JP2005029868A - Surface treatment method for aluminum material - Google Patents
Surface treatment method for aluminum material Download PDFInfo
- Publication number
- JP2005029868A JP2005029868A JP2003272969A JP2003272969A JP2005029868A JP 2005029868 A JP2005029868 A JP 2005029868A JP 2003272969 A JP2003272969 A JP 2003272969A JP 2003272969 A JP2003272969 A JP 2003272969A JP 2005029868 A JP2005029868 A JP 2005029868A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- aluminum
- aluminum material
- aqueous solution
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- ing And Chemical Polishing (AREA)
Abstract
Description
本発明は、アルミニウム又はアルミニウム合金からなる、押出材や圧延材等のアルミニウム材表面の金属光沢を均一に制御し、仕上り外観に斑のない均一な低光沢表面状態を有する表面処理アルミニウム材を製造するためのアルミニウム材の表面処理方法に関する。 The present invention produces a surface-treated aluminum material made of aluminum or an aluminum alloy, which uniformly controls the metallic luster on the surface of an aluminum material such as an extruded material or a rolled material, and has a uniform low-gloss surface state with no spots on the finished appearance. The present invention relates to a surface treatment method for an aluminum material.
アルミニウム材は、軽量で耐蝕性や耐久性、加工性、表面処理性等に優れており、また、適度な強度を有することから、外装材、内装材、表層材等の建築材料や電気機器等のケーシング材料を始めとして、極めて多くの分野で広範囲に使用されている。 Aluminum materials are lightweight, excellent in corrosion resistance, durability, workability, surface treatment properties, etc., and because they have moderate strength, building materials such as exterior materials, interior materials, surface layer materials, electrical equipment, etc. It is widely used in many fields including the casing material.
そして、このようなアルミニウム材については、その使用目的に応じて周囲の環境との調和や意匠性等の向上を図る目的で、梨地処理、ブラスト処理等の方法で表面光沢を調整したり、あるいは、電解着色処理、塗装処理等の方法で着色する表面処理が行われたりしている。 And for such an aluminum material, the surface gloss is adjusted by a method such as a satin treatment or a blast treatment for the purpose of improving the harmony with the surrounding environment or improving the design depending on the purpose of use, or In addition, a surface treatment for coloring by a method such as electrolytic coloring treatment or painting treatment is performed.
この種の表面処理の具体例としては、例えば、Ｆｅ、Ｍｎ、Ｚｒ、Ｓｉ、Ｃｒ、Ｍｇ、Ｚｎ、Ｃｕ等の合金成分の添加量を調整し、粗面化処理で表面色調を白色に調整した後に陽極酸化処理を施して色調が白色のアルミニウム材を得る方法（特許文献１）、熱処理とエッチング処理を施して結晶粒を粗大化させ、結晶模様を有するアルミニウム材を得る方法（特許文献２）、完全軟化焼鈍処理を施した後に塑性変形を加え、次いで熱処理を施して結晶粒を粗大化させ、結晶模様を有するアルミニウム材を得る方法（特許文献３）、Ｆｅ成分とＣｕ成分とを所定の割合で含むＡｌ−Ｍｇ−Ｓｉ系合金を押出加工し、次いでエッチング処理して結晶模様を有するアルミニウム材を得る方法（特許文献４）が提案されている。更に、酸化皮膜処理の後、アノード電解処理、アルカリ処理する方法（特許文献５〜１０）等が提案されている。 Specific examples of this type of surface treatment include, for example, adjusting the additive amount of alloy components such as Fe, Mn, Zr, Si, Cr, Mg, Zn, and Cu, and adjusting the surface color tone to white by roughening treatment. After that, a method of obtaining an aluminum material having a white color tone by performing anodizing treatment (Patent Document 1), and a method of obtaining an aluminum material having a crystal pattern by applying heat treatment and etching treatment to coarsen crystal grains (Patent Document 2). ), A method in which plastic deformation is applied after complete softening annealing treatment, and then heat treatment is performed to coarsen the crystal grains to obtain an aluminum material having a crystal pattern (Patent Document 3). (Patent Document 4) has been proposed in which an Al—Mg—Si based alloy contained at a ratio of 1 is extruded and then etched to obtain an aluminum material having a crystal pattern. Furthermore, after the oxide film treatment, anode electrolytic treatment, alkali treatment methods (Patent Documents 5 to 10) and the like have been proposed.
しかしながら、このような従来の表面処理方法では、アルミニウム材の表面に付与される表面光沢の選択の幅が狭く、観察角度によって色調が異なる角度依存性があり、また、処理後の外観を制御できないために表面光沢や色調において均一性や再現性に乏しく、更に、特に建築材料等の分野で嗜好の多様化に伴って要求される広範囲でバラエティに富む表面光沢や色調、特に手で触れてもザラザラした感じがあり、金属光沢感がなくて目にやさしいザラザラ感を有する表面光沢や色調に対応できないという問題があった。また、酸化皮膜処理の後、アノード電解処理、アルカリ処理する方法によっては、これらの問題を解決したが、より、低光沢のアルミニウム材を達成する表面処理方法が求められていた。 However, in such a conventional surface treatment method, the selection range of the surface gloss imparted to the surface of the aluminum material is narrow, the color tone varies depending on the observation angle, and the appearance after the treatment cannot be controlled. Therefore, the surface gloss and color tone are poor in uniformity and reproducibility, and furthermore, the surface gloss and color tone with a wide variety that is required in accordance with the diversification of preference especially in the field of building materials etc. There was a problem that there was a rough feeling and there was no metallic luster and it was not possible to cope with surface luster and color tone having a rough feeling that was kind to the eyes. Moreover, although these problems were solved depending on the method of anodic electrolytic treatment and alkali treatment after the oxide film treatment, a surface treatment method for achieving a low gloss aluminum material has been demanded.
そこで、本発明者らは、このような課題を解決すべく鋭意検討した結果、アルミニウム材を陽極酸化処理等の酸化処理に続いて、酸性水溶液中での酸エッチングを行い、中間処理としてのアノード電解処理しなくとも、更に引き続いてアルカリ性水溶中でのアルカリエッチングを行うことにより、表面光沢や色調において均一性や再現性に富み、広範囲に亘って制御された目にやさしいザラザラ感のある表面光沢や色調を付与することができ、同時にアルミニウム素材に由来する圧延痕や押出痕等も消失しうることを見出し、本発明を完成した。 Therefore, as a result of intensive studies to solve such problems, the present inventors conducted an acid etching in an acidic aqueous solution following an oxidation treatment such as anodization treatment on an aluminum material, and an anode as an intermediate treatment. Even without electrolytic treatment, by performing alkaline etching in an alkaline aqueous solution, the surface gloss has a uniform and reproducible surface gloss and color tone, and is controlled over a wide range and has a rough and glossy surface gloss. The present invention has been completed by discovering that rolling marks, extrusion marks and the like derived from an aluminum material can also disappear at the same time.
従って、本発明の目的は、素材形成時の圧延痕や押出痕等が消失すると共に、表面光沢や色調において均一性や再現性に富み、広範囲に亘って極めて低い表面光沢度を付与することができるアルミニウム材の表面処理方法を提供することにある。 Accordingly, the object of the present invention is to eliminate the rolling marks and extrusion marks at the time of forming the material, and to provide a very low surface gloss over a wide range, which is rich in uniformity and reproducibility in surface gloss and color tone. An object of the present invention is to provide a surface treatment method for an aluminum material.
すなわち、本発明は、アルミニウム又はアルミニウム合金からなるアルミニウム材表面に酸化皮膜を形成する酸化処理を行う第一工程と、酸性水溶液に浸漬し酸エッチング処理を行う第二工程と、アルカリ性水溶液に浸漬しアルカリエッチング処理を行う第三工程とを含む低光沢表面処理であって、第一工程乃至第三工程の間においてアノード電解処理しないことを特徴とする、アルミニウム材の表面処理方法である。本発明のアルミニウム材の表面処理方法により、第三工程のアルカリエッチング処理後の表面処理アルミニウム材は、光沢度６以下、表面粗さ（Ｒａ）９μｍ以下とすることができる。第三工程のアルカリエッチング処理後の表面処理アルミニウム材は、より好ましくは、光沢度５以下、表面粗さ（Ｒａ）３〜６μｍである。 That is, the present invention includes a first step of performing an oxidation treatment for forming an oxide film on the surface of an aluminum material made of aluminum or an aluminum alloy, a second step of performing an acid etching treatment by immersion in an acidic aqueous solution, and an immersion in an alkaline aqueous solution. A surface treatment method for an aluminum material, comprising: a low gloss surface treatment including a third step of performing an alkali etching treatment, wherein no anode electrolytic treatment is performed between the first step and the third step. By the surface treatment method for an aluminum material of the present invention, the surface-treated aluminum material after the alkali etching treatment in the third step can have a glossiness of 6 or less and a surface roughness (Ra) of 9 μm or less. More preferably, the surface-treated aluminum material after the alkali etching treatment in the third step has a glossiness of 5 or less and a surface roughness (Ra) of 3 to 6 μm.
本発明において、アルミニウム材の表面に酸化皮膜を形成せしめる第一工程の酸化処理には、多塩基酸及び／又はその塩を含む水溶液中での陽極酸化処理、酸素雰囲気中における熱酸化処理又は熱水溶液中に浸漬する水和酸化処理がある。 In the present invention, the oxidation treatment in the first step of forming an oxide film on the surface of the aluminum material includes an anodization treatment in an aqueous solution containing a polybasic acid and / or a salt thereof, a thermal oxidation treatment or heat in an oxygen atmosphere. There is a hydration oxidation treatment immersed in an aqueous solution.
本発明において、アルミニウム材の表面に陽極酸化皮膜を形成せしめる第一工程の酸化処理で使用される多塩基酸及び／又はその塩としては、例えば、ホウ酸、リン酸、硫酸、シュウ酸、酒石酸等の多塩基酸や、そのアンモニウム、ナトリウム（Na）、カリウム（Ｋ）等の塩を挙げることができる。これらはその１種のみを単独で用いることができるほか、２種以上を混合して得られた混酸及びその塩として用いることもできる。 In the present invention, examples of the polybasic acid and / or salt thereof used in the oxidation treatment in the first step for forming an anodized film on the surface of the aluminum material include boric acid, phosphoric acid, sulfuric acid, oxalic acid, and tartaric acid. And a salt of ammonium, sodium (Na), potassium (K) or the like. These can be used alone, or can be used as a mixed acid obtained by mixing two or more and salts thereof.
そして、このような多塩基酸及び／又はその塩を含む水溶液としては、例えば、四ホウ酸ナトリウム-ホウ酸、ホウ酸アンモニウム、リン酸アンモニウム等の中性浴や、硫酸、リン酸、シュウ酸、酒石酸等の酸性浴を挙げることができ、中性浴を用いる場合には、形成される陽極酸化皮膜が障壁型皮膜を形成しているので、その膜厚を実用上０．０１〜１μｍの範囲とするのがよく、また、酸性浴を用いる場合には、形成される陽極酸化皮膜が多孔質皮膜を形成しているので、その膜厚を実用上０．０１〜１０μｍの範囲とするのがよい。この陽極酸化皮膜の膜厚が不足すると凹凸の均一性が低下し、反対に、必要以上に厚くしても効果の向上が認められず、時間及び電力の点で経済的でない。 Examples of the aqueous solution containing such a polybasic acid and / or a salt thereof include, for example, neutral baths such as sodium tetraborate-boric acid, ammonium borate, and ammonium phosphate, sulfuric acid, phosphoric acid, and oxalic acid. An acidic bath such as tartaric acid can be used. When a neutral bath is used, the formed anodic oxide film forms a barrier-type film, so that the film thickness is practically 0.01 to 1 μm. In the case of using an acidic bath, the formed anodic oxide film forms a porous film, so that the film thickness is practically in the range of 0.01 to 10 μm. Is good. If the film thickness of this anodic oxide film is insufficient, the uniformity of the unevenness is lowered, and conversely, even if it is thicker than necessary, the improvement of the effect is not recognized, and it is not economical in terms of time and power.
この第一工程の陽極酸化処理における処理条件については、中性浴を用いるか又は酸性浴を用いるか、形成される陽極酸化皮膜の膜厚をどの程度に設計するか等によって異なるが、例えば、中性浴の場合には、浴濃度１〜３００ｇ／ｌ、ｐＨ４〜１０、浴温度０〜８０℃、定電流（電流密度）１〜１００Ａ／ｍ２、最終電圧１０〜１０００Ｖ（好ましくは１０〜５００Ｖ）であり、また、酸性浴の場合には、浴濃度１〜３００ｇ／ｌ、浴温度０〜５０℃、定電流（電流密度）５〜３００Ａ／ｍ２又は定電圧５〜１５０Ｖ、時間５〜３６００秒である。 The treatment conditions in the first step anodizing treatment vary depending on whether a neutral bath or an acidic bath is used, how much the thickness of the formed anodized film is designed, etc. In the case of a neutral bath, the bath concentration is 1 to 300 g / l, pH 4 to 10, bath temperature 0 to 80 ° C., constant current (current density) 1 to 100 A / m 2 , final voltage 10 to 1000 V (preferably 10 to 10 V). In the case of an acidic bath, the bath concentration is 1 to 300 g / l, the bath temperature is 0 to 50 ° C., the constant current (current density) is 5 to 300 A / m 2, or the constant voltage is 5 to 150 V, and the time is 5 ~ 3600 seconds.
本発明において、第一工程の酸化処理として熱酸化皮膜を形成せしめる処理条件は、アルミニウム材を酸素雰囲気中で、加熱温度３００〜６００℃、好ましくは４５０〜５５０℃で、加熱時間が５〜６０分、好ましくは５〜３０分である。加熱温度が３００℃に達しない、又は加熱時間が５分に満たない熱酸化処理では、アルミニウム材の表面に十分な熱酸化皮膜が生成されず、第二工程において均一な凹凸の分布が得られない。反対に、加熱温度が６００℃を超えるとアルミニウム材の溶融が生じてしまう。また、加熱時間が６０分を超える熱酸化処理では、例えば、本発明の表面処理方法を適用するアルミニウム材が、ＪＩＳ Ａ６０６３等のＡｌ−Ｍｇ−Ｓｉ系合金のアルミニウム材である場合、Ｍｇ２Ｓｉの時効析出が進行して、十分な材料強度が得られなくなる。 In the present invention, the treatment conditions for forming a thermal oxide film as the oxidation treatment in the first step are as follows: an aluminum material in an oxygen atmosphere, a heating temperature of 300 to 600 ° C., preferably 450 to 550 ° C., and a heating time of 5 to 60. Minutes, preferably 5 to 30 minutes. In the thermal oxidation treatment in which the heating temperature does not reach 300 ° C. or the heating time is less than 5 minutes, a sufficient thermal oxide film is not generated on the surface of the aluminum material, and a uniform uneven distribution is obtained in the second step. Absent. On the contrary, when the heating temperature exceeds 600 ° C., the aluminum material is melted. Further, in the thermal oxidation treatment in which the heating time exceeds 60 minutes, for example, when the aluminum material to which the surface treatment method of the present invention is applied is an aluminum material of an Al—Mg—Si based alloy such as JIS A6063, Mg 2 Si As the aging precipitation proceeds, sufficient material strength cannot be obtained.
この熱酸化処理における加熱温度は、理論的にはアルミニウム材の表面に熱酸化皮膜をできるだけ均一に形成せしめるための温度ということであり、具体的には、加熱温度が４５０℃以下では、熱酸化処理の時間に比例してアルミニウム材の表面に無定型γ−アルミナの緻密な皮膜が生成し、５００℃以上では、熱酸化処理の初期には緻密な無定型γ−アルミナの皮膜が生成し、その後は結晶性のγ−アルミナが生成する。 The heating temperature in this thermal oxidation treatment is theoretically a temperature for forming a thermal oxide film on the surface of the aluminum material as uniformly as possible. Specifically, when the heating temperature is 450 ° C. or less, thermal oxidation is performed. A dense amorphous γ-alumina film is formed on the surface of the aluminum material in proportion to the treatment time. At 500 ° C. or higher, a dense amorphous γ-alumina film is formed at the beginning of the thermal oxidation treatment, Thereafter, crystalline γ-alumina is formed.
ここで、無定型のγ−アルミナは、アルミニウム材の表面に均一に生成するため、アルミニウム材の表面酸化物の厚さは均一となる。また、結晶性のγ−アルミナは、アルミニウム材の表面に点在するように生成し、加熱温度が高温になるほど、また、加熱時間が長くなるほどその生成量が多くなり、アルミニウム材の表面を被覆する。熱酸化皮膜を形成したアルミニウム材は、第二工程の酸エッチング処理を施すと、熱酸化皮膜の欠陥部を破壊してピットを形成するが、この際に、結晶性酸化物によって被覆された部分は、他の部分に比べ、破壊が起こりにくくなる。従って、アルミニウム材の表面に形成されるピットの数は、結晶性のγ−アルミナの被覆率が高くなるにつれ少なくなる。 Here, since amorphous γ-alumina is uniformly formed on the surface of the aluminum material, the thickness of the surface oxide of the aluminum material becomes uniform. In addition, crystalline γ-alumina is generated so as to be scattered on the surface of the aluminum material, and the amount of generation increases as the heating temperature becomes higher and the heating time becomes longer, covering the surface of the aluminum material. To do. When the aluminum material on which the thermal oxide film is formed is subjected to the acid etching treatment in the second step, the defective portion of the thermal oxide film is destroyed to form pits. At this time, the portion covered with the crystalline oxide Is less susceptible to destruction than other parts. Therefore, the number of pits formed on the surface of the aluminum material decreases as the coverage of crystalline γ-alumina increases.
本発明において、第一工程の酸化処理として水和酸化皮膜を形成せしめる第一工程は、アルミニウム材の表面に水和酸化皮膜を生成させる処理であればよく、アルミニウム材を熱水中に浸漬する熱水処理であっても、アルミニウム材を水蒸気雰囲気中に放置する水蒸気処理であってもよい。この熱水処理、又は水蒸気処理は、理論的にはアルミニウム材の表面に擬似ベーマイト皮膜を形成せしめるためのものであり、表面に水和酸化皮膜を形成したアルミニウム材に対し、第二工程の酸エッチング処理を施すと、水和酸化皮膜の一部が破壊され、アルミニウム材の表面にピットを形成させることができる。 In the present invention, the first step of forming the hydrated oxide film as the oxidation treatment in the first step may be any treatment that forms a hydrated oxide film on the surface of the aluminum material, and the aluminum material is immersed in hot water. Even hot water treatment may be steam treatment in which an aluminum material is left in a steam atmosphere. This hot water treatment or steam treatment is theoretically intended to form a pseudo boehmite film on the surface of the aluminum material, and the acid in the second step is applied to the aluminum material having a hydrated oxide film formed on the surface. When the etching treatment is performed, a part of the hydrated oxide film is destroyed and pits can be formed on the surface of the aluminum material.
本発明の上記第一工程における熱水処理の処理条件は、熱水が温度６０℃以上、好ましくは８０℃以上、ｐＨ５〜１０の水溶液であって、アルミニウム材を熱水に浸漬する浸漬時間が１〜３０分である。水溶液の温度が６０℃未満、又はｐＨが５より小さい、又はｐＨが１０を超える、又は浸漬時間が１分未満の熱水処理では、アルミニウム材の表面に十分な厚さの水和酸化皮膜が生成されず、均一な外観を得ることができない。反対に、浸漬時間が３０分を超える浸漬を行っても、効果の向上は認められず、時間及び熱量の点で経済的ではない。 The treatment conditions for the hot water treatment in the first step of the present invention are as follows: hot water is an aqueous solution having a temperature of 60 ° C. or higher, preferably 80 ° C. or higher, and a pH of 5 to 10; 1-30 minutes. In hydrothermal treatment where the temperature of the aqueous solution is less than 60 ° C., the pH is less than 5, or the pH is greater than 10, or the immersion time is less than 1 minute, a hydrated oxide film having a sufficient thickness is formed on the surface of the aluminum material. It is not generated and a uniform appearance cannot be obtained. On the contrary, even if the immersion time exceeds 30 minutes, the effect is not improved, and it is not economical in terms of time and heat amount.
また、水和酸化皮膜の生成を促進するために、上記水溶液にアルカリ性添加剤を加えてもよく、具体的には、アンモニア及び／又はアミノアルコールを使用してもよい。アミノアルコールとしては、トリエタノールアミンが望ましい。また、上記アルカリ性添加剤の濃度は０.１〜１質量％、好ましくは０.３〜０.５質量％である。第一工程における水蒸気処理の処理条件は、温度７５〜２００℃、好ましくは７５〜１２０℃の飽和水蒸気雰囲気中に、アルミニウム材を放置する放置時間が１〜３０分、好ましくは３〜２０分である。 In order to promote the formation of a hydrated oxide film, an alkaline additive may be added to the aqueous solution, and specifically, ammonia and / or amino alcohol may be used. As the amino alcohol, triethanolamine is desirable. The concentration of the alkaline additive is 0.1 to 1% by mass, preferably 0.3 to 0.5% by mass. The treatment conditions of the water vapor treatment in the first step are as follows: the time for leaving the aluminum material in a saturated water vapor atmosphere at a temperature of 75 to 200 ° C., preferably 75 to 120 ° C., is 1 to 30 minutes, preferably 3 to 20 minutes. is there.
また、本発明において、第二工程における酸性水溶液は、アルミニウム材を浸蝕する化合物から成る水溶液であることが好ましい。アルミニウム材を浸蝕する化合物は、例えば、フッ酸、塩酸、硝酸、第二銅化合物又は第二鉄化合物の少なくとも一種から成る。この際に用いられる第二銅化合物及び第二鉄化合物には塩酸、硝酸、酢酸、硫酸等の塩が挙げられ、好ましくは塩化第二銅、硝酸第二銅、硫酸第二銅、塩化第二鉄、硫酸第二鉄、酢酸第二鉄、硝酸第二鉄等が挙げられる。フッ酸、塩酸、硝酸、第二銅化合物又は第二鉄化合物は、その１種のみを単独で用いてもよいほか、２種以上を混合して得られた混酸及びその塩として用いてもよい。この第二工程の酸エッチング処理により、第一工程の酸化処理によってアルミニウム材の表面に形成された酸化皮膜を破壊し、このアルミニウム材の表面に極めて微細なピットが均一に形成される。 In the present invention, the acidic aqueous solution in the second step is preferably an aqueous solution composed of a compound that erodes the aluminum material. The compound that corrodes the aluminum material is made of, for example, at least one of hydrofluoric acid, hydrochloric acid, nitric acid, a cupric compound, or a ferric compound. The cupric compound and ferric compound used at this time include salts of hydrochloric acid, nitric acid, acetic acid, sulfuric acid, etc., preferably cupric chloride, cupric nitrate, cupric sulfate, cupric chloride. Examples thereof include iron, ferric sulfate, ferric acetate, and ferric nitrate. Hydrofluoric acid, hydrochloric acid, nitric acid, cupric compound or ferric compound may be used alone or as a mixed acid obtained by mixing two or more and salts thereof. . By this acid etching treatment in the second step, the oxide film formed on the surface of the aluminum material by the oxidation treatment in the first step is destroyed, and extremely fine pits are uniformly formed on the surface of the aluminum material.
この第二工程の酸エッチング処理における処理条件については、溶質濃度が好ましくは１０〜３００ｇ／ｌ、より好ましくは３０〜２００ｇ／ｌであり、また、処理温度が好ましくは２０〜５０℃、より好ましくは２５〜４０℃であり、更に、処理時間が好ましくは２０分以下、より好ましくは３〜１５分である。この酸性水溶液による酸エッチング処理は、溶質濃度１０ｇ／ｌ以上、処理温度２０℃以上で進行し、反対に、溶質濃度が２００ｇ／ｌより高くなったり、あるいは、処理温度が５０℃より高くなったりすると、化学溶解反応が激しくなって微細な凹凸の抑制が難しくなり、また、処理時間が２０分を超えると均一溶解が過度に進行してかえって凹凸が目立たなくなるほか、アルミニウムの溶解減量も大きくなって好ましくない。 Regarding the treatment conditions in the acid etching treatment of the second step, the solute concentration is preferably 10 to 300 g / l, more preferably 30 to 200 g / l, and the treatment temperature is preferably 20 to 50 ° C., more preferably. Is 25 to 40 ° C., and the treatment time is preferably 20 minutes or less, more preferably 3 to 15 minutes. The acid etching treatment with the acidic aqueous solution proceeds at a solute concentration of 10 g / l or more and a treatment temperature of 20 ° C. or more, and conversely, the solute concentration becomes higher than 200 g / l or the treatment temperature becomes higher than 50 ° C. Then, the chemical dissolution reaction becomes intense and it becomes difficult to suppress fine unevenness, and when the treatment time exceeds 20 minutes, the uniform dissolution proceeds excessively, and the unevenness becomes inconspicuous, and the dissolution loss of aluminum also increases. It is not preferable.
そして、本発明においては、上記第二工程の酸エッチング処理に引き続いて、第三工程としてアルカリ性水溶液中に浸漬するアルカリ処理を行う。第三工程では、第二工程で生成したピットを拡大することができる。この第三工程のアルカリ処理における処理条件については、遊離アルカリ濃度が好ましくは２０〜１００ｇ／ｌ、より好ましくは４０〜７０ｇ／ｌであり、処理温度が好ましくは３０〜７０℃、より好ましくは４０〜６０℃であり、また、ｐＨ値が好ましくは１３以上であり、更に、処理時間が好ましくは３〜２０分、より好ましくは５〜１５分である。遊離アルカリ濃度２０ｇ／ｌ未満、処理温度３０℃未満、又はｐＨ値１３未満では、いずれの場合も、溶解速度が遅く、生産性が低下する。反対に、遊離アルカリ濃度１００ｇ／ｌ超、又は処理温度７０℃超では、溶解速度が速くなりすぎる。ピットの拡大も過多となり、表面がなだらかになってしまい、所望の表面状態を得るのが困難になる。 In the present invention, subsequent to the acid etching treatment in the second step, an alkali treatment of immersing in an alkaline aqueous solution is performed as a third step. In the third step, the pits generated in the second step can be enlarged. Regarding the treatment conditions in the alkali treatment in the third step, the free alkali concentration is preferably 20 to 100 g / l, more preferably 40 to 70 g / l, and the treatment temperature is preferably 30 to 70 ° C., more preferably 40. The pH value is preferably 13 or more, and the treatment time is preferably 3 to 20 minutes, more preferably 5 to 15 minutes. If the free alkali concentration is less than 20 g / l, the treatment temperature is less than 30 ° C., or the pH value is less than 13, in any case, the dissolution rate is slow and the productivity is lowered. On the other hand, when the free alkali concentration exceeds 100 g / l, or the processing temperature exceeds 70 ° C., the dissolution rate becomes too fast. The pits are enlarged too much, the surface becomes smooth, and it becomes difficult to obtain a desired surface state.
また、処理時間についても、遊離アルカリ濃度、処理温度、ｐＨ値等の条件によっても異なるが、３分に達しない短時間浸漬では均一溶解が進行せずに所望の凹凸を得ることが難しく、また、２０分を超える長時間浸漬では均一溶解が過度に進行してかえって凹凸が目立たなくなるほか、アルミの溶解減量も大きくなって好ましくない。 Also, the treatment time varies depending on conditions such as free alkali concentration, treatment temperature, pH value, etc., but it is difficult to obtain desired irregularities without uniform dissolution in short-time immersion that does not reach 3 minutes, In the case of soaking for more than 20 minutes, uniform dissolution proceeds excessively, and the unevenness becomes inconspicuous, and the dissolution loss of aluminum becomes large.
更に、上記第三工程のアルカリ処理の後に、スマット除去処理、陽極酸化処理、染色又は金属の電解析出による着色処理、あるいは封孔処理又は電着塗装等の塗装処理を行ってもよく、また、これらの処理に代えて、クロメート処理を行ってもよい。これらの陽極酸化処理、着色処理、封孔処理、電着塗装処理及びクロメート処理については、従来公知の方法で実施することができる。 Further, after the alkali treatment in the third step, smut removal treatment, anodizing treatment, coloring treatment by dyeing or electrolytic deposition of metal, or coating treatment such as sealing treatment or electrodeposition coating may be performed. Instead of these treatments, chromate treatment may be performed. These anodizing treatment, coloring treatment, sealing treatment, electrodeposition coating treatment and chromate treatment can be carried out by conventionally known methods.
また、本発明においては、第一工程の酸化処理に先駆けて、アルミニウム材の前処理として、脱脂処理及び／又はアルカリエッチング処理を行ってもよい。また、アルカリエッチング処理の後に必要に応じてスマット除去処理を行ってもよい。これらの脱脂処理、アルカリエッチング処理及びスマット除去処理についても、従来公知の方法で実施することができる。 Moreover, in this invention, you may perform a degreasing process and / or an alkali etching process as a pre-process of an aluminum material prior to the oxidation process of a 1st process. Moreover, you may perform a smut removal process as needed after an alkali etching process. These degreasing treatments, alkali etching treatments and smut removal treatments can also be carried out by conventionally known methods.
本発明によれば、上記酸化処理によりアルミニウム材の表面に酸化皮膜を形成せしめ、次いで酸エッチング処理を行うことによりこの酸化皮膜を破壊し、アルミニウム材の素地の金属組織に影響されること無く、このアルミニウム材の表面に均一かつ微細で大きさの揃ったピットを形成せしめることができる。 According to the present invention, an oxide film is formed on the surface of the aluminum material by the oxidation treatment, and then the oxide film is destroyed by performing an acid etching treatment, without being affected by the metal structure of the base material of the aluminum material. Uniform, fine and uniform pits can be formed on the surface of the aluminum material.
本発明のアルミニウム材の表面処理方法によれば、素材形成時の圧延痕や押出痕等が消失すると共に、表面光沢や色調において均一性や再現性に富み、広範囲に亘って制御された表面光沢や色調を付与することができる。 According to the surface treatment method for an aluminum material of the present invention, rolling marks and extrusion marks at the time of forming the material disappear, surface gloss and color tone are uniform and reproducible, and the surface gloss is controlled over a wide range. And color tone can be imparted.
以下、実施例に基づいて、本発明の好適な実施の形態を具体的に説明する。 Hereinafter, preferred embodiments of the present invention will be specifically described based on examples.
Ａ６０６３アルミニウム押出形材を、前処理として、水酸化ナトリウム濃度５０ｇ／ｌ、浴温５０℃の水溶液中に３００秒間浸漬し、このアルミニウム押出形材表面の自然酸化皮膜を除去した。その後、硝酸濃度６０ｇ／ｌ、常温の水溶液中に１８０秒間浸漬してスマット除去を行った。 As a pretreatment, the A6063 aluminum extruded profile was immersed in an aqueous solution having a sodium hydroxide concentration of 50 g / l and a bath temperature of 50 ° C. for 300 seconds to remove the natural oxide film on the surface of the aluminum extruded profile. Thereafter, smut removal was performed by immersing in an aqueous solution at a nitric acid concentration of 60 g / l for 180 seconds.
次に、前処理済のアルミニウム押出形材を硫酸濃度１５０ｇ／ｌの水溶液中、浴温２０℃及び電流密度１００Ａ／ｍ２で１８０秒間定電流にて陽極酸化した（第一工程）。次いで、浴温４０℃及び塩酸濃度１００ｇ／ｌの水溶液中に３００秒間浸漬してアルミニウム押出形材表面に多数の微細なピットを形成せしめた（第二工程）。更に、水酸化ナトリウム濃度５０ｇ／ｌ、浴温５０℃の水溶液中に６００秒間浸漬して、第二工程で形成された微細ピットを拡大させ（第三工程）、表面処理されたアルミニウム押出形材を得た。 Next, the pretreated aluminum extruded profile was anodized in an aqueous solution having a sulfuric acid concentration of 150 g / l at a bath temperature of 20 ° C. and a current density of 100 A / m 2 at a constant current for 180 seconds (first step). Next, it was immersed in an aqueous solution having a bath temperature of 40 ° C. and a hydrochloric acid concentration of 100 g / l for 300 seconds to form a large number of fine pits on the surface of the aluminum extruded profile (second step). Further, the aluminum extruded profile was surface-treated by immersing it in an aqueous solution having a sodium hydroxide concentration of 50 g / l and a bath temperature of 50 ° C. for 600 seconds to enlarge the fine pits formed in the second step (third step). Got.
得られたアルミニウム押出形材の光沢度及び表面粗さ（Ｒａ、Ｒmax）を測定した。この表面処理アルミニウム押出形材は、その光沢度及び表面粗さにおいてバラツキがなく、触感においても視覚においても凹凸のザラツキ感があり、表面光沢度が極めて低く、質感のある均一な表面外観であった。また、アルミニウム押出形材に特有のダイスマークが消失し、アルミニウム押出形材の表面欠陥（ウエルダーラインやストリーク等）がなく、表面品質が安定した。 The resulting aluminum extruded profile was measured for glossiness and surface roughness (Ra, Rmax). This surface-treated aluminum extruded shape has no variation in glossiness and surface roughness, has a rough feeling in tactile sensation and vision, has a very low surface glossiness, and has a textured and uniform surface appearance. It was. In addition, the die mark peculiar to the aluminum extruded shape disappeared, and there was no surface defect (welder line, streak, etc.) of the aluminum extruded shape, and the surface quality was stabilized.
実施例１と同様にして自然酸化皮膜を除去した前処理済みのアルミニウム押出形材をシュウ酸濃度３０ｇ／ｌの水溶液中、浴温２５℃及び電流密度５０Ａ／ｍ２で１２０秒間定電流にて陽極酸化した（第一工程）。次いで、浴温が４０℃で、塩酸濃度１００ｇ／ｌ及び塩化第二鉄４０ｇ／ｌの混合水溶液中に３００秒間浸漬してアルミニウム押出形材表面に多数の微細なピットを形成せしめた（第二工程）。更に、水酸化ナトリウム濃度５０ｇ／ｌ、浴温５０℃の水溶液中に６００秒間浸漬して、第二工程で形成された微細ピットを拡大させ（第三工程）、表面処理されたアルミニウム押出形材を得た。 In the same manner as in Example 1, the pretreated aluminum extruded profile from which the natural oxide film had been removed was placed in an aqueous solution with an oxalic acid concentration of 30 g / l at a bath temperature of 25 ° C. and a current density of 50 A / m 2 at a constant current for 120 seconds. Anodized (first step). Next, it was immersed for 300 seconds in a mixed aqueous solution having a hydrochloric acid concentration of 100 g / l and ferric chloride 40 g / l at a bath temperature of 40 ° C. to form a large number of fine pits on the surface of the aluminum extruded profile (secondary Process). Further, the aluminum extruded profile was surface-treated by immersing it in an aqueous solution having a sodium hydroxide concentration of 50 g / l and a bath temperature of 50 ° C. for 600 seconds to enlarge the fine pits formed in the second step (third step). Got.
得られたアルミニウム押出形材の光沢度及び表面粗さ（Ｒａ、Ｒmax）を実施例1と同様にして測定した。次いで、このアルミニウム押出形材を陽極酸化、電解着色及び艶消し電着塗装を行い処理を終了した。この実施例２の表面処理アルミニウム押出形材は、その光沢度及び表面粗さにおいてバラツキがなく、触感においても視覚においても凹凸のザラツキ感があり、表面光沢度が極めて低く、質感のある均一な表面外観であった。また、アルミニウム押出形材に特有のダイスマークが消失し、アルミニウム押出形材の表面欠陥がなくて均一な表面外観であった。 The gloss and surface roughness (Ra, Rmax) of the obtained aluminum extruded profile were measured in the same manner as in Example 1. Next, the aluminum extruded profile was subjected to anodization, electrolytic coloring and matte electrodeposition coating to finish the treatment. The surface-treated aluminum extruded profile of Example 2 has no variation in its glossiness and surface roughness, has a rough feeling in the tactile sensation and visual sense, has a very low surface glossiness, and has a uniform texture. It was a surface appearance. In addition, the die mark peculiar to the aluminum extruded profile disappeared, and there was no surface defect of the aluminum extruded profile, and the surface appearance was uniform.
実施例１と同様にして自然酸化皮膜を除去した前処理済みのＡ１１００アルミ板材をホウ酸濃度３０ｇ／ｌの水溶液中、浴温３０℃及び電流密度１０Ａ／ｍ２で最終電圧が８０Ｖに達するまで定電流にて陽極酸化した（第一工程）。次いで、浴温４０℃及び塩酸濃度１００ｇ／ｌ−塩化第二銅３０ｇ／ｌの水溶液中に３００秒間浸漬してアルミ板材表面に多数の微細なピットを形成せしめた（第二工程）。更に、水酸化ナトリウム濃度５０ｇ／ｌ、浴温５０℃の水溶液中に６００秒間浸漬して、第二工程で形成された微細ピットを拡大させ（第三工程）、表面処理されたアルミ板材を得た。 In the same manner as in Example 1, the pretreated A1100 aluminum plate from which the natural oxide film was removed was dissolved in an aqueous solution having a boric acid concentration of 30 g / l until the final voltage reached 80 V at a bath temperature of 30 ° C. and a current density of 10 A / m 2. Anodized with a constant current (first step). Subsequently, it was immersed in an aqueous solution having a bath temperature of 40 ° C. and a hydrochloric acid concentration of 100 g / l-cupric chloride 30 g / l for 300 seconds to form a large number of fine pits on the surface of the aluminum plate (second step). Furthermore, it is immersed in an aqueous solution having a sodium hydroxide concentration of 50 g / l and a bath temperature of 50 ° C. for 600 seconds to enlarge the fine pits formed in the second step (third step) to obtain a surface-treated aluminum sheet. It was.
得られたアルミ板材の光沢度及び表面粗さ（Ｒａ、Ｒmax）を実施例1と同様にして測定した。この実施例３の表面処理アルミ板材は、その光沢度及び表面粗さにおいてバラツキがなく、触感においても視覚においても凹凸のザラツキ感があり、表面光沢度が極めて低く、質感のある均一な表面外観であった。また、アルミ板材に特有の圧延模様が消失し、アルミ板材の表面欠陥（圧延痕やストレインマーク）がなくて均一な表面外観であった。 The gloss and surface roughness (Ra, Rmax) of the obtained aluminum plate were measured in the same manner as in Example 1. The surface-treated aluminum sheet of Example 3 has no variation in its glossiness and surface roughness, has a rough texture in the tactile sensation and the visual sense, has a very low surface glossiness, and has a uniform surface appearance with a texture. Met. Moreover, the rolling pattern peculiar to the aluminum plate material disappeared, and there was no surface defect (rolling trace or strain mark) of the aluminum plate material, and the surface appearance was uniform.
実施例１と同様にして自然酸化皮膜を除去した前処理済みのアルミニウム押出形材を電気炉にて空気中で５００℃、３００秒間加熱処理して熱酸化皮膜した（第一工程）。次いで、浴温４０℃及び塩酸濃度１００ｇ／ｌの水溶液中に３００秒間浸漬してアルミニウム押出形材表面に多数の微細なピットを形成せしめた（第二工程）。更に、水酸化ナトリウム濃度５０ｇ／ｌ、浴温５０℃の水溶液中に６００秒間浸漬して、第二工程で形成された微細ピットを拡大させ（第三工程）、表面処理されたアルミニウム押出形材を得た。 In the same manner as in Example 1, the pretreated aluminum extruded profile from which the natural oxide film had been removed was heat-treated in air at 500 ° C. for 300 seconds to form a thermal oxide film (first step). Next, it was immersed in an aqueous solution having a bath temperature of 40 ° C. and a hydrochloric acid concentration of 100 g / l for 300 seconds to form a large number of fine pits on the surface of the aluminum extruded profile (second step). Further, the aluminum extruded profile was surface-treated by immersing it in an aqueous solution having a sodium hydroxide concentration of 50 g / l and a bath temperature of 50 ° C. for 600 seconds to enlarge the fine pits formed in the second step (third step). Got.
得られたアルミニウム押出形材の光沢度及び表面粗さ（Ｒａ、Ｒmax）を測定した。この表面処理アルミニウム押出形材は、その光沢度及び表面粗さにおいてバラツキがなく、触感においても視覚においても凹凸のザラツキ感があり、表面光沢度が極めて低く、質感のある均一な表面外観であった。また、アルミニウム押出形材に特有のダイスマークが消失し、アルミニウム押出形材の表面欠陥がなく、表面品質が安定した。 The resulting aluminum extruded profile was measured for glossiness and surface roughness (Ra, Rmax). This surface-treated aluminum extruded shape has no variation in glossiness and surface roughness, has a rough feeling in tactile sensation and vision, has a very low surface glossiness, and has a textured and uniform surface appearance. It was. In addition, the die mark peculiar to the aluminum extruded profile disappeared, and there was no surface defect of the aluminum extruded profile, and the surface quality was stabilized.
（比較例１）
実施例１と同様にして自然酸化皮膜を除去した前処理済みのアルミニウム合金押出形材を、濃度１５０ｇ／リットルの硫酸水溶液中、浴温２０℃及び電流密度３０Ａ／ｍ２、処理時間６００秒の条件で陽極酸化し、次いで濃度１００ｇ／リットルの塩酸水溶液中、浴温２０℃及び処理時間６０秒の条件でアノード電解して多数の微細なピットを形成せしめ、更に、濃度５５ｇ／リットルの塩酸水溶液中、浴温３５℃及び処理時間１２０秒の条件で浸漬した。次いで、濃度５０ｇ／リットルの水酸化ナトリウム水溶液中、浴温５０℃及び処理時間１０分の条件で浸漬して上記塩酸浸漬処理で形成されたピットを更に拡大させ、表面処理されたアルミニウム合金押出形材を得た。
(Comparative Example 1)
A pretreated aluminum alloy extruded shape from which a natural oxide film was removed in the same manner as in Example 1, in a sulfuric acid aqueous solution having a concentration of 150 g / liter, a bath temperature of 20 ° C., a current density of 30 A / m 2, and a treatment time of 600 seconds. And then anodically electrolyzing in an aqueous hydrochloric acid solution having a concentration of 100 g / liter in a bath temperature of 20 ° C. and a treatment time of 60 seconds to form a large number of fine pits, and further in an aqueous hydrochloric acid solution having a concentration of 55 g / liter. The bath was immersed under conditions of a bath temperature of 35 ° C. and a treatment time of 120 seconds. Next, the aluminum alloy extruded form was surface-treated by further expanding the pit formed by the hydrochloric acid immersion treatment by dipping in a 50 g / liter sodium hydroxide aqueous solution at a bath temperature of 50 ° C. and a treatment time of 10 minutes. The material was obtained.
得られた表面処理アルミニウム合金押出形材の光沢度及び表面粗さ（Ra）を測定した。この比較例１の表面処理アルミニウム合金押出形材は、その光沢度及び表面粗さにおいてばらつきがなく、手で触れてもザラザラした感触はなく均一な外観であったが、光沢度が目標とする値よりも大きかった。 The glossiness and surface roughness (Ra) of the obtained surface-treated aluminum alloy extruded profile were measured. The surface-treated aluminum alloy extruded profile of Comparative Example 1 had no variation in its glossiness and surface roughness and had a uniform appearance with no rough feel even when touched by hand, but the glossiness was the target. It was bigger than the value.
（比較例２）
実施例１と同様にして自然酸化皮膜を除去した前処理済みのアルミニウム押出形材を第一工程の酸化処理を行わずに、浴温４０℃及び塩酸濃度１００ｇ／ｌの水溶液中に３００秒間浸漬した後、水酸化ナトリウム濃度５０ｇ／ｌ、浴温５０℃の水溶液中に６００秒間浸漬して、アルミニウム押出形材の表面処理を完了した。
(Comparative Example 2)
A pretreated aluminum extruded shape from which the natural oxide film was removed in the same manner as in Example 1 was immersed in an aqueous solution having a bath temperature of 40 ° C. and a hydrochloric acid concentration of 100 g / l for 300 seconds without performing the oxidation treatment in the first step. Then, it was immersed in an aqueous solution having a sodium hydroxide concentration of 50 g / l and a bath temperature of 50 ° C. for 600 seconds to complete the surface treatment of the aluminum extruded profile.
得られたアルミニウム押出形材の光沢度及び表面粗さ（Ｒａ、Ｒmax）を、実施例1と同様にして測定した。この比較例の表面処理アルミニウム押出形材は、その光沢度及び表面粗さにおいてバラツキがあり、アルミニウム押出形材のダイスマークやウエルダーラインの押出欠陥が強調された不均一な表面外観であった。 The gloss and surface roughness (Ra, Rmax) of the obtained aluminum extruded profile were measured in the same manner as in Example 1. The surface-treated aluminum extruded profile of this comparative example had variations in glossiness and surface roughness, and had a non-uniform surface appearance in which the extrusion marks of the aluminum extruded profile and welder line extrusion defects were emphasized.
実施例１〜５及び比較例の６０度鏡面光沢度と表面粗さの測定値を表1に示す。 Table 1 shows the measured values of 60 degree specular gloss and surface roughness of Examples 1 to 5 and Comparative Example.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003272969A JP4043419B2 (en) | 2003-07-10 | 2003-07-10 | Surface treatment method of aluminum material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003272969A JP4043419B2 (en) | 2003-07-10 | 2003-07-10 | Surface treatment method of aluminum material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005029868A true JP2005029868A (en) | 2005-02-03 |
| JP4043419B2 JP4043419B2 (en) | 2008-02-06 |
Family
ID=34210359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003272969A Expired - Fee Related JP4043419B2 (en) | 2003-07-10 | 2003-07-10 | Surface treatment method of aluminum material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4043419B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114808079A (en) * | 2022-05-22 | 2022-07-29 | 王海建 | Surface treatment process for aluminum material |
| CN116732518A (en) * | 2023-06-06 | 2023-09-12 | 上海奢藏科技有限公司 | Etching treatment process for surface patterns of special-shaped multi-surface aluminum material |
-
2003
- 2003-07-10 JP JP2003272969A patent/JP4043419B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114808079A (en) * | 2022-05-22 | 2022-07-29 | 王海建 | Surface treatment process for aluminum material |
| CN114808079B (en) * | 2022-05-22 | 2023-09-29 | 山西钰沙新材料科技有限公司 | Surface treatment process of aluminum material |
| CN116732518A (en) * | 2023-06-06 | 2023-09-12 | 上海奢藏科技有限公司 | Etching treatment process for surface patterns of special-shaped multi-surface aluminum material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4043419B2 (en) | 2008-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4363970B2 (en) | Surface treatment method of aluminum material | |
| JP4043419B2 (en) | Surface treatment method of aluminum material | |
| JPH0559591A (en) | Surface treatment of high-temperature worked body of aluminum alloy | |
| JP3828387B2 (en) | Surface treatment method of aluminum material and surface-treated aluminum material | |
| JP4048462B2 (en) | Surface treatment method of aluminum material | |
| JP3828388B2 (en) | Surface treatment method of aluminum material and surface-treated aluminum material | |
| JP3930706B2 (en) | Surface treatment method of aluminum material and surface-treated aluminum material | |
| JP2005042199A (en) | Surface treated aluminum material | |
| JP3930709B2 (en) | Surface treatment method of aluminum material and surface-treated aluminum material | |
| US5288372A (en) | Altering a metal body surface | |
| JP3930707B2 (en) | Surface treatment method of aluminum material and surface-treated aluminum material | |
| JPS6259192B2 (en) | ||
| JPS6213563A (en) | Method for coloring stainless steel | |
| JP3930708B2 (en) | Surface treatment method of aluminum material and surface-treated aluminum material | |
| KR20100085702A (en) | Method on printing on the surface of treated aluminium material | |
| JPH0551711A (en) | Production of high temperature-worked product of aluminum alloy | |
| JP2002256490A (en) | Surface treatment method for aluminum material | |
| JP2005042198A (en) | Surface treated aluminum material | |
| JP2005042197A (en) | Surface treated aluminum material | |
| JPS6029489A (en) | Surface treatment of aluminum alloy for patterning | |
| JPH09165697A (en) | Patina copper sheet like colored titanium or titanium alloy material and its production | |
| JP2005042196A (en) | Surface treated aluminum material | |
| KR100496674B1 (en) | a surface treatment solution for aluminum or aluminum allay and aluminum or aluminum allay treatmented thereby | |
| JP3344973B2 (en) | How to color aluminum material | |
| JPS61183497A (en) | Surface treatment for patterning of aluminum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060127 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20071024 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20071106 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20071113 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101122 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101122 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111122 Year of fee payment: 4 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111122 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121122 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131122 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |