148247/1983, after the anodic oxide film is formed,
This is a method in which current recovery processing is performed at a voltage lower than the applied voltage to produce a gray color. However, in this method, in order to obtain a gray colored oxide film, the current recovery treatment requires more than 30 minutes, and as a result, the film performance deteriorates due to the long immersion time in the weakly acidic electrolyte. Another problem is that if you try to shorten the color development time by increasing the electrolyte concentration, temperature, or controlling the waveform, the color becomes chromatic, making it difficult to obtain an achromatic gray-black color. be.
また、合金法としては、例えば特開昭51−
99610号公報に、Si1〜５％、Mg0.3〜0.9％を含
有するアルミニウム合金ビレツトを480〜550℃の
温度にて均質化処理し、それを380〜480℃の温度
で予熱して押出し、その後Ｔ−５（焼もどし）処
理した後、陽極酸化処理し、淡灰色の発色皮膜を
生成する方法が記載されている。しかし、このよ
うな方法の場合、Si含量が多いため押出スピード
が遅くなり、作業性が悪いと共に、形状の複雑な
形材では発色物質であるSiの含有量が押出温度、
押出スピードにより押出材の先端部と後端部とで
違うため、均一な発色となり難いという難点があ
る。 In addition, as an alloy method, for example, JP-A-51-
No. 99610 discloses that an aluminum alloy billet containing 1 to 5% Si and 0.3 to 0.9% Mg is homogenized at a temperature of 480 to 550°C, and then extruded by preheating at a temperature of 380 to 480°C. A method is described in which the material is then subjected to T-5 (tempering) treatment, followed by anodization treatment to produce a pale gray colored film. However, in the case of such a method, the extrusion speed is slow due to the high Si content, resulting in poor workability.In addition, in the case of complex-shaped shapes, the content of Si, which is a color-forming substance, increases due to the extrusion temperature.
Since the extrusion speed is different between the front end and the rear end of the extruded material, it is difficult to achieve uniform coloring.
さらに、時効処理を伴なう方法としては、例え
ば特公昭57−23759号公報に、6063系アルミニウ
ム合金を押出し、冷却後Mg2Si析出相を過時効状
態にしてβ′中間相となるように焼戻処理し、その
後苛性エツチング処理及び酸浸漬処理の前所後に
陽極酸化することによりグレー発色皮膜を生成す
る方法が記載され、また、特公昭54−32615号公
報には、Mg、Siを主成分とするアルミニウム合
金を過時効ぎみに焼戻し処理した後、硫酸を主体
とした電解液中にて陽極酸化処理し、その後その
印加電圧より低い電圧にて処理することにより、
グレー発色皮膜を生成する方法が記載されてい
る。しかし、このような方法の場合、アルミニウ
ム合金形材を過時効にさせるため、強度的に劣
り、また熱エネルギー消費量の増大にもなり、し
かも生産性も悪いという難点がある。 Furthermore, as a method involving aging treatment, for example, Japanese Patent Publication No. 57-23759 discloses a method in which a 6063 series aluminum alloy is extruded, and after cooling, the Mg 2 Si precipitated phase is brought into an overaged state and becomes a β' intermediate phase. A method is described in which a gray colored film is produced by tempering, followed by anodizing before and after caustic etching and acid immersion. After tempering the aluminum alloy as a component to avoid overaging, anodizing it in an electrolyte mainly composed of sulfuric acid, and then treating it at a voltage lower than that applied voltage.
A method of producing a gray colored film is described. However, in the case of such a method, since the aluminum alloy shape is over-aged, it is inferior in strength, increases thermal energy consumption, and has disadvantages in that productivity is also poor.
前記したように、アルミニウム合金表面に不透
明無彩色系の着色皮膜を形成させる方法としては
種々の方法が知らてれいるが、いずれも一長一短
を有する。
As described above, various methods are known for forming an opaque achromatic colored film on the surface of an aluminum alloy, but each method has advantages and disadvantages.
ところで、アルミニウム合金を陽極酸化してい
る際に電圧を急激に低電圧に切替えるか、あるい
は一旦通電を停止して電圧を零に下げてから陽極
酸化処理の印加電圧よりも低い電圧を印加する
と、電流は初期に殆ど流れないが、次第に流れ始
め、やがて定常状態に達する。これは電流回復現
象と呼ばれ、この現象を利用することによつてほ
ぼ無色透明の陽極酸化皮膜を透明無彩色系に着色
できることはよく知られている。 By the way, when anodizing an aluminum alloy, if the voltage is abruptly switched to a lower voltage, or if the current is turned off and the voltage is lowered to zero, then a voltage lower than the applied voltage for anodizing treatment is applied. Initially, almost no current flows, but it gradually begins to flow and eventually reaches a steady state. This is called a current recovery phenomenon, and it is well known that by utilizing this phenomenon, an almost colorless and transparent anodic oxide film can be colored into a transparent achromatic color.
前記した特開昭50−148247号公報、特公昭54−
32615号公報に記載の方法などは、この回復現象
を利用した方法である。 The above-mentioned Japanese Patent Application Publication No. 148247/1983, Japanese Patent Publication No. 1987-148-
The method described in Publication No. 32615 is a method that utilizes this recovery phenomenon.
この電流回復法による着色酸化皮膜の形成方法
は、陽極酸化処理に用いた単一の電解液で行なえ
るなど種々の利点を有するが、前記従来技術の説
明でも述べたように、無彩色系の特に灰黒色の着
色酸化皮膜とするためには、電流回復処理に30分
以上の長時間を要するという基本的な問題があ
る。そのため、弱酸性の電解液中での浸漬時間が
長くなり、その結果、耐食性等の面で皮膜性能が
悪くなるという欠点を有する。一方、電解液の濃
度や温度を上げたり、波形をコントロールしたり
することにより発色時間を短縮しようとすると、
有彩色になつてしまい無彩色系の着色皮膜が得ら
れ難いという問題がある。 This method of forming a colored oxide film using the current recovery method has various advantages such as being able to perform the process using a single electrolytic solution used for anodizing treatment, but as mentioned in the explanation of the prior art, it is difficult to form a colored oxide film. In particular, in order to obtain a gray-black colored oxide film, there is a fundamental problem in that the current recovery treatment requires a long time of 30 minutes or more. Therefore, the immersion time in the weakly acidic electrolyte becomes long, resulting in a disadvantage that the film performance deteriorates in terms of corrosion resistance and the like. On the other hand, if you try to shorten the color development time by increasing the concentration or temperature of the electrolyte or controlling the waveform,
There is a problem in that the color becomes chromatic and it is difficult to obtain an achromatic colored film.
このような電流回復法の問題を解決すべく、前
記特公昭54−32615号公報に記載の方法では、押
出加工したアルミニウム合金を過時効ぎみに焼戻
し処理したものに陽極酸化処理及び電流回復によ
る発色処理を適用しようとするものである。しか
し、この場合、前記したように過時効処理のため
に強度的に劣ることは否めず、また熱エネルギー
消費量の増大につながり、生産性も悪いという新
たな問題が派生する。 In order to solve the problem of the current recovery method, the method described in the above-mentioned Japanese Patent Publication No. 54-32615 involves anodizing and coloring an extruded aluminum alloy that has been tempered to avoid overaging. It is intended to apply processing. However, in this case, as mentioned above, it is undeniable that the strength is inferior due to the over-aging treatment, and new problems arise such as increased thermal energy consumption and poor productivity.
従つて、本発明の目的は、このような問題を解
決し、強度及び耐食性、耐魔耗性等の皮膜性能に
有れた無彩色系灰黒色の着色酸化皮膜を短時間に
生産性よく形成できる方法を提供することにあ
る。 Therefore, the purpose of the present invention is to solve these problems and to form an achromatic grayish-black colored oxide film with high productivity in a short time and having film properties such as strength, corrosion resistance, and wear resistance. The goal is to provide a method that can be used.
本発明の他の目的は、上記目的と関連して、塗
膜の密着性能、塗膜性能に優れた無彩色系灰黒色
の複合皮膜をアルミニウム合金表面に形成できる
方法を提供することにある。 Another object of the present invention, in conjunction with the above object, is to provide a method for forming an achromatic gray-black composite film on the surface of an aluminum alloy, which has excellent adhesion and film performance.
本発明によれば、前記第１の目的を達成するた
め
(A) 押出成型後のアルミニウム合金表面に機械的
操作を加えて応力歪を起こさせ、
(B) 次いで、該アルミニウム合金に時効処理を施
し、
(C) しかる後、前記アルミニウム合金を陽極に接
続して直流電解することにより陽極酸化皮膜を
形成し、
(D) 続いて上記陽極酸化処理の印加電圧より低い
電圧にて直流電解することにより電流回復現象
を生じさせ、無彩色系の着色酸化皮膜を形成す
る
ことを特徴とするアルミニウム合金の不透明無彩
色系皮膜の形成方法が提供される。
According to the present invention, in order to achieve the first object, (A) mechanical operation is applied to the aluminum alloy surface after extrusion molding to cause stress strain, and (B) the aluminum alloy is then subjected to aging treatment. (C) Thereafter, the aluminum alloy is connected to an anode and subjected to direct current electrolysis to form an anodized film, and (D) Subsequently, direct current electrolysis is carried out at a voltage lower than the applied voltage for the above anodizing treatment. Provided is a method for forming an opaque achromatic film on an aluminum alloy, which is characterized by causing a current recovery phenomenon and forming an achromatic colored oxide film.
さらに本発明によれば、前記第２の目的を達成
するため、上記方法により着色酸化皮膜を形成し
た後、さらに(E)電着塗装後、焼付することを特徴
とするアルミニウム合金の不透明無彩色系複合被
膜の形成方法が提供される。 Furthermore, according to the present invention, in order to achieve the second object, an opaque and achromatic color of an aluminum alloy is obtained by forming a colored oxide film by the method described above, and further (E) baking after electrodeposition coating. A method of forming a composite coating is provided.
本発明の方法は、時効処理前の表面調整と電流
回復現象とを組合わせ利用することによつて前記
目的を達成するものである。
The method of the present invention achieves the above object by utilizing a combination of surface conditioning before aging treatment and current recovery phenomenon.
以下、その作用について詳しく説明する。 The effect will be explained in detail below.
一般に6063S合金など、Mg、Siを主要添加元
素とするアルミニウム合金では、強度を上げるた
めに、押出加工後、時効処理を行なつているが、
その際、アルミニウム合金中に固溶している
Mg2SiをGP（）とβ′中間相が共存している析出
相にすることが再も強度を増大させるためには良
いとされている。 Generally, aluminum alloys containing Mg and Si as main additive elements, such as 6063S alloy, are subjected to aging treatment after extrusion processing to increase their strength.
At that time, solid solution in the aluminum alloy
It is said that it is good to make Mg 2 Si into a precipitated phase in which GP() and β' intermediate phase coexist in order to increase the strength.
しかしながら、その後電流回復法による皮膜発
色工程では、Mg2SiがGP（）とβ′中間相が共存
している状態では、前述したように、発色にかな
りの時間を要し、しかも弱酸性液中での滞在時間
が長くなるため着色酸化皮膜の性能も悪くなり、
また仕上り外観、付廻り等も悪くなる。 However, in the subsequent film coloring step using the current recovery method, when Mg 2 Si coexists with GP() and β' intermediate phase, it takes a considerable amount of time for coloring to occur, as mentioned above, and moreover, it takes a long time to develop the color in a weakly acidic solution. As the residence time inside becomes longer, the performance of the colored oxide film deteriorates.
In addition, the finished appearance, handling, etc. will also deteriorate.
逆に、時効処理時間を長く、あるいは時効温度
を高くしてβ′中間相を多くした場合は、短い時間
で発色させることができるが、GP（）相がなく
なるために、強度的にはかなり弱く、建材等には
使用できない。また、熱エネルギー的にも大変な
無駄となる。 On the other hand, if the aging treatment time is increased or the aging temperature is increased to increase the amount of the β′ intermediate phase, color can be developed in a short time, but the strength will be significantly reduced due to the loss of the GP() phase. It is weak and cannot be used as a building material. Moreover, it is a great waste of thermal energy.
本発明の方法は、時効処理前に機械的操作によ
る加工硬化を起こさせる表面調整を行なうことに
よつて、上記２つのポイントを同時に満足させる
ものであり、該表面調整工程により応力歪を起こ
した表面は、その後の時効処理により、応力歪を
起こしていない箇所に比べてMg2Siの析出形態
（析出スピード）に差を生じさせる。 The method of the present invention satisfies the above two points at the same time by performing surface conditioning to cause work hardening by mechanical operation before aging treatment, and the surface conditioning process causes stress strain. The subsequent aging treatment causes a difference in the precipitation form (precipitation speed) of Mg 2 Si on the surface compared to areas where no stress strain has occurred.
すなわち、本発明の方法では、押出加工後時効
処理前に、前記表面調整工程においてアルミニウ
ム合金形材表面部に応力歪を起こさせ、転位状態
を作る。尚、この応力歪を起こさせる力はせいぜ
い0.5〜10Kg／cm3程度のものであるから、応力歪
は形材表層部のみに止まり、形材内深部迄には至
らない。その後、通常の時効処理を施すことによ
り、表面調整工程において応力歪による転位を起
こした表層部のみが、昇温によるMg2Siの析出形
態の移行が早く、通常の時効処理においてもβ′中
間相にまで変化し、その結果、その後の電流回復
法による皮膜発色工程において発色に要する時間
がかなり短くなる。一方、応力歪を起こしていな
い形材内深部では、応力歪が及んでいないため、
Mg2Siの析出形態は当然通常通りであり、従つて
時効処理においても強度を最も増大させるGP
（）＋β′中間相が共存している析出相のままであ
る。その結果、強度は通常の時効処理を施したも
のと同等であり、建材等に使用しても何ら問題は
ない。 That is, in the method of the present invention, after extrusion processing and before aging treatment, stress strain is caused in the surface portion of the aluminum alloy shape in the surface conditioning step to create a dislocation state. Note that the force that causes this stress strain is at most about 0.5 to 10 kg/cm 3 , so the stress strain is limited to only the surface layer of the shape material and does not reach deep inside the shape material. After that, by applying normal aging treatment, only the surface layer where dislocations occurred due to stress strain in the surface conditioning process, the Mg 2 Si precipitation form transitions quickly due to temperature rise, and even in normal aging treatment, the β' intermediate As a result, the time required for coloring in the subsequent film coloring step using the current recovery method is considerably shortened. On the other hand, in the deep part of the shape where no stress strain occurs, the stress strain does not apply.
The precipitation form of Mg 2 Si is naturally the same as usual, and therefore GP, which increases the strength the most even in aging treatment.
It remains a precipitated phase in which the ( ) + β′ intermediate phase coexists. As a result, the strength is equivalent to that of a material subjected to normal aging treatment, and there is no problem in using it as a building material.
この様にして処理した結果、電流回復による発
色法に比べて極めて短時間の発色工程で、しかも
付廻性よく、強度、耐薬品性等の性能においても
極めて優れた無彩色系灰黒色の着色皮膜を得るこ
とが可能となつた。また、アルミニウム合金表層
部には、電導性が良好なβ′中間相が多く存在して
いるため、電気が通り易く、従つて発色工程にお
いて発色ムラが少なく、また陽極酸化皮膜自体の
発色であつて２次電解着色等のような異種金属に
よる発色ではないため、異常腐食の問題もない。
さらに、エツチング処理が可能で皮膜表面に均一
なすべり性を付与でき、従つてその後電着塗装を
行なつた場合に、塗膜の均一性が良いと共に、皮
膜表面のなめらかな凹凸により塗膜の密着性も優
れたものとなる。 As a result of this treatment, an achromatic grayish-black coloring is obtained, which is an extremely short coloring process compared to the coloring method using current recovery, has good spreadability, and is extremely superior in performance such as strength and chemical resistance. It became possible to obtain a film. In addition, the surface layer of the aluminum alloy contains a large amount of β' intermediate phase with good conductivity, so electricity can easily pass through it, resulting in less uneven coloring during the coloring process, and less coloring due to the coloring of the anodic oxide film itself. Since the coloring is not caused by dissimilar metals as is the case with secondary electrolytic coloring, there is no problem of abnormal corrosion.
Furthermore, it is possible to perform etching treatment to impart uniform slipperiness to the film surface. Therefore, when electrodeposition is applied afterwards, the film has good uniformity, and the smooth unevenness of the film surface makes the film smooth. Adhesion is also excellent.
なお、後述する比較例からも明らかなように、
単に前記のような表面調整を行なうだけで電流回
復による発色工程を行なわない場合には、表面が
梨地状になるだけで無彩色系の灰黒色の皮膜は得
られない。一方、表面調整工程及び電流回復によ
る発色工程の両方を行なつた場合でも、表面調整
を時効処理の後に行なつた場合には本発明の効果
は得られない。すなわち、本発明の方法による前
記したような作用効果は、時効処理前の表面調
整、時効処理及び電流回復による発色処理の組合
せによつてのみ初めて奏される特有のものであ
る。 Furthermore, as is clear from the comparative examples described later,
If the above-mentioned surface adjustment is simply carried out without carrying out the coloring step by current recovery, the surface will only become satin-like and an achromatic gray-black film will not be obtained. On the other hand, even if both the surface conditioning step and the coloring step by current recovery are performed, the effects of the present invention cannot be obtained if the surface conditioning is performed after the aging treatment. That is, the above-mentioned effects of the method of the present invention are unique and can only be achieved by a combination of surface conditioning before aging treatment, aging treatment, and coloring treatment by current recovery.
以下、本発明の方法の各工程について説明す
る。 Each step of the method of the present invention will be explained below.
(A) 表面調整処理
まず、常法に従つて押出成型したアルミニウ
ム合金に、機械的操作による表面調整を施す。
この表面調整は、押出後時効処理（Ｔ−５処
理）前に、形材表面に部分的に又は全体的に圧
力等を加えることにより、その表層部のみに応
力歪（転位、格子ひずみ）を起こさせることを
目的とし、従つて食刻など化学的処理は含まな
い。(A) Surface conditioning treatment First, an aluminum alloy extruded according to a conventional method is subjected to surface conditioning by mechanical operation.
This surface conditioning is done by applying pressure, etc. partially or completely to the surface of the profile before aging treatment (T-5 treatment) after extrusion, to create stress strain (dislocation, lattice strain) only in the surface layer. The purpose is to induce this process, and therefore it does not include chemical treatments such as etching.
この表面調整の手法としては、ガラス粒、
砂、鉄粉、アルミナ粒子等の砥粒を吹き付ける
ブラスト法、水等の液体を高圧にて噴射する高
圧噴射法、ブラシ等によりアルミニウム合金表
面を傷付けるブラシ法、エンボス版ロールを使
用するローラー法、型プレスにより圧刻するプ
レス法等の各種機械的手段がある。 As a method for this surface adjustment, glass grains,
A blasting method that sprays abrasive grains such as sand, iron powder, or alumina particles, a high-pressure jetting method that sprays liquid such as water at high pressure, a brush method that scratches the aluminum alloy surface with a brush, etc., a roller method that uses an embossed roll, There are various mechanical means such as a press method in which stamping is performed using a die press.
この表面調整は、押出後冷却された常温の押
出形材に施してもよいし、押出直後の比較的高
温状態の押出形材に施してもよい。例えば、作
業性の向上を狙い、押出直後のアルミニウム合
金に、その押出金型と同形状で一定間隔のクリ
アランスのある金型もしくは金枠（治具）に多
数の高圧噴射の噴射溝（穴）を設け、水又は研
磨材等を噴射しながら連続的に表面調整した
り、あるいは上記高圧噴射に代えて、押出金型
後に配設した金型もしくは金枠内部に、例えば
金属もしくはセラミツクの爪状の治具を配設
し、これによつて一定圧力で形材表面をこする
方法も採用できる。 This surface conditioning may be performed on an extruded shape at room temperature that has been cooled after extrusion, or may be performed on an extruded shape in a relatively high temperature state immediately after extrusion. For example, with the aim of improving workability, a large number of high-pressure injection grooves (holes) are installed in a mold or metal frame (jig) that has the same shape as the extrusion mold and has a certain gap of clearance in the aluminum alloy immediately after extrusion. The surface may be adjusted continuously by spraying water or an abrasive, or instead of the high-pressure spray described above, a metal or ceramic nail-shaped It is also possible to use a method in which a jig is installed and the surface of the profile is rubbed with a constant pressure.
例えば、シヨツトブラスト法（砥粒Al2O3）
により表面調整を行なつた場合の砥粒投射圧力
と発色度との関係を第２図に示す。ここでいう
発色度とは（以下同じ）、発色の度合を意味し
ており、発色の濃淡をL*（JIS規格）で表現し
ている。発色度は数値L*が大きい程淡く、数
値L*が小さい程濃いことを示している。同図
から、投射圧力2.0〜5.0Kg／cm2でほぼ一定の発
色度が得られることがわかり、このことにより
製品の発色ムラの生じるのを回避する対策の一
助にすることができ、またこの程度の応力によ
る歪は形材上層部のみに止まり、その後酸化皮
膜生成後においても、このような歪あるいは傷
による性能抵下は全く認められない程度のもの
である。 For example, shot blasting method (abrasive Al 2 O 3 )
FIG. 2 shows the relationship between the abrasive projection pressure and the degree of color development when the surface is adjusted by the following methods. The degree of color development here (the same applies hereinafter) means the degree of color development, and the shade of color development is expressed in L * (JIS standard). The degree of color development indicates that the larger the value L * is, the lighter the color is, and the smaller the value L * is, the darker the color is. From the same figure, it can be seen that a nearly constant degree of color development can be obtained with a projection pressure of 2.0 to 5.0 Kg/ cm2 , which can be used as a measure to avoid uneven color development of products. The distortion due to the stress is limited to only the upper layer of the shape, and even after the oxide film is formed, there is no noticeable deterioration in performance due to such distortion or scratches.
(B) 時効処理（Ｔ−５処理）
上記表面調整を行なつたアルミニウム形材
に、次に常法に従つて時効処理を施す。これに
より、上記表面調整にて応力歪を起こした所
が、Mg2Siの析出相がβ′中間相になる。一方、
形材内深部は表面調整の影響が及ばないため、
通常のGP（）とβ′中間相が共存する状態にな
つている。(B) Aging treatment (T-5 treatment) The aluminum profile subjected to the above surface conditioning is then subjected to an aging treatment according to a conventional method. As a result, the precipitated Mg 2 Si phase becomes a β' intermediate phase at the location where stress strain occurs during the surface adjustment. on the other hand,
The deep part inside the shape is not affected by surface conditioning, so
The normal GP() and β' intermediate phase coexist.
時効処理について説明すると、例えばアルミ
ニウム合金Ａ−6063S材の場合、時効硬化温度
と時間との合金の硬度に及ぼす影響は第１図に
示すとおりである。すなわち、いずれの温度に
おいてもある時間経過後に硬度は最大値とな
り、この段階の時効硬化を完全時効硬化と定義
する。本発明においても、この時効処理におい
て完全時効硬化に至る程度まで処理することが
好ましい。 To explain the aging treatment, for example, in the case of aluminum alloy A-6063S material, the influence of age hardening temperature and time on the hardness of the alloy is as shown in FIG. That is, the hardness reaches its maximum value after a certain period of time at any temperature, and age hardening at this stage is defined as complete age hardening. Also in the present invention, it is preferable to carry out this aging treatment to the extent that complete age hardening is achieved.
第１図から明らかなような、処理温度が高け
れば完全時効に至るまでの処理時間が短く、処
理温度が低ければ処理時間も長い。また、アル
ミニウム合金の材質や処理温度によつては、一
旦完全時効の硬度に達した後、処理時間が長く
なると硬度が低下する傾向にあるので、アルミ
ニウム合金の材質に応じて最適条件を設定すれ
ばよい。 As is clear from FIG. 1, the higher the treatment temperature, the shorter the treatment time until complete aging, and the lower the treatment temperature, the longer the treatment time. Also, depending on the material and processing temperature of the aluminum alloy, once the hardness reaches full aging, the hardness tends to decrease as the processing time increases, so it is necessary to set the optimum conditions according to the material of the aluminum alloy. Bye.
時効処理の条件としては、アルミニウム合金
の材質によつても相違するが、一般に130〜250
℃の温度条件で１〜30時間行なうとよい。130
℃未満では希望する硬度に達する迄に時間がか
かり過ぎるため、生産性が悪く、一方、250℃
を越えると均一なる時効硬化ができないので好
ましくない。また、１時間未満では同様に均一
なる時効硬化ができず、一方、30時間を越える
と時間がかかり過ぎるため、生産性が悪くな
る。 The aging treatment conditions vary depending on the material of the aluminum alloy, but generally 130 to 250
It is preferable to carry out the reaction at a temperature of 1 to 30 hours. 130
Below 250°C, it takes too long to reach the desired hardness, resulting in poor productivity;
Exceeding this is not preferable because uniform age hardening cannot be achieved. Moreover, if it is less than 1 hour, uniform age hardening cannot be achieved, whereas if it exceeds 30 hours, it will take too much time, resulting in poor productivity.
(C) 陽極酸化処理
前記各工程を経たアルミニウム合金を、通常
の方法により脱脂、水洗、必要に応じてスマツ
ト除去等の処理を施した後、常法に従つて、前
記アルミニウム合金を陽極に接続して直流電解
することにより陽極酸化皮膜を形成する。(C) Anodizing treatment After the aluminum alloy that has gone through each of the above steps is subjected to treatments such as degreasing, washing with water, and removing smut as necessary, the aluminum alloy is connected to an anode according to a conventional method. An anodic oxide film is formed by direct current electrolysis.
すなわち、周知の無機酸及び／又は有機酸の
電解液、例えば、硫酸、クロム酸、リン酸等、
あるいはこれらの混酸、シユウ酸、マロン酸等
あるいはこれらのまたは無機酸との混酸などを
含有する電解液中で、直流もしくはこれに類似
の電流波形を使用して、前記アルミニウム合金
を陽極酸化処理する。陽極酸化処理の印加電
圧、印加時間等は常法通りで充分であるが、通
常、処理液の種類によるものが、５〜100Vの
範囲で行なう。5V未満では希望する皮膜厚を
得るのに長時間必要であり、生産性が悪く、一
方、100Vを越えると皮膜厚のバラツキが大き
く、また高電圧での処理のためのエネルギー的
にも無駄が大きいので望ましくない。 That is, well-known inorganic acid and/or organic acid electrolytes, such as sulfuric acid, chromic acid, phosphoric acid, etc.
Alternatively, the aluminum alloy is anodized using direct current or a current waveform similar to this in an electrolytic solution containing a mixed acid of these, oxalic acid, malonic acid, etc., or a mixed acid of these or an inorganic acid. . The applied voltage, application time, etc. for the anodizing treatment may be the same as usual and are sufficient, but it is usually carried out at a voltage in the range of 5 to 100 V, depending on the type of treatment liquid. If it is less than 5V, it will take a long time to obtain the desired film thickness, resulting in poor productivity.On the other hand, if it exceeds 100V, there will be large variations in film thickness, and there will be a waste of energy due to high voltage processing. It is undesirable because it is large.
(D) 電流回復法による皮膜発色処理
上記陽極酸化処理後、その印加電圧より低い
電圧にて、アルミニウム合金を陽極として直流
通電し、電流回復させる。この電流回復の条件
は、処理液の種類にもよるが、陽極酸化処理の
印加電圧よりも低い0.5〜80.0Vの範囲で１〜
100分、好ましくは1.0〜50.0Vの範囲で１〜50
分行なう。0.5V未満では発色に長時間を要し、
生産性、皮膜性能が悪くなるので好ましくな
く、一方、80Vを越えると発色ムラを生ずるの
で好ましくない。また同様に、１分未満では発
色ムラを生じ、一方、100分を越えると発色時
間が長過ぎるため生産性、皮膜性能が悪くなる
ので好ましくない。(D) Film coloring treatment by current recovery method After the above-mentioned anodizing treatment, DC current is applied to the aluminum alloy as an anode at a voltage lower than the applied voltage to recover the current. The conditions for this current recovery depend on the type of treatment solution, but the voltage range is 1 to 80.0 V, which is lower than the applied voltage for anodizing treatment.
1-50 for 100 minutes, preferably in the range of 1.0-50.0V
Let's do it in minutes. If it is less than 0.5V, it will take a long time for color development.
It is not preferable because it deteriorates productivity and film performance. On the other hand, when it exceeds 80V, uneven coloring occurs and therefore it is not preferable. Similarly, if it is less than 1 minute, uneven coloring will occur, while if it exceeds 100 minutes, the coloring time will be too long, which will deteriorate productivity and film performance, which is not preferable.
尚、電流回復処理液は、陽極酸化処理液と同
一でも、異なつていてもよい。異なる場合に
は、電流回復処理液としては例えば、シユウ
酸、リン酸、マロン酸等を用いるのが望まし
く、また液の電導度に応じて陽極酸化処理電圧
よりも高い電圧を印加する場合もある。同じ処
理液を用いる場合には、陽極酸化処理電流密度
をやや上げ、短時間で陽極酸化皮膜を生成し、
残り時間内にその処理槽にて発色処理の一部を
行ない、その後、本来の皮膜発色工程で発色度
の調整をすればなお良い。また、電流回復は、
陽極酸化処理の印加電圧を低電圧に切り替える
か、一旦通電を停止して電圧を零に下げてから
印加するか、いずれの方法も採用できる。ま
た、電流回復現象は一回出現させるだけでもよ
いが、定常状態に達した後にその印加電圧より
も高いが陽極酸化処理の印加電圧よりも低い電
圧に短時間内に上げ、再度印加電圧を下げる操
作を複数回行なつて、着色度を高めるようにす
ることもできる。 Note that the current recovery treatment liquid may be the same as or different from the anodization treatment liquid. In different cases, it is desirable to use oxalic acid, phosphoric acid, malonic acid, etc. as the current recovery treatment liquid, and a voltage higher than the anodizing treatment voltage may be applied depending on the conductivity of the liquid. . When using the same treatment solution, the anodizing current density is slightly increased to generate an anodized film in a short time.
It is better if a part of the coloring treatment is performed in the processing tank within the remaining time, and then the degree of coloring is adjusted in the original film coloring step. In addition, the current recovery is
Either method can be adopted, such as switching the applied voltage for the anodizing treatment to a lower voltage, or temporarily stopping the current supply to lower the voltage to zero, and then applying the voltage. In addition, the current recovery phenomenon may occur only once, but after reaching a steady state, the applied voltage is increased within a short time to a voltage higher than that applied voltage but lower than the applied voltage for anodizing treatment, and then the applied voltage is lowered again. The degree of coloring can also be increased by performing the operation multiple times.
この電流回復法による皮膜発色処理において
は、前記表面調整処理及び時効処理による効果
によりMg2Siがβ′中間相となつているので、表
面調整を行なわない場合に比べて、発色に要す
る時間が大巾に短かくて済み、その効果種々の
効果が得られる。また、付廻り等もかなり均一
になるため、発色度のコントロールが大変し易
くなる。この発色工程において、一つの形材で
表面調整した所とそうでない所とでの発色度の
比較は第３図に示すとおりであり、前記表面調
整処理により発色度が大巾に改善されることが
わかる。 In film coloring treatment using this current recovery method, Mg 2 Si has become a β' intermediate phase due to the effects of the surface conditioning treatment and aging treatment, so the time required for coloring is shorter than when surface conditioning is not performed. It only needs to be very short, and various effects can be obtained. In addition, since the coverage becomes fairly uniform, it becomes much easier to control the degree of color development. In this color development process, a comparison of the degree of color development between areas where the surface has been conditioned and areas where the surface has not been conditioned using one profile is as shown in Figure 3, and it can be seen that the degree of color development is greatly improved by the surface conditioning treatment. I understand.
(E) 電着塗装
前記各工程により着色酸化皮膜が得られる
が、その後必要に応じて、封孔、半封孔等の処
理を施し、周知の方法に従つて電着塗装、焼付
処理される。(E) Electrodeposition coating A colored oxide film is obtained through each of the above steps, and then, if necessary, treatments such as pore sealing and semi-sealing are performed, followed by electrodeposition coating and baking treatment according to well-known methods. .
前記電流回復による発色法は、多孔質皮膜底
部に存在するバリヤー層の構造を微細な枝分れ
構造することにより、これに当たる光の屈折に
よつて無彩色灰黒色を呈するものであるが、そ
の表面に電着塗膜を付加することにより、光の
屈折がさらに複雑になり、結果的にはアルミニ
ウムの透明感をなくした塗りつぶし感の強い無
彩色系不透明灰黒色（パステル調）を得ること
ができる。また、酸化皮膜表面の凹凸により塗
膜の密着性も向上し、耐食性、耐候性等性能の
優れた塗膜が得られる。 In the coloring method using current recovery, the structure of the barrier layer present at the bottom of the porous film is made into a fine branched structure, and the light that hits it is refracted to produce an achromatic grayish-black color. By adding an electrodeposition coating to the surface, the refraction of light becomes more complicated, and as a result, it is possible to obtain an achromatic opaque gray-black color (pastel tone) with a strong solid appearance that eliminates the transparency of aluminum. can. Moreover, the adhesion of the coating film is improved due to the irregularities on the surface of the oxide film, resulting in a coating film with excellent performance such as corrosion resistance and weather resistance.
なお、前記電流回復法による発色工程後、必
要に応じて無機金属塩を含む電解液中で電解着
色を行なうこともでき、この電解着色工程との
組合せによりパステル調の不透明ブロンズ系、
ゴールド系灰色に着色することが可能となる。 After the coloring step using the current recovery method, electrolytic coloring can be performed in an electrolytic solution containing an inorganic metal salt if necessary, and in combination with this electrolytic coloring step, a pastel-like opaque bronze type,
It becomes possible to color it in a gold-like gray.
また、素材としては、本発明の方法では純ア
ルミニウムは除かれ、Mg、Siを主要添加元素
とするアルミニウム合金、例えばJIS6063S合
金が好適に用いられ、また合金成分を変化さ
せ、Mg2Siの析出がより多くなるようにSi含有
量を多くすれば、さらに大きな効果が得られ
る。 In addition, as for the material, pure aluminum is excluded in the method of the present invention, and aluminum alloys containing Mg and Si as main additive elements, such as JIS6063S alloy, are preferably used. An even greater effect can be obtained by increasing the Si content so that the amount of Si increases.
以上のように、本発明の方法によれば、機械的
操作による表面調整、時効処理及び電流回復法に
よる発色処理の相互作用により、通常の電流回復
による発色法に比べて極めて短時間に、しかも付
廻性よく、無彩色系灰黒色の着色皮膜を得ること
ができる。その結果、例えばこれまでの陽極酸化
処理の時間内に、陽極酸化処理＋皮膜発色処理を
処理でき、形材の部分あるいは全体など任意に無
彩色系不透明灰色に発色させることができる。し
かも、処理時間が短いため耐食性、耐薬品性に優
れ、また発色ムラが少なく、また強度も良好であ
り、そのまま外装材として使用することができ
る。その他、処理が比較的簡単であり、縦吊り、
横吊り、形材形状の規制も必要ないなどの利点が
ある。
As described above, according to the method of the present invention, due to the interaction of surface conditioning by mechanical operation, aging treatment, and coloring treatment by current recovery method, the process can be completed in an extremely short time compared to the usual coloring method by current recovery method. It has good adhesion properties and can produce an achromatic grayish-black colored film. As a result, for example, the anodizing treatment and the film coloring treatment can be carried out within the time required for the conventional anodizing treatment, and the part or the whole of the shape can be arbitrarily colored in an achromatic opaque gray color. In addition, since the processing time is short, it has excellent corrosion resistance and chemical resistance, has little uneven coloring, and has good strength, so it can be used as an exterior material as it is. In addition, processing is relatively easy, vertical hanging,
It has advantages such as no need for horizontal suspension or regulation of the shape of the shape.
また、請求項２に記載のように、発色工程後に
電着塗装を行なうことにより、密着性、均一性に
優れ、しかも皮膜性能の優れた塗りつぶし感の強
い無彩色不透明灰黒色の電着塗膜が得られる。 In addition, as described in claim 2, by performing electrodeposition coating after the coloring step, an achromatic opaque grayish-black electrodeposition coating with excellent adhesion and uniformity and a strong filling feeling with excellent film performance can be obtained. is obtained.
以下、実施例を示して本発明について具体的に
説明する。
The present invention will be specifically described below with reference to Examples.
実施例 １
アルミニウム合金6063Sを押出機にて常法によ
り熱間押出した後、表面調整工程としてシヨツト
ブラスト（砥粒Al2O3、３Kg／cm2）にて表面全体
をわずかに粗面化した。Example 1 After hot extruding aluminum alloy 6063S using an extruder using a conventional method, the entire surface was slightly roughened by shot blasting (abrasive grains Al 2 O 3 , 3 Kg/cm 2 ) as a surface conditioning step. did.
その後、常法通り190℃で４時間時効処理を行
なつた後、希硫酸（15W／ｖ％）液中にて直流
16.7V（電流密度1.3A／ｄm2）で30分間通電して
陽極酸化処理し、11μｍの陽極酸化皮膜を生成し
た。次いで発色工程として、同液中にて該アルミ
ニウム合金を陽極としたまま電圧を6Vにおとし
て電流で15分間通電したところ、無彩色系の灰黒
色の皮膜となつた。 After that, after aging treatment at 190℃ for 4 hours as usual, DC current was applied in dilute sulfuric acid (15W/v%) solution.
Anodic oxidation treatment was performed by applying current at 16.7 V (current density 1.3 A/dm 2 ) for 30 minutes to form an anodic oxide film of 11 μm. Next, as a coloring step, the aluminum alloy was used as an anode in the same solution, and when the voltage was set to 6 V and a current was applied for 15 minutes, an achromatic gray-black film was formed.
その後、常法により沸騰水封孔をした後、キヤ
ス耐食性（JISH−8681）を調べたところ、48時
間でRN10であり、また砂落し摩耗試験（JISH
−8682）を行なつたところ80秒／μｍであり、性
能上問題はなかつた。 After that, after sealing the hole with boiling water using the usual method, the case corrosion resistance (JISH-8681) was examined, and it was found to be RN10 in 48 hours, and the sand abrasion test (JISH-8681) was performed.
-8682), it was 80 seconds/μm, and there was no problem in terms of performance.
また、上記実施例１において、シヨツトブラス
トの際に砥粒投射圧力を種々変えてその発色度へ
の影響を調べた。その結果を第２図に示す。同図
から、砥粒投射圧力を適切に選定することによ
り、製品の発色ムラの発生を回避することができ
る。 Furthermore, in Example 1, the abrasive projection pressure was varied during shot blasting to examine its effect on the degree of color development. The results are shown in FIG. As shown in the figure, by appropriately selecting the abrasive projection pressure, it is possible to avoid uneven coloring of the product.
さらに、発色工程において、１つの形材で表面
調整した所とそうでない所との発色度を調査し
た。その結果を第３図に示す。同図から、形材に
表面調整したり、表面調整しなかつたり、あるい
は発色処理時間を適宜選定することにより、好み
の発色度の製品を得ることができる。 Furthermore, in the color development process, the degree of color development was investigated in areas where the surface had been conditioned using one shape and in areas where it had not. The results are shown in FIG. From the figure, it is possible to obtain a product with a desired degree of coloration by subjecting the shape to surface conditioning or not, or by appropriately selecting the coloring treatment time.
実施例 ２
実施例１において、生成した灰黒色皮膜を沸騰
水封孔の代わりに72℃で５分間半封孔する以外は
全く同様に処理し、その後電着塗装（塗料品名：
エレクロン3700N−関西ペイント(株)製）を130V
で３分行なつた後、170℃で40分間焼付処理をし
た。Example 2 The produced gray-black film was treated in exactly the same manner as in Example 1, except that instead of boiling water sealing, it was semi-sealed at 72°C for 5 minutes, and then electrocoated (paint product name:
Elekron 3700N (manufactured by Kansai Paint Co., Ltd.) at 130V
After 3 minutes at 170°C, it was baked at 170°C for 40 minutes.
その結果、実施例１とは異なり、かなり塗りつ
ぶし感のある不透明無彩色系の灰黒色の皮膜とな
つた。尚、このサンプルについて耐アルカリ性
（0.5％NaOH）を試験したたころ（JISH−
8602）、72時間でRN10であり、性能上問題はな
かつた。 As a result, unlike in Example 1, the film became an opaque, achromatic, grayish-black film with a fairly solid appearance. This sample was tested for alkali resistance (0.5% NaOH) using Takoro (JISH-
8602), RN10 in 72 hours, and there were no performance problems.
比較例 １
実施例１において、表面調整を行なわなかつた
以外は実施例１と全く同じ処理をしたところ、陽
極酸化皮膜に全く発色は見られなかつた。Comparative Example 1 When the same treatment as in Example 1 was performed except that no surface adjustment was performed, no color development was observed in the anodic oxide film.
また、発色工程として、アルミニウム合金を陽
極として直流6Vにて50分間通電したところ、実
施例１と同程度の無彩色系の灰黒色の皮膜となつ
たが、その後キヤス耐食性を調べたところ48時間
でRN9.0であり、また砂落し摩耗試験でも55秒／
μｍであり、実施例１で得られたものに比べて明
らかに性能が劣つていた。 In addition, as a coloring process, when electricity was applied for 50 minutes at 6 V DC using an aluminum alloy as an anode, an achromatic gray-black film similar to that of Example 1 was obtained, but after that, when the corrosion resistance of the cast was examined, it was found that the film was energized for 48 hours. It is RN9.0 and also lasts for 55 seconds/3 in sand drop abrasion test.
μm, and the performance was clearly inferior to that obtained in Example 1.
比較例 ２
実施例２において、表面調整を行なわなかつた
以外は実施例２と全く同じ処理をしたところ、陽
極酸化皮膜に全く発色は見られなかつた。Comparative Example 2 In Example 2, the same treatment as in Example 2 was performed except that no surface adjustment was performed, and no color development was observed in the anodic oxide film.
また、発色工程として、アルミニウム合金を陽
極として直流6Vにて50分間通電したところ、実
施例２と同程度の無彩色系の灰黒色の皮膜となつ
たが、その後の耐アルカリ性試験では72時間で
RN9.0であり、実施例２で得られたものに比べて
明らかに性能が劣つていた。 In addition, as a coloring process, when electricity was applied for 50 minutes at 6 V DC using an aluminum alloy as an anode, an achromatic gray-black film similar to that of Example 2 was obtained, but in the subsequent alkali resistance test, it was found that the film was energized for 72 hours.
RN9.0, and the performance was clearly inferior to that obtained in Example 2.
比較例 ３
実施例１において、発色工程を行なわなかつた
以外は実施例１と全く同じ処理をしたところ、表
面が梨地状になるだけで、無彩色系の灰黒色とは
程遠いものであつた。Comparative Example 3 When the same treatment as in Example 1 was carried out except that the color development step was not performed, the surface only became satin-like, which was far from an achromatic gray-black color.
比較例 ４
実施例１において、表面調整工程を時効処理後
にした以外は実施例１と全く同じ処理をしたとこ
ろ、表面が梨地状になるだけで、無釈色系の灰黒
色とは程遠いものであつた。Comparative Example 4 In Example 1, the same treatment as in Example 1 was carried out except that the surface conditioning step was carried out after the aging treatment. However, the surface only became satin-like, which was far from the plain gray-black color. It was hot.
第１図はアルミニウム合金（Ａ−6063S）の硬
度に及ぼす時効処理温度と処理時間の影響を示す
グラフ、第２図はシヨツトブラスト法の砥粒投射
圧力と発色度との関係を示すグラフ、第３図は表
面調整の発色度に及ぼす影響を示すグラフであ
る。
Fig. 1 is a graph showing the influence of aging treatment temperature and treatment time on the hardness of aluminum alloy (A-6063S), Fig. 2 is a graph showing the relationship between abrasive blasting pressure of shot blasting method and degree of coloration, FIG. 3 is a graph showing the influence of surface conditioning on the degree of color development.
Claims (1)
械的操作を加えて応力歪を起こさせ、 (B) 次いで、該アルミニウム合金に時効処理を施
し、 (C) しかる後、前記アルミニウム合金を陽極に接
続して直流電解することにより陽極酸化皮膜を
形成し、 (D) 続いて上記陽極酸化処理の印加電圧より低い
電圧にて直流電解することにより電流回復現象
を生じさせ、無彩色系の着色酸化皮膜を形成す
る ことを特徴とするアルミニウム合金の不透明無彩
色系皮膜の形成方法。 ２ 請求項１に記載のアルミニウム合金の不透明
無彩色皮膜の形成方法により無彩色系の着色酸化
膜を形成した後、さらに(E)電着塗装後、焼付する
ことを特徴とするアルミニウム合金の不透明無彩
色系複合皮膜の形成方法。[Claims] 1. (A) Applying a mechanical operation to the surface of the aluminum alloy after extrusion molding to cause stress strain, (B) Then subjecting the aluminum alloy to an aging treatment, (C) After that, (D) forming an anodized film by connecting the aluminum alloy to an anode and subjecting it to direct current electrolysis; (D) subsequently causing a current recovery phenomenon by carrying out direct current electrolysis at a voltage lower than the applied voltage for the anodizing treatment; A method for forming an opaque achromatic film on an aluminum alloy, the method comprising forming an achromatic colored oxide film. 2. An opaque aluminum alloy film characterized by forming an achromatic colored oxide film by the method for forming an opaque achromatic film on an aluminum alloy according to claim 1, and then baking after (E) electrodeposition coating. Method for forming an achromatic composite film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3765788A JPH01212796A (en) | 1988-02-22 | 1988-02-22 | Formation of opaque gray film of aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3765788A JPH01212796A (en) | 1988-02-22 | 1988-02-22 | Formation of opaque gray film of aluminum alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01212796A JPH01212796A (en) | 1989-08-25 |
| JPH052751B2 true JPH052751B2 (en) | 1993-01-13 |
Family
ID=12503712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3765788A Granted JPH01212796A (en) | 1988-02-22 | 1988-02-22 | Formation of opaque gray film of aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01212796A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054185A1 (en) * | 2003-12-03 | 2005-06-16 | Construction Research & Technology Gmbh | Azetidine derivatives, method for producing said derivatives and use thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5570134B2 (en) * | 2009-03-30 | 2014-08-13 | アイシン軽金属株式会社 | Method for forming pearl-like anodized film and pastel-colored anodized film |
| CN111235618B (en) * | 2020-01-16 | 2021-10-29 | 长沙鼎日成金属表面处理有限公司 | Anodic oxidation electrophoresis process for high-silicon high-copper aluminum alloy parts |
-
1988
- 1988-02-22 JP JP3765788A patent/JPH01212796A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005054185A1 (en) * | 2003-12-03 | 2005-06-16 | Construction Research & Technology Gmbh | Azetidine derivatives, method for producing said derivatives and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01212796A (en) | 1989-08-25 |
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