JPS61183497A - Surface treatment for patterning of aluminum alloy - Google Patents

Abstract

PURPOSE:To form a colored film which has various densities and is beautiful and resistant to corrosion by machining the surface of an extrusion-molded Al alloy to condition the surface so as to have a pattern and subjecting the surface to anodic oxidation and electrolytic coloring after age hardening. CONSTITUTION:The surface of the Al alloy shape material which is in an non-age-hardened or imperfectly age-hardened state after extrusion molding is flawed or strained to the pattern shape by a mechanical working operation by which the surface is conditioned. The surface is then subjected to the age hardening treatment to put the non-surface-conditioned part into the perfectly or over-age-hardened state. The surface is thereafter subjected to an anodic oxidation film treatment and reforming treatment then to an electrolytic coloring treatment. The surface is otherwise subjected simultaneously to the anodic oxidation film treatment and electrolytic coloring treatment. The colored pattern having the excellent resistance to corrosion, weather, wear, etc., various densities and good contrast is thus formed on the surface of the Al material.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、時効硬化性能を有するアルミニウム合金（
純アルミニウムを除く）の表面に、例えば木目調、プリ
ント調など各種の装飾模様を鮮明に生成できる表面処理
方法に関するものであり、更に詳しくは、アルミニウム
合金の表面に、金属工学的な時効処理操作、機械的な加
工操作並びに電学化学的な電解処理操作を巧みに組合わ
せて施すことにより、極めて簡単な方法で前記アルミニ
ウム合金の表面に濃淡差のある美麗な着色模様を生成で
きると同時に、耐食性の優れた着色皮膜が得られる新規
なアルミニウム合金の模様付は表面処理方法に関する。[Detailed Description of the Invention] [Industrial Application Field] This invention provides an aluminum alloy (
The present invention relates to a surface treatment method that can clearly produce various decorative patterns such as woodgrain or printed patterns on the surface of aluminum alloys (excluding pure aluminum). By skillfully combining mechanical processing operations and electrochemical electrolytic treatment operations, it is possible to generate a beautiful colored pattern with differences in shading on the surface of the aluminum alloy in an extremely simple manner, and at the same time, This invention relates to a surface treatment method for patterning a new aluminum alloy that provides a colored film with excellent corrosion resistance.

〔従来の技術〕[Conventional technology]

従来、アルミニウム材の表面に人工時効硬化処理を利用
して濃淡差のある着色模様を生成させる方法としては、
特開昭５３−８３９４１号の技術、即ちアルミニウムの
素材表面に、所望の模様入りシートを付着し、これを通
常の条件下で人工時効硬化処理したのち、冷却前又は後
に前記模様入りシートを取除き、次いでそのアルミニウ
ム材を陽極として電解着色処理を行なう方法が知られて
おり、この方法に於ける着色模様の生成機構は１時効硬
化処理中に、アルミニウム材の表面に模様入りシートの
付着している部分と付着していない部分とに加熱による
結晶構造の差異をもたらすことによって、その後の電解
着色処理時に着色模様を生成させるようになっている。Conventionally, methods of creating colored patterns with different shades of light and shade using artificial age hardening treatment on the surface of aluminum materials include:
The technique of JP-A No. 53-83941 is to apply a desired patterned sheet to the surface of an aluminum material, subject it to artificial aging hardening under normal conditions, and then remove the patterned sheet before or after cooling. A method is known in which the aluminum material is removed and then subjected to electrolytic coloring using the aluminum material as an anode.The mechanism for producing the colored pattern in this method is that a patterned sheet is attached to the surface of the aluminum material during the 1-age hardening treatment. By heating, a difference in crystal structure is created between the adhered portion and the unadhered portion, thereby producing a colored pattern during the subsequent electrolytic coloring treatment.

また、他の技術による模様付き陽極酸化皮膜の形成方法
としては、特公昭４３−６３６５号公報に記載の方法が
知られており、この方法ではＡ　Ｑ　−Ｍｎ−Ｍｇ系合
金の組成を特別に選定したアルミニウム合金を用い、前
記アルミニウム合金を展伸加工し、該加工工程中または
加工後に特別の熱処理を加え、その後、陽極酸化処理を
行なうことにより、アルミニウム合金の表面にＡＱ−Ｍ
ｎ二元化合物の析出に起因するコントラストのある黒色
模様を生成させている。In addition, as a method for forming a patterned anodic oxide film using another technique, the method described in Japanese Patent Publication No. 43-6365 is known, and in this method, the composition of the A Q -Mn-Mg alloy is specially adjusted. Using the selected aluminum alloy, the aluminum alloy is stretched, subjected to special heat treatment during or after the processing process, and then anodized, thereby forming AQ-M on the surface of the aluminum alloy.
A contrasting black pattern is generated due to the precipitation of the n-binary compound.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

けれども、前記両方法のうち、前者（特開昭５３−８３
９４１号）の方法には次の各項に記載するような問題点
がある。However, of the above two methods, the former (Japanese Unexamined Patent Publication No. 53-83
The method of No. 941) has problems as described in the following sections.

（ａ）アルミニウム材の人工時効硬化処理に際し、時効
硬化処理炉の内部空間は、左右、上下、前後の各端部と
中央部の温度が必ずしも均一ではなく相当な温度差があ
るため、得られる製品の模様のコントロールが難かしい
。(a) During artificial age hardening treatment of aluminum materials, the internal space of the age hardening treatment furnace is not necessarily uniform in temperature between the left and right, top and bottom, front and rear ends and the center, and there is a considerable temperature difference. It is difficult to control the pattern of the product.

（ｂ）他の金属に較べてアルミニウム材の熱伝導率が非
常に高いので、模様入りシートの付着している部分と付
着していない部分との温度差を出すことに困難性が伴な
う関係上、鮮明な濃淡差のある着色模様の生成が至難で
あり、また斑点模様、水玉模様、木目調模様など小さな
模様をアルミニウム材に表出させることが困難である。(b) Since the thermal conductivity of aluminum material is extremely high compared to other metals, it is difficult to create a temperature difference between the areas where the patterned sheet is attached and the areas where it is not attached. For this reason, it is extremely difficult to produce colored patterns with clear shading differences, and it is also difficult to produce small patterns such as spots, polka dots, and woodgrain patterns on aluminum materials.

（Ｃ）人工時効硬化処理を行なう際に、模様入りシート
を付着する工程及び剥脱する工程が必要になり、押出形
材の形状毎に模様入りシートを用意せねばならぬ為、極
めて作業性が悪く、得られる製品もコスト高になる。(C) When performing artificial aging hardening treatment, a process of attaching and peeling off the patterned sheet is required, and a patterned sheet must be prepared for each shape of the extruded shape, making the work extremely difficult. Unfortunately, the resulting product also costs more.

また、後者の方法（特公昭４３−６３６５号）は、この
方法によって得られる模様の形態が全くランダムであり
、任意の模様が得られない事は勿論、その模様が黒白の
コントラストにのみ限定されるため、装飾性のある美麗
な着色模様が得られないと云う難点があった。In addition, in the latter method (Japanese Patent Publication No. 43-6365), the form of the pattern obtained by this method is completely random, and not only is it impossible to obtain an arbitrary pattern, but the pattern is limited to only black and white contrast. Therefore, it was difficult to obtain a decorative and beautiful colored pattern.

この発明の主たる目的は、上記の問題点を悉く解決し、
アルミニウム合金（純アルミニウムを除く）の表面に、
美麗な木目調、プリント調など所望の各種着色模様を簡
単に生成させることのできる新規な模様付は表面処理方
法を確立し、他の目的は、前記の方法と関連して、耐食
性、耐候性、耐摩耗性等の諸性能に優れ、且つ、濃淡差
のあるコントラストの良好な着色模様の生成と、アルミ
ニウム合金への機械的強度の付与を一連の工程で生産性
よく行えるアルミニウム合金の表面処理方法を提供する
ことにある。The main purpose of this invention is to solve all the above problems,
On the surface of aluminum alloys (excluding pure aluminum),
We have established a new patterned surface treatment method that can easily produce various desired colored patterns such as beautiful woodgrain and printed patterns. , a surface treatment for aluminum alloys that has excellent performance such as wear resistance, creates a colored pattern with good contrast between light and shade, and imparts mechanical strength to the aluminum alloy in a series of processes with high productivity. The purpose is to provide a method.

〔問題点を解決するための手段〕[Means for solving problems]

本発明者は前記の目的を達成するため、多年に亘り種々
研究と実験を重ねた結果、押出成形後の完全時効硬化処
理を施す前のアルミニウム合金を未時効硬化又は不完全
時効硬化の状態に於いて、機械的な加工操作により傷や
歪み等を与える表面調整処理を施した後で時効硬化処理
を行ない、非表面調整部を完全時効硬化乃至過時効硬化
としてから陽極酸化皮膜処理と電解着色処理とを同時又
は別々に行なうと、これら各処理の相乗作用によって、
表面調整部（下地模様部）と非表面調整部（下地模様部
以外の背景部）との間に着色の濃淡差が生じ、アルミニ
ウム合金の表面に前記の下地模様が鮮明に表出すること
を知見し、このような新しい知見に基いて特許請求の範
囲中、第１番目に記載せる新規な模様付は表面処理方法
を確立することに成功したものである。In order to achieve the above object, the present inventor has conducted various research and experiments over many years, and as a result, the present inventor has developed an aluminum alloy that has not been subjected to complete age hardening treatment after extrusion molding to an unage hardened or incomplete age hardened state. After surface conditioning treatment that causes scratches, distortions, etc. through mechanical processing operations, age hardening treatment is performed to completely age harden or overage harden the non-surface conditioned areas, and then anodic oxide coating treatment and electrolytic coloring are performed. When these treatments are performed simultaneously or separately, the synergistic effect of each of these treatments will result in
There is a difference in the shade of color between the surface adjustment area (base pattern area) and the non-surface adjustment area (background area other than the base pattern area), and the base pattern clearly appears on the surface of the aluminum alloy. Based on this new knowledge, we have succeeded in establishing a surface treatment method for the novel patterning described in the first aspect of the claims.

また本発明者は前記第１番目の発明について更に研究と
追試を続けるうち、当該発明に於ける時効硬化処理後の
陽極酸化皮膜処理工程と電解着色処理工程との間に、無
機酸又は有機酸もしくはこれらの混酸の水溶液中で交流
電解又は直流陰極電解により前記陽極酸化皮膜を改質す
る工程を介在させて処理すれば、着色模様の濃淡差を更
に明確にし、模様のコントラストを一層鮮明にした着色
模様皮膜が得られることを知見し、このような知見に基
いて特許請求の範囲中、第２番目に記載せる模様付は表
面処理方法を提供することに成功したものである。Further, while continuing research and supplementary tests on the first invention, the present inventor found that in the invention, between the anodic oxide film treatment step after age hardening treatment and the electrolytic coloring treatment step, inorganic acid or organic acid Alternatively, if the anodic oxide film is modified by alternating current electrolysis or direct current cathodic electrolysis in an aqueous solution of these mixed acids, the difference in shade of the colored pattern becomes clearer and the contrast of the pattern becomes even clearer. It was discovered that a colored patterned film could be obtained, and based on this knowledge, the second claim in the claims has succeeded in providing a surface treatment method.

即ち、本発明によるアルミニウム合金の模様付表面処理
方法は、その構成を要約すると、第１番目の発明による
方法では、押出成形後の未時効硬化又は不完全時効硬化
状態に於けるアルミニウム合金の表面に、機械的な加工
操作により所望の模様状に傷又は歪み等を与える表面調
整処理を施した後で時効硬化処理を行ない、非表面調整
部を完全時効硬化乃至過時効硬化としてから陽極酸化皮
膜処理と電解着色処理とを同時又は別々に行なうことを
特徴とし、また、第２番目の発明による方法では、押出
成形後の未時効硬化又は不完全時効硬化状態に於けるア
ルミニウム合金の表面に、機械的な加工操作により所望
の模様状に傷又は歪み等を与える表面調整処理を施した
後で時効硬化処理を行ない、非表面調整部を完全時効硬
化乃至過時効硬化としてから陽極酸化皮膜処理を施し、
次いで無機酸又は有機酸もしくはこれらの混酸の水溶液
中で交流電解又は直流陰極電解により前記陽極酸化皮膜
の改質処理を施した後、電解着色処理を行なうことを特
徴とするものである。That is, to summarize the structure of the patterned surface treatment method for aluminum alloy according to the present invention, in the method according to the first invention, the surface treatment of an aluminum alloy in an unage hardened or incompletely age hardened state after extrusion molding is performed. After surface conditioning treatment to create scratches or distortions in the desired pattern by mechanical processing, age hardening treatment is performed to completely age harden or overage harden the non-surface conditioned areas, and then apply anodized coating. The method according to the second invention is characterized in that the treatment and the electrolytic coloring treatment are performed simultaneously or separately. After performing surface conditioning treatment to create scratches or distortions in the desired pattern by mechanical processing, age hardening treatment is performed to completely age harden or overage harden the non-surface conditioned portions, and then anodic oxide film treatment is performed. alms,
Next, the anodic oxide film is modified by alternating current electrolysis or direct current cathodic electrolysis in an aqueous solution of an inorganic acid, an organic acid, or a mixed acid thereof, and then an electrolytic coloring treatment is performed.

上記のように、本発明によるアルミニウム合金の模様付
は表面処理方法は、 （Ａ）不完全時効硬化処理工程（未時効硬化を含む）（
Ｂ）表面調整による模様形成工程 （Ｃ）完全時効硬化乃至過時効硬化処理工程（Ｄ）陽極
酸化皮膜形成処理工程 （Ｅ）陽極酸化皮膜改質処理工程 （Ｆ）電解着色処理工程 の各工程に分けることができ、第１番目の発明では、（
Ｅ）の陽極酸化皮膜改質処理工程が存在せず、（Ａ）→
（Ｂ）→（Ｃ）→（Ｄ）→（Ｆ）の順にアルミニウム合
金を処理し、このうち、（Ｄ）の陽極酸化皮膜形成処理
工程と（Ｆ）の電解着色処理工程とは同時に行なうこと
もあるが、第２番目の発明では、（Ａ）→（Ｂ）→（Ｃ
）→（Ｄ）→（Ｅ）→（Ｆ）の順序で全工程の処理が行
なわれるので、次にこれらの各処理工程について、その
処理方法と実施に際して留意すべき事項を各工程別に詳
しく説明する。As mentioned above, the method for patterning and surface treatment of aluminum alloy according to the present invention includes (A) incomplete age hardening treatment step (including unaged hardening);
B) Pattern formation process by surface conditioning (C) Complete aging hardening to overage hardening process (D) Anodic oxide film forming process (E) Anodic oxide film modification process (F) Electrolytic coloring process In the first invention, (
There is no anodic oxide film modification process in E), and (A)→
The aluminum alloy should be treated in the order of (B) → (C) → (D) → (F), of which the (D) anodic oxide film forming process and (F) electrolytic coloring process should be performed at the same time. However, in the second invention, (A) → (B) → (C
) → (D) → (E) → (F) All processes are performed in the order of (F), so next we will explain in detail the processing method and matters to keep in mind when implementing each of these processing steps. do.

（Ａ）不完全時効硬化処理工程 本発明の表面処理方法では、まず押出成形後のアルミニ
ウム合金に不完全時効硬化処理を施すが、この時効硬化
処理は、アルミニウム合金が完全時効硬化に至らない条
件（未時効を含む）で行なう。(A) Incomplete age hardening treatment step In the surface treatment method of the present invention, the aluminum alloy after extrusion is first subjected to incomplete age hardening treatment, but this age hardening treatment is performed under conditions that do not cause complete age hardening of the aluminum alloy. (including untimely cases).

アルミニウム合金の一般的な時効硬化特性を説明すると
、時効硬化処理温度と処理時間とがアルミニウム合金の
硬度に及ぼす影響は、例えば、アルミニウム合金Ａ−６
０６３８材の場合、第１図に示すような曲線となる。即
ち、アルミニウム合金は１７０℃〜２２０℃迄いずれの
時効硬化処理温度でも、ある時間を経過後に硬度が最大
となり、この段階での時効硬化を本明細書中では完全時
効硬化と定義する。従って、前記の不完全時効硬化処理
は、逆に未時効硬化をも含めてこの段階に到達する以前
の時効硬化処理を意味する。To explain the general age hardening characteristics of aluminum alloys, the effects of age hardening treatment temperature and treatment time on the hardness of aluminum alloys are, for example, aluminum alloy A-6.
In the case of 0638 material, the curve is as shown in FIG. That is, the hardness of aluminum alloy reaches its maximum after a certain period of time at any age hardening treatment temperature from 170°C to 220°C, and age hardening at this stage is defined as complete age hardening in this specification. Therefore, the incomplete age hardening treatment described above means age hardening treatment before reaching this stage, including unaged hardening.

図面は高温時効硬化あるいは人工時効硬化の状態を示す
が、こ＼で云う不完全時効硬化処理は、それのみに限ら
ず、室温時効硬化及び自然時効硬化をも含むものであっ
て、極端に云えば長期間放置して自然時効硬化させても
差支えない。けれども、通常は作業性等の点から人工時
効硬化処理を施すことが望ましく、この場合、アルミニ
ウム合金の材質によっても異なるが、一般に１５０℃〜
２０５℃の温度条件で１〜１０時間程度の処理を行なう
ことが好ましい。The drawing shows the state of high temperature age hardening or artificial age hardening, but the incomplete age hardening treatment referred to here is not limited to that, but also includes room temperature age hardening and natural age hardening, and is extremely difficult to describe. For example, it may be allowed to stand for a long period of time to allow natural aging and hardening. However, it is usually desirable to perform artificial age hardening treatment from the point of view of workability, etc. In this case, although it varies depending on the material of the aluminum alloy, it is generally
It is preferable to perform the treatment at a temperature of 205° C. for about 1 to 10 hours.

（Ｂ）表面調整による模様形成工程 この工程では、前記のように未時効硬化又は不完全時効
硬化処理させたアルミニウム合金の押出形材（時効硬化
処理直後の高温状態の御出形材でもよいし、冷却後の常
温の押出形材でもよい）の表面に、次のように機械的な
加工操作により着色模様の下地になる模様を形成するが
、本工程での機械的な加工操作とは、酸やアルカリ液に
よる食刻なと化学的処理以外の総べての加工操作を含む
。つまり、この模様状の表面調整の手段は５例えば、砂
、鉄等の吹付けによるブラスト法、水などの液を高い圧
力でノズルから噴射する高圧噴射法、ブラシによりアル
ミニウム合金の表面を傷付けるブラシ法、レーザー光線
を照射するレーザー光線法、エンボス版ロールを用いる
ローラー法、型プレスにより圧刻するプレス法等のよう
に機械的な加工操作によってアルミニウム合金の表面に
施される。(B) Pattern formation step by surface conditioning In this step, an extruded aluminum alloy shape that has been subjected to unage hardened or incomplete age hardening treatment as described above (an extruded shape in a high temperature state immediately after age hardening treatment may be used) A pattern that will serve as the base for the colored pattern is formed on the surface of the material (which may be an extruded shape at room temperature after cooling) by mechanical processing operations as follows.The mechanical processing operations in this step are as follows: Includes all processing operations other than etching with acids or alkaline liquids and chemical treatments. In other words, there are 5 methods for preparing the patterned surface, for example, a blasting method by spraying sand, iron, etc., a high-pressure injection method in which a liquid such as water is injected at high pressure from a nozzle, and a brush that scratches the surface of the aluminum alloy with a brush. It is applied to the surface of an aluminum alloy by a mechanical processing operation such as a method, a laser beam method in which a laser beam is irradiated, a roller method in which an embossing plate roll is used, a press method in which stamping is performed using a die press, and the like.

前記加工操作の具体的な手段を更に詳しく説明すると、
作業性を向上し得る加工手段の一例としては、アルミニ
ウム合金の押出形状と同形状で一定間隔のクリアランス
のある金型または金枠（治具）に、例えば柾目模様間隔
に高圧噴射用の溝又は孔を配列して設け、水又は研磨材
等を押出形材表面に噴射しながら連続的に表面調整を行
なうようにすれば、複雑な形状の凹凸部にも着色模様の
下地になる模様を施すことができる。この場合、所望の
連続模様（印刷のように長く通った柾目の間隔、ぼかし
に変化のある模様等）を容易に付与できる。また、上記
の高圧噴射に代えて金型もしくは金枠内部に柾目模様間
隔に硬質の金属やセラミック等の爪状の治具を配設し、
これによって一定の圧力でアルミニウム合金の押出形材
を擦る方法も採用することができる。To explain the specific means of the processing operation in more detail,
As an example of a processing method that can improve workability, a mold or a metal frame (jig) that has the same shape as the extruded shape of the aluminum alloy and has a certain clearance, for example, has grooves or grooves for high-pressure injection at straight-grain intervals. By arranging holes and continuously adjusting the surface while spraying water or abrasive material onto the surface of the extruded shape, it is possible to create patterns that serve as the base for colored patterns even on complexly shaped uneven parts. be able to. In this case, a desired continuous pattern (such as long straight-grain intervals like in printing, a pattern with varying shading, etc.) can be easily provided. In addition, instead of the above-mentioned high-pressure injection, claw-shaped jigs made of hard metal or ceramic are placed inside the mold or metal frame at straight-grain intervals,
This also makes it possible to adopt a method of rubbing an extruded aluminum alloy section with a constant pressure.

このほか、未時効硬化又は不完全時効硬化処理されたア
ルミニウム合金の押出形材に傷又は歪み等を与える装置
として、例えばエンボス版ロールで任意の模様に圧刻す
る方法を使用すれば、柾目、板目、文字、絵柄など所望
の模様を容易に形成し、その装飾性を高めることが可能
になり、また、被処理物がパネル形状のものは型プレス
による圧刻手段を用い、複雑な任意の模様を付与するこ
とができる。In addition, if a method of stamping an arbitrary pattern with an embossing plate roll is used as a device to damage or distort an extruded aluminum alloy material that has been subjected to unage hardening or incomplete age hardening treatment, for example, straight grain, straight grain, It is now possible to easily form desired patterns such as board grains, letters, and pictures, and to enhance their decorativeness.In addition, when the object to be processed is in the form of a panel, it is possible to easily form a desired pattern such as a board grain, a letter, a picture, etc. A pattern can be added.

さらに別の方法として、押出成形の段階で形材自体に模
様状の凹凸を付け、金属、セラミック、カーボン等で形
材表面を擦ることによっても模様を付与することができ
るが、表面調整のための機械的な加工手段は、以上の方
法のみに限定されるものではなく、作業性の良好な手段
でアルミニウム合金の表面に模様状の表面調整が行える
方法であればよい。Another method is to create a pattern on the shape itself during the extrusion molding process, and then rub the surface of the shape with metal, ceramic, carbon, etc., to create a pattern. The mechanical processing means is not limited to the above-mentioned methods, but any method may be used as long as the surface of the aluminum alloy can be patterned with a method with good workability.

上記の表面調整による模様形成工程は、前述の未時効硬
化又は不完全時効硬化処理と後述の陽極酸化皮膜着色処
理（陽極酸化皮膜の改質処理を含む）との相乗作用によ
り着色模様表出の下地乃至核となるものであって、傷痕
等による凹部の深さは、必ずしも表面調整（下地模様形
成）の不可決要素ではなく、外観上合格となるダイスマ
ークの深さ程度以内で充分であり、後工程の陽極酸化皮
膜生成後における顕微鏡観察でも、前記の傷痕による性
能低下は全黙認められず、また歪みを与えた部分につい
ても同様に性能の低下は全くない。The above-mentioned pattern formation process by surface conditioning is achieved by the synergistic effect of the above-mentioned unaged hardening or incomplete aging hardening treatment and the later-described anodic oxide film coloring treatment (including modification treatment of the anodic oxide film). The depth of the recesses caused by scratches, etc., which form the base or core, is not necessarily an indispensable factor for surface preparation (base pattern formation), and it is sufficient that it is within the depth of the dice mark to pass the appearance. Microscopic observation after the anodic oxide film was formed in the post-process showed no deterioration in performance due to the scratches, and similarly there was no deterioration in performance at all in the strained portions.

なお、押出成形直後の高温のアルミニウム合金に機械的
な加工操作で下地模様を形成する際には、材料の硬度が
かなり軟かく形状不良となる恐れがあるので、未時効硬
化状態での表面調整に於いては、特にこの点に注意しな
ければならない。In addition, when forming a base pattern by mechanical processing on a high-temperature aluminum alloy immediately after extrusion, the hardness of the material is quite soft and there is a risk of the shape being defective, so surface preparation in an unageed hardened state is necessary. Particular attention must be paid to this point.

（Ｃ）完全時効硬化乃至過時効硬化処理工程この工程で
行なわれる時効硬化処理は、前に述べた（Ａ）の不完全
時効硬化処理工程（未時効硬化を含む）での不完全な時
効硬化を補足し、非表面調整部を完全時効硬化乃至過時
効硬化とするものであって、前記（Ａ）工程でのアルミ
ニウム合金の時効硬化度合により処理条件が異なるが、
この場合、完全時効硬化とは１図面に示す如くいずれの
時効硬化処理温度に於いても成る時間経過後に硬度が最
大値となる段階とし、過時効硬化とは、いずれの時効硬
化処理温度に於いても成る時間経過後に硬度が最大値を
経て下降する時点以後のものを云う。(C) Complete age hardening to overage hardening treatment step The age hardening treatment performed in this step is the incomplete age hardening treatment performed in the incomplete age hardening treatment step (including unaged hardening) of (A) described above. In addition, the non-surface-adjusted part is completely age-hardened or over-age hardened, and the treatment conditions differ depending on the degree of age hardening of the aluminum alloy in the step (A).
In this case, complete age hardening is the stage at which the hardness reaches its maximum value after a period of time at any age hardening temperature as shown in Figure 1, and overage hardening is the stage at which the hardness reaches its maximum value at any age hardening temperature. This refers to the point at which the hardness reaches its maximum value and then decreases after a certain amount of time has elapsed.

そして、本工程（Ｃ）での完全時効硬化乃至過時効硬化
処理は、（Ａ）工程の不完全時効硬化処理の温度と同じ
でなくてもよく、任意の温度で処理してもよいが、一般
には同じか又はそれよりも高い温度に設定した方が作業
性の点で有利であり、また−次より二次時効硬化処理の
温度を高める二段時効硬化処理で完全時効硬化乃至過時
効硬化処理としてもよい。The complete age hardening to overage hardening treatment in this step (C) does not need to be the same as the temperature of the incomplete age hardening treatment in step (A), and may be performed at any temperature. In general, it is advantageous in terms of workability to set the temperature at the same or higher temperature, and in addition, complete age hardening or overage hardening can be achieved by two-stage age hardening treatment in which the temperature of the second age hardening treatment is raised from next. It may also be processed.

第２図は本工程での完全時効硬化乃至過時効硬化処理時
に於ける処理温度と処理時間との関係を示した曲線グラ
フであって、このグラフに示された数値から実用に好適
な条件は、処理工程の作業性等を考慮すれば、処理温度
１９０〜２２５℃、約７時間前後までの処理が有効な範
Ｉｌ！（図中の斜線で示した領域）である。Figure 2 is a curve graph showing the relationship between treatment temperature and treatment time during the complete age hardening to overage hardening treatments in this process, and from the values shown in this graph, the conditions suitable for practical use are determined. Considering the workability of the treatment process, treatment at a treatment temperature of 190 to 225°C for up to about 7 hours is effective. (area indicated by diagonal lines in the figure).

（Ｄ）陽極酸化皮膜形成処理工程 前記の各工程（Ａ）　（Ｂ）　（Ｃ）を経たアルミニウ
ム合金は、次に通常の方法により脱脂、水洗し、必要に
応じてスマット除去等の前処理を行なっ□た後１周知の
電解浴による陽極酸化処理を施してその表面に陽極酸化
皮膜を形成する。(D) Anodic oxide film formation treatment process The aluminum alloy that has gone through each of the above steps (A), (B), and (C) is then degreased and washed with water using the usual method, and if necessary, pre-treated to remove smut. After this, an anodic oxidation treatment is performed using a well-known electrolytic bath to form an anodic oxide film on the surface.

この場合の電解条件については別段新しい方法を用いる
必要がなく、常法の通り無機酸又は有機酸の電解液１例
えば硫酸、クロム酸、リン酸、あるいはこれらの混酸、
シュウ酸、マロン酸もしくはこれらと無機酸との混酸等
を含有する電解液中で、直流もしくは交流又はこれらと
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
酸化処理すればよく、電解処理の印加電圧及び印加時間
等は常法通りで充分である。Regarding the electrolysis conditions in this case, there is no need to use a new method, and as usual, an inorganic acid or organic acid electrolyte 1 such as sulfuric acid, chromic acid, phosphoric acid, or a mixed acid thereof,
The aluminum alloy may be anodized using direct current, alternating current, or a similar current waveform in an electrolytic solution containing oxalic acid, malonic acid, or a mixed acid of these and an inorganic acid. The applied voltage, application time, etc. are sufficient as usual.

（Ｅ）　Ｉｌｌｌｌ化皮膜改質処理工程この工程は、本
発明による二つの表面処理方法のうち、特に第２番目の
発明に係る方法にのみ適用するもので、前記の各工程（
Ａ）　（Ｂ）　（Ｃ）　（Ｄ）を経て得られたアルミニ
ウム合金表面の陽極酸化皮膜を以下に述べる交流電解改
質処理法と直流陰極電解改質法のいずれかによって処理
する。(E) Illllization film modification treatment step This step is applied only to the method according to the second invention among the two surface treatment methods according to the present invention.
A) (B) (C) The anodic oxide film on the surface of the aluminum alloy obtained through (D) is treated by either the AC electrolytic reforming method or the DC cathodic electrolytic reforming method described below.

これらの陽極酸化皮膜改質処理は、後記する（Ｆ）の工
程で着色される模様をより一層鮮明に表示させるために
行なうもので、その処理条件としては、前記（Ｄ）の陽
極酸化皮膜形成処理工程で用いた電解質、あるいはそれ
に後記する金属塩等の添加剤を加えたもの、または異な
った電解質でもよいが、これらの電解液中で交流電解又
は直流陰極電解する方法で処理されるので、その処理方
法を次に掲げて説明する。　　　　　　（（イ）交流電
解改質処理方法 この方法では、前記のアルミニウム合金を硫酸、リン酸
、クロム酸等の無機酸又はシュウ酸等の有機酸もしくは
これらの混酸の水溶液中で交流またはこれと同等の性質
を有する電流波形を通電することにより、前記陽極酸化
皮膜を二重皮膜構造に改質する。その際の電解条件は常
法の通りで充分可能であるが、好ましくは電解電圧５〜
３０Ｖ、電解時間１〜３０分の条件で行なう。These anodic oxide film modification treatments are performed in order to display the pattern colored in the step (F) described later more clearly, and the processing conditions include the above-mentioned (D) anodic oxide film formation. The electrolyte used in the treatment process, or a different electrolyte with additives such as metal salts described later may be used, but since the treatment is performed using AC electrolysis or DC cathodic electrolysis in these electrolytes, The processing method will be described below. ((a) AC electrolytic reforming treatment method In this method, the aluminum alloy described above is heated in an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, chromic acid, an organic acid such as oxalic acid, or a mixed acid thereof in an alternating current or equivalent solution. The anodic oxide film is modified into a double film structure by applying current with a current waveform having the following properties.The electrolytic conditions at this time may be the same as the usual method, but preferably the electrolytic voltage is 5 to 5.
The electrolysis is carried out under conditions of 30V and electrolysis time of 1 to 30 minutes.

本工程での交流電解による二次陽極酸化処理は、着色皮
膜の生成を目的とするものではなく、前工程での一次陽
極酸化処理と相俟って二重皮膜構造の陽極酸化皮膜を形
成させるものであって、この二重皮膜の生成によってそ
の後の電解着色処理により得られる着色模様は、下地模
様部分と背景部分との着色濃淡差が一層顕著になり、着
色模様のコントラストがより鮮明なものになる。The secondary anodic oxidation treatment by AC electrolysis in this process is not intended to produce a colored film, but in conjunction with the primary anodization treatment in the previous process, it forms an anodic oxide film with a double film structure. Due to the formation of this double film, the colored pattern obtained by the subsequent electrolytic coloring treatment will have a more pronounced difference in color shading between the base pattern part and the background part, and the contrast of the colored pattern will be clearer. become.

口）直流陰極電解改質法 この方法は、陽極酸化皮膜の改質に交流を使用せずに、
硫酸−リン酸等の無機酸からなる電解液中で前記アルミ
ニウム合金（−次陽極酸化皮膜が形成されているもの）
を陰極に接続し、直流またはこれと同等の性質を有する
電流波形を用いて前記アルミニウム合金を通電処理する
。(1) Direct current cathodic electrolytic modification method This method does not use alternating current to modify the anodic oxide film.
The above aluminum alloy (on which a sub-anodized film is formed) in an electrolytic solution consisting of an inorganic acid such as sulfuric acid and phosphoric acid.
is connected to the cathode, and the aluminum alloy is energized using direct current or a current waveform having properties equivalent to direct current.

この通電処理によりアルミニウム合金表面の酸化皮膜に
は溶解作用が生じるが、その際、下地模様部分と他の部
分（背景部分）とでは電流の流れる量が異なるので、両
者間の皮膜の性質に違いができ、その結果、後工程での
電解着色処理によって着色模様のコントラストがより一
層顕著になる。This current treatment causes a dissolution effect on the oxide film on the aluminum alloy surface, but at this time, the amount of current flowing is different between the base pattern part and other parts (background part), so the properties of the film between the two are different. As a result, the contrast of the colored pattern becomes even more pronounced through the electrolytic coloring treatment in the subsequent process.

この場合、電解液の濃度、印加電圧、通電時間等は常法
通りで充分であるが、好ましくは印加電圧３〜２０Ｖ、
通電時間２０秒〜１０分の条件で行なう。In this case, the concentration of the electrolytic solution, the applied voltage, the current application time, etc. are sufficient as usual, but preferably the applied voltage is 3 to 20 V,
It is carried out under the condition that the current application time is 20 seconds to 10 minutes.

（Ｆ）電解着色処理工程 本工程では、第１番目の発明の場合は前記（０）の陽極
酸化皮膜形成処理を完了したアルミニウム合金、第２番
目の発明の場合は更に前記（Ｅ）の陽極酸化皮膜改質処
理を施したアルミニウム合金を被処理物として、次に無
機金属塩を含む電解液中で交流電解又は直流陰極電解し
、被処理物表面の陽極酸化皮膜を着色する。(F) Electrolytic coloring treatment step In this step, in the case of the first invention, the aluminum alloy that has been subjected to the anodic oxide film forming treatment of the above (0), and in the case of the second invention, the anode of the above (E) An aluminum alloy subjected to oxide film modification treatment is used as a workpiece, and then AC electrolysis or DC cathodic electrolysis is performed in an electrolytic solution containing an inorganic metal salt to color the anodic oxide film on the surface of the workpiece.

その際、電解液中の無機金属塩としては、例えばニッケ
ル、コバルト、クロム、銅、カドミウム、チタン、マン
ガン、モリブデン、スズ、マグネシウム、銀、鉛等の硫
酸塩、塩酸塩、シュウ酸塩など従来から周知の各種無機
金属塩を使用でき、また電解条件も常法の通りで充分で
ある。In this case, inorganic metal salts in the electrolyte include sulfates, hydrochlorides, oxalates of nickel, cobalt, chromium, copper, cadmium, titanium, manganese, molybdenum, tin, magnesium, silver, lead, etc. Various well-known inorganic metal salts can be used, and conventional electrolytic conditions are sufficient.

このような電解着色処理を行なうと、アルミニウム合金
の表面には、耐食性や耐候性などの各種性能に優れた着
色皮膜が形成されると共に、前記（Ｂ）の工程で表面調
整された下地模様の部分（傷又は歪み等を与えた部分）
が完全時効硬化乃至過時効硬化に加え表面調整による加
工硬化によりこれ以外の背景部分（模様のついてない部
分）よりも過時効硬化の状態になっているので淡く着色
され、機械的な加工操作でアルミニウム合金の表面に施
された表面調整による模様そのものが着色模様として鮮
明に表出し、着色処理後のアルミニウム合金は、必要に
応じて更に次の塗装工程に送られ、周知の方法によって
塗装処理及び焼付乾燥処理される。When such electrolytic coloring treatment is performed, a colored film with excellent corrosion resistance, weather resistance, and various other properties is formed on the surface of the aluminum alloy, and the underlying pattern that has been surface-conditioned in the step (B) above is also formed. Part (part with damage or distortion, etc.)
Due to complete age hardening or over age hardening, as well as work hardening due to surface conditioning, it is in a state of over age hardening compared to the other background areas (areas with no pattern), so it is colored faintly, and due to mechanical processing operations. The pattern itself created by the surface conditioning applied to the surface of the aluminum alloy clearly appears as a colored pattern, and the aluminum alloy after the coloring treatment is further sent to the next painting process as necessary, and is painted and coated using a well-known method. Baked and dried.

以上の各処理工程を経て本発明方法による表面処理は総
べて完了するが、最後にこの発明を適用し得るアルミニ
ウム合金の組成を説明すると、本発明では、当然なこと
ながら時効硬化の起り難い純アルミニウムは除かれる。The surface treatment according to the method of the present invention is completed through each of the above treatment steps.Finally, to explain the composition of the aluminum alloy to which the present invention can be applied, the present invention naturally makes it difficult for age hardening to occur. Pure aluminum is excluded.

そして、使用可能なアルミニウム合金には、焼入れや焼
戻し等の熱処理により強度を高めるアルミニウム合金、
即ち主要添加物としてＣｕ、　Ｍｇ−５ｉ、ｌｎ　　Ｍ
ｇ等を添加したものが好適例に挙げられるが、これだけ
に限定されるものではなく、また添加元素、加工硬化、
熱処理条件等の組合わせによって着色模様の色調、模様
のコントラストを自由に調整できる。The aluminum alloys that can be used include aluminum alloys whose strength is increased through heat treatment such as quenching and tempering;
That is, Cu, Mg-5i, lnM are used as main additives.
Preferred examples include those to which g is added, but the invention is not limited to this, and additional elements, work hardening,
The color tone of the colored pattern and the contrast of the pattern can be freely adjusted by combining heat treatment conditions, etc.

また、熱処理効果を高め処理時間の短縮を図るために添
加元素量を変えることができる。例えばＡ　Ｑ−Ｍｇ−
Ｓｉ系の合金、　あるいはＡ　Ｑ−Ｍｇ−３ｉ−Ｆｅ系
の合金において、添加量の組合わせによりＳｉの含有量
を過剰とする等の手段によって時効硬化を促進させるこ
とができる。Furthermore, the amount of added elements can be changed in order to enhance the heat treatment effect and shorten the treatment time. For example, A Q-Mg-
In Si-based alloys or AQ-Mg-3i-Fe-based alloys, age hardening can be promoted by increasing the Si content by combining the amounts added.

従っＣ１本発明方法の場合、色調、模様のコントラスト
や処理工程の作業性改善等を目的として、その処理工程
及び処理条件に適合する合金成分のアルミニウム合金を
使用することができる。Therefore, in the case of the C1 method of the present invention, for the purpose of improving color tone, pattern contrast, workability of the processing process, etc., it is possible to use an aluminum alloy whose alloy composition is compatible with the processing process and processing conditions.

〔発明の効果〕〔Effect of the invention〕

以上のように、本発明に係るアルミニウム合金の模様付
は表−面処理方法によれば、未時効硬化又は不完全時効
硬化処理、機械的な加工操作による模様状表面調整処理
、完全時効硬化乃至過時効硬化処理、陽極酸化皮膜形成
処理、陽極酸化皮膜の改質処理及び電解着色処理の各工
程の組合わせによる相乗作用によって、前記模様状表面
調整部と背景部との間に着色濃淡差が生じ、アルミニウ
ム合金の表面に耐食性、耐候性、耐摩耗性等の各種性能
に優れている共に、木目調、プリント調など所望の美麗
な着色模様を生成できる。当然のことながら、このよう
な効果は上記各処理工程の相乗作用によるものであり、
特に陽極酸化皮膜改質処理工程が付加されている第２番
目の発明の方法では、模様のコントラストがより一層鮮
明であると共に、着色性の極めて優秀な着色皮膜が得ら
れるものである。As described above, the patterning of the aluminum alloy according to the present invention can be achieved by surface treatment methods such as unageed hardening or incomplete age hardening, patterned surface conditioning treatment by mechanical processing, complete age hardening or Due to the synergistic effect of the combination of each process of over-aging hardening treatment, anodic oxide film forming treatment, anodic oxide film modification treatment, and electrolytic coloring treatment, a difference in coloring density is created between the patterned surface adjustment part and the background part. It has excellent properties such as corrosion resistance, weather resistance, and abrasion resistance on the surface of the aluminum alloy, and can also produce desired beautiful colored patterns such as woodgrain or printed patterns. Naturally, this effect is due to the synergistic effect of each of the above treatment steps,
In particular, in the method of the second invention, in which an anodic oxide film modification treatment step is added, a colored film with an even clearer pattern contrast and extremely excellent coloring properties can be obtained.

また、本発明方法によれば、着色模様の生成が一連の処
理工程で連続的に行なえる事は勿論、模様状に表面調整
した状態がそのま＼着色コントラスト模様として現出す
るため、表面処理ラインに於ける被処理物のラッキング
形態は横吊り及び縦吊りいずれの方式でもよく、特別に
新しい技術を付加せねばならぬ要素もないので、現在標
準化されでいる設備でも充分に対処できる利点がある。In addition, according to the method of the present invention, not only can the colored pattern be generated continuously in a series of processing steps, but also the state in which the surface has been conditioned into a pattern appears as it is as a colored contrast pattern. The racking method for the workpieces on the line can be either horizontal or vertical suspension, and there is no need to add any special new technology, so it has the advantage that it can be handled satisfactorily with currently standardized equipment. be.

さらに、本発明方法によって処理されたアルミニウム合
金の押出形材は、下地模様の付与により性能低下を招来
する恐れが全熱なく、顕微鏡による陽極酸化皮膜あるい
は着色皮膜の観察によっても欠陥は全く認められず、他
の各種試験結果からも通常の電解着色による着色形材と
何等変りないので、従来製品と同じ用途、つまり内外装
の限定なく自由に選択使用することができるなど数々の
優れた利点を併有するものである。Furthermore, the aluminum alloy extruded shape processed by the method of the present invention has no risk of deterioration in performance due to the addition of an underlying pattern, and no defects are observed when observing the anodic oxide film or colored film under a microscope. Moreover, various test results show that it is no different from ordinary electrolytically colored shapes, so it has many excellent advantages such as being able to be used for the same purposes as conventional products, that is, to be freely selected and used without any restrictions on interior or exterior use. It is held together.

〔発明の実施例〕[Embodiments of the invention]

以下、この発明によるアルミニウム合金の模様付は表面
処理方法の具体的な実施例を次に掲げるが、本発明は必
ずしもこれらの各実施例のみに拘束されるものではない
。Specific examples of the surface treatment method for patterning aluminum alloy according to the present invention will be listed below, but the present invention is not necessarily limited to these examples.

実施例１ 押出成形直後のアルミニウム合金（Ａ　−６０６３８）
の形材表面に凹凸状のカーボンを圧接して模様状に表面
調整し、次いで、温度２１０℃、　４時間の条件にて過
時効硬化処理した後、この合金形材を脱脂、エツチング
、スマット除去し、常法により該形材を１８Ｗ／Ｖ％の
硫酸水溶液中に浸漬して、電流密度１．ＩＡ／ｄｉ　（
電圧約１２Ｖ）、液温２０℃、時間３０分の条件で陽極
酸化処理を行ない、その表面に厚さ約１０μｍの陽極酸
化皮膜を形成した。Example 1 Aluminum alloy (A-60638) immediately after extrusion molding
After applying uneven carbon to the surface of the alloy shape to adjust the surface into a pattern, the alloy shape was subjected to overage hardening treatment at a temperature of 210°C for 4 hours, and then the alloy shape was degreased, etched, and smut removed. Then, the shape was immersed in a 18 W/V% aqueous sulfuric acid solution using a conventional method, and the current density was 1. IA/di (
The anodic oxidation treatment was carried out under the conditions of a voltage of about 12 V), a liquid temperature of 20° C., and a time of 30 minutes to form an anodic oxide film with a thickness of about 10 μm on the surface.

次に、これを水洗後、着色処理として、長さ２００＋ｍ
＋、巾１５０■、高さ１５０ｍｍの容器の一側端部にカ
ーボン対極を配置したものを電解着色装置として用い、
長さ１５０ｎｎ、巾７０ｍｍ、厚さ１．３ｍの前記アル
ミニウム合金形材をカーボン対極との極間距離１８０Ｉ
Ｉｅにして、硫酸４０　ｇ　／　Ｑ、三チオン酸ナトリ
ウムＩｇ／［、硫酸第１錫４ｇＩＱの組成からなる液温
１６℃の電解液中に浸漬し、初期電流密度ＩＡ／ｄｒｒ
ｒ、ＩＯＶの印加電圧で５分３０秒間の交流電解処理を
行なったところ、前記の模様部が背景部に比べて淡色に
着色されている美麗な黄土色の装飾模様が表出した。Next, after washing it with water, it was colored to a length of 200+m.
+, a container with a width of 150 cm and a height of 150 mm with a carbon counter electrode placed at one end of the container was used as an electrolytic coloring device.
The aluminum alloy shape having a length of 150 nn, a width of 70 mm, and a thickness of 1.3 m was separated from the carbon counter electrode by a distance of 180 I.
Ie, sulfuric acid 40 g/Q, sodium trithionate Ig/[, and stannous sulfate 4 g IQ.
When AC electrolysis treatment was carried out for 5 minutes and 30 seconds at an applied voltage of r, IOV, a beautiful ocher decorative pattern in which the pattern part was colored lighter than the background part appeared.

実施例２ 押出成形後、自然冷却したアルミニウム合金（Ａ−６０
６３５）の形材表面に、高圧噴射装置を用いて水を００
２ｍｍのノズルから１０００ｋｇ／ｃｏ？の圧力で噴射
させて模様状に表面調整し、次に２００℃、８時間の条
件で過時効硬化処理を施した。Example 2 Aluminum alloy (A-60
635) using a high-pressure injection device to spray water onto the surface of the profile.
1000kg/co from a 2mm nozzle? The surface was adjusted into a pattern by spraying at a pressure of 200° C., and then an over-aging hardening treatment was performed at 200° C. for 8 hours.

その後、該アルミニウム合金形材を脱脂、エツチング、
スマット除去し、該形材を１８Ｗ／Ｖ％の硫酸水溶液中
に浸漬して、電流密度１　、　ＩＡ／ｄ　ｍ（電圧約１
２Ｖ）、液温２０℃、時間３０分の条件で陽極酸化処理
して厚さ約１０μｍの陽極酸化皮膜を形成した。After that, the aluminum alloy shape is degreased, etched,
After removing the smut, the profile was immersed in a 18 W/V% sulfuric acid aqueous solution at a current density of 1, IA/d m (voltage of approximately 1
2V), a liquid temperature of 20° C., and a time of 30 minutes to form an anodized film with a thickness of about 10 μm.

続いて、陽極酸化皮膜改質処理として、前記陽極酸化処
理浴と同濃度、同温度条件にてカーボン対極との間で電
流密度３Ａ／ｄｒｆ　（電圧約８Ｖ）で８分間交流電解
を行ない、その後、着色処理として、実施例１と同様な
装置を使用し、かつ同条件にて前記アルミニウム合金形
材に交流電解による着色処理を施したところ、模様状に
表面調整された部分が背景に比べてかなり淡い黄土色に
着色された鮮明な装飾模様が表出した。Subsequently, as an anodic oxide film modification treatment, alternating current electrolysis was performed for 8 minutes at a current density of 3 A/drf (voltage approximately 8 V) between a carbon counter electrode at the same concentration and temperature as in the anodic oxidation treatment bath, and then As a coloring treatment, the aluminum alloy shape was colored by alternating current electrolysis using the same equipment as in Example 1 and under the same conditions, and the pattern-like surface-adjusted portions were compared to the background. A clear decorative pattern colored in a fairly pale ocher color appeared.

実施例３ 実施例２の陽極酸化皮膜改質処理を、電流密度ＩＡ／ｄ
ｒｆ（電圧約５Ｖ）で２分間、アルミニウム合金形材を
陰極に接続して直流電解した以外は、前記実施例２と全
く同じ方法で前記アルミニウム合金形材を処理したとこ
ろ、該形材表面に、模様状に表面調整された部分が背景
よりも淡い濃淡差のある美麗な装飾模様が表出した。Example 3 The anodic oxide film modification treatment of Example 2 was carried out at a current density of IA/d.
The aluminum alloy profile was treated in exactly the same manner as in Example 2, except that the aluminum alloy profile was connected to the cathode and subjected to DC electrolysis using RF (voltage of about 5 V) for 2 minutes. , the pattern-like surface adjustment revealed a beautiful decorative pattern with a difference in shading that was lighter than the background.

実施例４ 押出成形直後のアルミニウム合金（Ａ−６０６３３）の
形材表面に、珪砂（粒度１００）を６．４Ｉφのノズル
より空気圧２ｋｇ／ｃｉで噴射して模様状に表面調整を
行なった。Example 4 Silica sand (grain size 100) was sprayed onto the surface of an aluminum alloy (A-60633) profile immediately after extrusion molding at an air pressure of 2 kg/ci from a 6.4 Iφ nozzle to condition the surface in a pattern.

次いで、温度１６０℃、４時間の条件で１次不完全時効
硬化処理を施し、一旦、室温まで冷却した後、温度２０
０℃、２時間の条件で２次時効硬化処理を行ない、然る
後に、実施例３と同様に脱脂、エツチング、スマット除
去し、該形材を１７Ｗ／Ｖ％の硫酸水溶液中に浸漬して
、電流密度１．２Ａ／ｄｍ　（電圧約１２．５Ｖ）　、
液温２０℃、時間３５分の条件で陽極酸化処理し、厚さ
約ｌ００５μｍの陽極酸化皮膜を形成した。その後、陽
極酸化皮膜改質処理として、電流密度１．２Ａ／ｄｉｒ
ｒ（電圧約６Ｖ）で１分３０秒間アルミニウム合金形材
に陰極を接続して直流電解を行なった。次いで、電解着
色処理として、実施例１と同じ容器を使用し、下記の組
成を有する浴温２８℃の電解液中に浸漬して、初期電流
密度ＩＡ／ｄ　ｒｒｒ、１１ｖの印加電圧で３分間交流
電解を行なったところ、サンドブラストを当てた面のみ
が濃茶色となり、他方、サンドブラストを当てない面は
濃茶色となり形材の面により着色の異なる美しい形材と
なった。Next, a primary incomplete age hardening treatment was performed at a temperature of 160°C for 4 hours, and once cooled to room temperature, a temperature of 20°C was applied.
A secondary age hardening treatment was performed at 0°C for 2 hours, followed by degreasing, etching, and smut removal in the same manner as in Example 3, and the shape was immersed in a 17 W/V% sulfuric acid aqueous solution. , current density 1.2A/dm (voltage approximately 12.5V),
Anodizing was carried out at a liquid temperature of 20° C. for 35 minutes to form an anodized film with a thickness of about 1005 μm. After that, as an anodic oxide film modification treatment, a current density of 1.2A/dir was applied.
DC electrolysis was carried out by connecting the cathode to the aluminum alloy shape at r (voltage of about 6 V) for 1 minute and 30 seconds. Next, as an electrolytic coloring treatment, using the same container as in Example 1, it was immersed in an electrolytic solution having the following composition at a bath temperature of 28°C, and was applied for 3 minutes at an initial current density IA/d rrr and an applied voltage of 11 V. When AC electrolysis was performed, only the sandblasted side became dark brown, while the non-sandblasted side became dark brown, resulting in a beautiful shape with different colors depending on the side of the shape.

電解液組成：硫酸ニッケル　　　　２５　ｇ　／　Ｑ硫
酸マグネシウム　　　１５ｇＩＱ 硫酸アンモニウム　　３０ｇＩＱ 硼酸　　　　　　　　２０　ｇ　／　Ｑチオ硫酸アンモ
ニウム　Ｉｇ／Ｑ ｐＨ５，５ 実施例５ 押出成形後、自然冷却したアルミニウム合金（Ａ−６０
６３５）形材を温度１７０℃、１時間の条件で不完全時
効硬化処理し、その後、形材表面に毎秒Ｌｏｎｅの速度
で周波数３０ＫＨｚ、１６Ａのレーザー光線を照射して
模様状に表面調整した。Electrolyte composition: Nickel sulfate 25 g / Q magnesium sulfate 15 g IQ Ammonium sulfate 30 g IQ Boric acid 20 g / Q Ammonium thiosulfate Ig/Q pH 5,5 Example 5 Aluminum alloy (A-60) naturally cooled after extrusion molding
635) The shape was subjected to incomplete age hardening treatment at a temperature of 170° C. for 1 hour, and then the surface of the shape was irradiated with a laser beam of 16 A and a frequency of 30 KHz at a speed of 1 second to condition the surface in a pattern.

次いで、温度２２０℃、２時間の条件にて時効硬化処理
をし、形材を過時効硬化した、その後、該アルミニウム
合金形材を脱脂、エツチング、スマット除去し、この形
材を１８Ｗ／Ｖ％の硫酸水溶液中に浸漬して、液温２０
℃、時間３０分の条件で陽極酸化処理し、厚さ約１０μ
ｍの陽極酸化皮膜を形成した。次に電解着色処理として
実施例１と同様の装置を使用し、下記の組成を有する液
温２０℃の電解液中に前記形材を浸漬して、初期電流密
度ＬＡ／ｄ　ｒｒｒ、１１ｖの印加電圧で５分３０秒間
交流電解処理を行なったところ、模様状に表面調整した
部分が背景に比べて、かなり淡いブロンズ着色の装飾模
様となった。Next, the shape was subjected to age hardening treatment at a temperature of 220°C for 2 hours to overage harden the shape.Then, the aluminum alloy shape was degreased, etched, and smut removed, and the shape was reduced to 18W/V%. Immerse it in a sulfuric acid aqueous solution of
Anodized at ℃ for 30 minutes to a thickness of approximately 10μ
An anodized film of m was formed. Next, for electrolytic coloring treatment, using the same apparatus as in Example 1, the shape was immersed in an electrolytic solution having the following composition at a temperature of 20°C, and an initial current density LA/d rrr of 11 V was applied. When AC electrolytic treatment was carried out at voltage for 5 minutes and 30 seconds, the patterned surface-adjusted area became a bronze-colored decorative pattern that was considerably lighter than the background.

電解液組成：硫酸　　　　　　　　　２０１１ＩＱＩＱ
硫酸ニツケル　　　　　３０ｇ／Ｑ 硫酸第１錫　　　　　　　５ｇ／ｎ クレゾールスルフォン酸１０ｇ１Electrolyte composition: Sulfuric acid 2011IQIQ
Nickel sulfate 30g/Q Stannous sulfate 5g/n Cresol sulfonic acid 10g1

【図面の簡単な説明】[Brief explanation of drawings]

第１図は一般的なアルミニウム合金の人工時効硬化処理
時に於ける処理温度と処理時間及び硬度との関係を示し
た曲線グラフ、第２図は本発明の完全時効硬化乃至過時
効硬化処理工程に於ける処理温度と処理時間との関係を
示す曲線グラフである。Figure 1 is a curve graph showing the relationship between treatment temperature, treatment time, and hardness during artificial age hardening treatment of general aluminum alloys, and Figure 2 is a curve graph showing the relationship between treatment temperature, treatment time, and hardness during artificial age hardening treatment of general aluminum alloys. It is a curve graph showing the relationship between processing temperature and processing time.

Claims (1)

【特許請求の範囲】 １）押出成形後の未時効硬化又は不完全時効硬化状態に
於けるアルミニウム合金の表面に、機械的な加工操作に
より所望の模様状に傷又は歪み等を与える表面調整処理
を施した後で時効硬化処理を行ない、非表面調整部を完
全時効硬化乃至過時効硬化としてから陽極酸化皮膜処理
と電解着色処理とを同時又は別々に行なうことを特徴と
するアルミニウム合金の模様付け表面処理方法。 ２）押出成形後の未時効硬化又は不完全時効硬化状態に
於けるアルミニウム合金の表面に、機械的な加工操作に
より所望の模様状に傷又は歪み等を与える表面調整処理
を施した後で時効硬化処理を行ない、非表面調整部を完
全時効硬化乃至過時効硬化としてから陽極酸化皮膜処理
を施し、次いで無機酸又は有機酸もしくはこれらの混酸
の水溶液中で交流電解又は直流陰極電解により前記陽極
酸化皮膜の改質処理を施した後、電解着色処理を行なう
ことを特徴とするアルミニウム合金の模様付け表面処理
方法。[Scope of Claims] 1) A surface conditioning treatment in which the surface of an aluminum alloy in an unageed hardened or incompletely aged hardened state after extrusion molding is subjected to a mechanical processing operation to create scratches or distortions in a desired pattern. Patterning of an aluminum alloy characterized by performing an age hardening treatment after the above treatment, completely age hardening or overage hardening the non-surface-adjusted portion, and then performing an anodic oxide film treatment and an electrolytic coloring treatment simultaneously or separately. Surface treatment method. 2) After extrusion molding, the surface of the aluminum alloy in the unageed hardened or incompletely aged hardened state is subjected to surface conditioning treatment to create scratches or distortion in a desired pattern by mechanical processing, and then aged. A hardening treatment is performed to completely age-harden or over-age harden the non-surface-adjusted portion, and then an anodic oxide film treatment is performed, and then the anodic oxidation is performed by AC electrolysis or DC cathodic electrolysis in an aqueous solution of an inorganic acid, an organic acid, or a mixed acid thereof. A patterned surface treatment method for an aluminum alloy, which comprises performing electrolytic coloring treatment after a film modification treatment.