JP2717555B2 - Method for sealing anodized aluminum or aluminum alloy film - Google Patents
Method for sealing anodized aluminum or aluminum alloy filmInfo
- Publication number
- JP2717555B2 JP2717555B2 JP22733188A JP22733188A JP2717555B2 JP 2717555 B2 JP2717555 B2 JP 2717555B2 JP 22733188 A JP22733188 A JP 22733188A JP 22733188 A JP22733188 A JP 22733188A JP 2717555 B2 JP2717555 B2 JP 2717555B2
- Authority
- JP
- Japan
- Prior art keywords
- sealing
- aluminum
- film
- aluminum alloy
- alloy film
- 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 - Lifetime
Links
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- Sealing Material Composition (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
本発明は、アルミニウム又はアルミニウム合金の陽極
酸化皮膜の新規な封孔処理方法に関するものである。The present invention relates to a novel method for sealing a anodic oxide film of aluminum or an aluminum alloy.
アルミニウム及びアルミニウム合金の陽極酸化皮膜は
多孔質であるため、そのままでは耐食性、耐汚染性が著
しく劣るという欠点をもつ。そこで、この欠点を補うた
めに陽極酸化皮膜には通常封孔処理が施される。 封孔処理方法としては、加圧水蒸気による方法、沸騰
水による方法、酢酸ニッケル等の金属塩水溶液中で沸騰
状態で行う方法等があり、従来から実施されている。こ
れらの処理方法のうち、加圧水蒸気方法は他の封孔処理
方法に比べ皮膜の耐食性を向上させるという点で優れて
いるものの、建材等の大型材料を処理するには設備的に
困難であるという欠点を持っている。これに対し沸騰水
法は、設備が比較的安価であり大型材料の連続処理に適
しているが、皮膜に充分な耐食性を与えることができ
ず、又皮膜表面に酸化アルミニウムの水和物等の微粒子
が付着した、いわゆる粉吹きが発生し、外観不良、耐食
性の低下、塗装加工する場合の塗膜との密着不良の原因
となるという問題点を持っている。さらに酢酸ニッケル
等の金属塩法においても、金属塩が加水分解を受けやす
いため封孔浴の安定性が悪く、加水分解生成物が処理皮
膜に付着し粉吹き状態になるという欠点をもっている。 この封孔処理時の粉吹きを防止するために封孔浴にリ
グニンスルホン酸塩、スルホサリチル酸塩、スルホン化
芳香族化合物のホルムアルデヒド縮合物等を添加する方
法が従来から提案されている。しかしこれらの粉吹き防
止剤のうちリグニンスルホン酸塩は粉吹き防止効果が不
十分であり、また封孔処理液が長期使用により黄褐色に
着色するという欠点をもつ。これに対しスルホサリチル
酸塩は封孔処理液の安定性は良いものの、被処理物が日
光により黄変し、封孔度も低下するという欠点がある。
また、スルホン化芳香族化合物のホルムアルデヒド縮合
物においても、やはり被処理物の日光による黄変、封孔
処理液の着色という問題点をもっている。Since the anodic oxide film of aluminum and aluminum alloy is porous, there is a drawback that the corrosion resistance and the stain resistance are extremely poor as it is. Therefore, in order to compensate for this defect, the anodic oxide film is usually subjected to a sealing treatment. As a sealing treatment method, there are a method using pressurized steam, a method using boiling water, a method of performing boiling in an aqueous solution of a metal salt such as nickel acetate, and the like. Among these treatment methods, the pressurized steam method is superior in that it improves the corrosion resistance of the film as compared with other sealing treatment methods, but it is difficult in terms of equipment for treating large materials such as building materials. Has disadvantages. On the other hand, the boiling water method is relatively inexpensive and is suitable for continuous processing of large-sized materials, but cannot provide sufficient corrosion resistance to the film, and the surface of the film such as hydrated aluminum oxide has There is a problem in that so-called powder blowing to which fine particles adhere is generated, which causes poor appearance, reduced corrosion resistance, and poor adhesion to a coating film in coating. Furthermore, the metal salt method such as nickel acetate also has the disadvantage that the stability of the sealing bath is poor because the metal salt is easily susceptible to hydrolysis, and the hydrolysis products adhere to the treated film to form a powdery state. A method of adding a lignin sulfonate, a sulfosalicylate, a formaldehyde condensate of a sulfonated aromatic compound, or the like to a sealing bath has been proposed in order to prevent powder blowing during the sealing treatment. However, among these powder blowing inhibitors, lignin sulfonate has a disadvantage that the powder blowing preventing effect is insufficient, and the sealing solution is colored yellow-brown after long-term use. On the other hand, although sulfosalicylates have good stability of the pore-sealing solution, they suffer from the disadvantage that the object to be treated is yellowed by sunlight and the degree of sealing is reduced.
Further, the formaldehyde condensate of the sulfonated aromatic compound also has the problems of yellowing of the article to be treated by sunlight and coloring of the pore-sealing solution.
本発明者は、沸騰水封孔における上記問題を解消すべ
く鋭意研究した結果、アルミニウム又はアルミニウム合
金の陽極酸化皮膜を式 （l,mはl:m＝1:50〜50:1の任意の自然数を示し、X+はア
ルカリ金属イオン、アルカノールアミン又はアンモニウ
ムイオンを示す）で示される化合物の少なくとも１種を
0.005g/〜0.1g/含む水溶液に浸漬することにより、
粉吹きが無く、日光による黄変も見られない封孔された
上記陽極酸化皮膜が得られ、しかも上記水溶液は長時間
連続封孔処理を行っても着色、白濁等が起こらず安定で
あるという実用上好ましい性質を持つことを見出した。The present inventor has conducted intensive studies to solve the above problem in boiling water sealing, and as a result, anodized film of aluminum or aluminum alloy was formed by the formula (L, m represents an arbitrary natural number of l: m = 1: 50 to 50: 1, and X + represents an alkali metal ion, an alkanolamine or an ammonium ion).
By immersing in an aqueous solution containing 0.005 g / ~ 0.1 g /
It is said that the sealed anodic oxide film without powder blowing and without yellowing due to sunlight is obtained, and that the aqueous solution is stable without coloring, turbidity, etc. even after continuous sealing treatment for a long time. It has been found that it has practically preferable properties.
本発明は、アルミニウム又はアルミニウム合金の陽極
酸化皮膜を式 （l,mはl:m＝1:50〜50:1の任意の自然数を示し、X+はア
ルカリ金属イオン、アルカノールアミン又はアンモニウ
ムイオンを示す）で示される化合物の少なくとも１種を
含む水溶液に浸漬処理することを特徴とする上記陽極酸
化皮膜の封孔処理方法に係わる。 本発明の処理対象であるアルミニウム又はその合金の
陽極酸化皮膜としては常法により形成される皮膜のいず
れでもよく、例えば硫酸法、シュウ酸法、リン酸法、ク
ロム酸法等により形成される一次電解皮膜のみならず、
二次電解により形成されるものも含まれる。 本発明に使用される上記化合物は、スチレンスルホン
酸と無水マレイン酸を主原料として既知の方法で合成さ
れる。スチレンスルホン酸と無水マレイン酸のモル比及
び合成物の分子量は特に限定されないが、通常モル比1:
50〜50:1、好ましくは1:3〜3:1程度、分子量は約700〜1
00,000が適当である。 本発明に使用される上記化合物の使用濃度は、0.005g
/から0.1g/が適当である。0.005g/以下では粉吹
き防止効果が不十分となる傾向にあり、又、0.1g/以
上では表面に虹色の干渉色が現れ、特に着色皮膜ではこ
の傾向が顕著となり好ましくない。 本発明に使用される上記化合物を含む水溶液は、酢酸
−酢酸ナトリウム等の適当な緩衝剤を用いてpHを4.0〜
8.5、好ましくは5.0〜6.0に調節するのがよい。pH4.0以
下では沸騰処理時に陽極酸化皮膜の劣化が起こり、封孔
度も上がらず、またpH8.5以上では水溶液に沈降物が生
成しやすくなるので好ましくない。 本発明では、一般に90〜100℃、好ましくは95〜100℃
で封孔処理が行われる。また封孔処理時間は陽極酸化皮
膜の膜厚に応じて適宜決定すればよいが、通常20〜30分
程度とするのが適当である。The present invention uses an anodic oxide film of aluminum or aluminum alloy to form (L, m represents an arbitrary natural number of l: m = 1: 50 to 50: 1, and X + represents an alkali metal ion, an alkanolamine or an ammonium ion) in an aqueous solution containing at least one compound represented by the following formula: The present invention relates to the above-described method for sealing the anodic oxide film, which is characterized by immersion. The anodized film of aluminum or an alloy thereof to be treated in the present invention may be any film formed by a conventional method, for example, a primary method formed by a sulfuric acid method, an oxalic acid method, a phosphoric acid method, a chromic acid method, or the like. Not only electrolytic film,
Those formed by secondary electrolysis are also included. The above compound used in the present invention is synthesized by a known method using styrenesulfonic acid and maleic anhydride as main raw materials. The molar ratio of styrene sulfonic acid to maleic anhydride and the molecular weight of the synthesized product are not particularly limited, but usually the molar ratio is 1:
50-50: 1, preferably about 1: 3-3: 1, molecular weight about 700-1
00,000 is appropriate. The working concentration of the compound used in the present invention is 0.005 g.
Suitable from / to 0.1 g /. If it is less than 0.005 g /, the effect of preventing dust blowing tends to be insufficient, and if it is more than 0.1 g /, a rainbow-colored interference color appears on the surface, and this tendency is particularly remarkable in a colored film, which is not preferable. The aqueous solution containing the compound used in the present invention is adjusted to pH 4.0 to 4.0 using an appropriate buffer such as acetic acid-sodium acetate.
It is good to adjust to 8.5, preferably 5.0 to 6.0. If the pH is lower than 4.0, the anodic oxide film is deteriorated during the boiling treatment, and the sealing degree is not increased, and if the pH is higher than 8.5, sediment is easily generated in the aqueous solution, which is not preferable. In the present invention, generally 90 ~ 100 ℃, preferably 95 ~ 100 ℃
The sealing process is performed. The time for the sealing treatment may be appropriately determined according to the thickness of the anodic oxide film, but is usually suitably about 20 to 30 minutes.
次に実施例を挙げて本発明をより具体的に説明する。 試料Ａの作成 アルミニウム板（JIS A1050）を常法に従いアルカリ
脱脂、酸洗浄を行い、これを15％硫酸水溶液中で温度21
±１℃、電流密度20mA/cm2の条件で15分間陽極酸化を行
った。 試料Ｂの作成 アルミニウム板（JIS A1080）を常法に従いアルカリ
脱脂、酸洗浄を行い、これを15％硫酸水溶液中で温度21
±１℃、電流密度10mA/cm2の条件下で45分間陽極酸化を
行った。つぎにこれを有機着色剤（Sanodal MLW、ブラ
ック、サンド社製）を使用して常法により黒色に着色し
た。 実施例及び比較例 上記試料Ａ及びＢを第１表に示す処理剤から成る封孔
処理液中に浸漬し、沸騰状態で30分間封孔処理を行っ
た。なお各封孔処理液にはイオン交換水を使用し、液の
pHは酢酸及びアンモニア水で5.0〜6.0に調節した。これ
ら封孔処理を施した試料のうち試料Ａに関しては耐食性
試験、封孔度試験、屋外暴露試験を行い、試料Ｂについ
ては外観（粉吹き、虹）の観察を行った。また各封孔処
理液の沸騰安定性を調べた。それらの結果も合わせて第
１表に示す。 第１表に示した試験方法の詳細を以下に示す。 （１）外観：粉吹き、虹色等の有無を目視により判定 ◎ まったく見られない ○ わずかに見られる △ 少し見られる × 多量に見られる （２）耐食性:JIS H8681−1980,3.1 アルカリ滴下試験 （３）封孔度:JIS H8683−1979,3.2 リン酸−クロム酸水溶液浸漬試験 （４）耐光性：屋外１ケ月暴露後遮蔽部と露光部の差を
色差計（ミノルタ製色彩色差計 CR−200）にて、ΔL,Δ
a,Δb,ΔＥを測定。露光部の変色を目視で観察。 （５）浴安定性：各浴を水道水（大阪市上水）で建浴
し、48時間煮沸後の状態を観察。 以上の実施例の結果から、アルミニウムの陽極酸化皮
膜を本発明で実施することにより、上記陽極酸化皮膜の
耐食性、耐光性を損なうことなく粉吹き、虹色の発生を
有効に防止することができ、しかも本発明法の封孔処理
液は長時間の連続処理にも安定であるという、実用上非
常に好ましい特徴を持っていることがわかる。Next, the present invention will be described more specifically with reference to examples. Preparation of Sample A An aluminum plate (JIS A1050) was subjected to alkali degreasing and acid washing according to a conventional method, and was subjected to a 21% aqueous sulfuric acid solution at a temperature of 21%.
Anodization was performed at ± 1 ° C. and a current density of 20 mA / cm 2 for 15 minutes. Preparation of Sample B An aluminum plate (JIS A1080) was subjected to alkali degreasing and acid washing according to a conventional method, and was subjected to a 21% aqueous sulfuric acid solution at a temperature of 21%.
Anodization was performed at ± 1 ° C. and a current density of 10 mA / cm 2 for 45 minutes. Next, this was colored black by an ordinary method using an organic colorant (Sanodal MLW, Black, manufactured by Sandoz Co., Ltd.). EXAMPLES AND COMPARATIVE EXAMPLES Samples A and B were immersed in a sealing solution containing the treating agents shown in Table 1 and sealed in a boiling state for 30 minutes. In addition, ion-exchanged water is used for each sealing treatment liquid,
The pH was adjusted to 5.0 to 6.0 with acetic acid and aqueous ammonia. Among the samples subjected to the sealing treatment, the sample A was subjected to a corrosion resistance test, a sealing degree test, and an outdoor exposure test, and the sample B was observed for appearance (blown powder, rainbow). In addition, the boiling stability of each sealing solution was examined. Table 1 also shows the results. Details of the test methods shown in Table 1 are shown below. (1) Appearance: Visually determine the presence or absence of dusting, iridescence, etc. ◎ Not observed at all ○ Slightly observed △ Slightly observed × Largely observed (2) Corrosion resistance: JIS H8681-1980, 3.1 Alkali dripping test (3) Sealing degree: JIS H8683-1979, 3.2 Phosphoric acid-chromic acid aqueous solution immersion test (4) Light resistance: After one month of outdoor exposure, measure the difference between the shielded part and the exposed part with a color difference meter (Minolta color difference meter CR- 200), ΔL, Δ
Measure a, Δb, ΔE. Discoloration of the exposed part was visually observed. (5) Bath stability: Each bath was built with tap water (Josui, Osaka City), and the condition after boiling for 48 hours was observed. From the results of the above examples, by performing an anodic oxide film of aluminum in the present invention, corrosion resistance of the anodic oxide film, powder blowing without impairing light resistance, it is possible to effectively prevent the occurrence of iridescence. Further, it can be seen that the pore-sealing solution of the present invention has a very practically preferable characteristic that it is stable even for long-time continuous processing.
Claims (1)
酸化皮膜を式 （l,mはl:m＝1:50〜50:1の任意の自然数を示し、X+はア
ルカリ金属イオン、アルカノールアミン又はアンモニウ
ムイオンを示す）で示される化合物の少なくとも１種を
0.005g/〜0.1g/含む水溶液に浸漬することを特徴と
する上記陽極酸化皮膜の封孔処理方法。An anodic oxide film of aluminum or an aluminum alloy is formed by a formula (L, m represents an arbitrary natural number of l: m = 1: 50 to 50: 1, and X + represents an alkali metal ion, an alkanolamine or an ammonium ion).
The above-mentioned method for sealing an anodized film, which is immersed in an aqueous solution containing 0.005 g / to 0.1 g /.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22733188A JP2717555B2 (en) | 1988-09-09 | 1988-09-09 | Method for sealing anodized aluminum or aluminum alloy film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22733188A JP2717555B2 (en) | 1988-09-09 | 1988-09-09 | Method for sealing anodized aluminum or aluminum alloy film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0273992A JPH0273992A (en) | 1990-03-13 |
| JP2717555B2 true JP2717555B2 (en) | 1998-02-18 |
Family
ID=16859132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22733188A Expired - Lifetime JP2717555B2 (en) | 1988-09-09 | 1988-09-09 | Method for sealing anodized aluminum or aluminum alloy film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2717555B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411607A (en) * | 1993-11-10 | 1995-05-02 | Novamax Technologies Holdings, Inc. | Process and composition for sealing anodized aluminum surfaces |
| CN110760912B (en) * | 2018-07-27 | 2021-08-10 | 比亚迪股份有限公司 | Surface treatment method for metal having anodic oxide film, and metal |
| CN110359073A (en) * | 2019-07-06 | 2019-10-22 | 彭斌 | A kind of aluminium alloy anode oxide film hole sealing agent and its application method |
-
1988
- 1988-09-09 JP JP22733188A patent/JP2717555B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0273992A (en) | 1990-03-13 |
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