JP3142152B2 - Manufacturing method of aluminum alloy plate for anodizing treatment - Google Patents
Manufacturing method of aluminum alloy plate for anodizing treatmentInfo
- Publication number
- JP3142152B2 JP3142152B2 JP03197117A JP19711791A JP3142152B2 JP 3142152 B2 JP3142152 B2 JP 3142152B2 JP 03197117 A JP03197117 A JP 03197117A JP 19711791 A JP19711791 A JP 19711791A JP 3142152 B2 JP3142152 B2 JP 3142152B2
- Authority
- JP
- Japan
- Prior art keywords
- plate
- casting
- pink
- color tone
- aluminum alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Continuous Casting (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は陽極酸化処理を施して
使用される用途のアルミニウム合金板、例えばビルのカ
ーテンウォールや外壁、屋根、ドア、門扉、あるいは内
装材などの建材、さらには各種器物、容器、銘板等に使
用されるアルミニウム合金板の製造方法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum alloy plate used for anodizing treatment, for example, a building material such as a curtain wall and an outer wall of a building, a roof, a door, a gate, an interior material, and various other objects. The present invention relates to a method for producing an aluminum alloy plate used for a container, a nameplate or the like.
【０００２】[0002]
【従来の技術】一般にカーテンウォールや建築外装材、
内装材などの建材、あるいは器物、容器、銘板などに使
用されるアルミニウム合金の圧延材は、耐食性の観点か
ら陽極酸化処理を施して用いられることが多い。これら
の用途の陽極酸化処理用アルミニウム合金としては、陽
極酸化処理後の色調が淡灰色系からシルバー系のものが
多く、このような合金の圧延材としては一般にＪＩＳ
１０５０合金、１１００合金、５００５合金等が使用さ
れることが多く、また灰色系のものとしてはＡｌ−１〜
４％Ｓｉ合金、Ａｌ−Ｆｅ−Ｍｎ−Ｍｇ合金が一般的で
ある。2. Description of the Related Art In general, curtain walls and building exterior materials,
Rolled materials of aluminum alloy used for building materials such as interior materials, or for objects, containers, nameplates, etc. are often used after being subjected to anodizing treatment from the viewpoint of corrosion resistance. Many aluminum alloys for anodizing for these uses have a color tone from light gray to silver after anodizing, and rolled materials of such alloys are generally JIS.
In many cases, 1050 alloy, 1100 alloy, 5005 alloy, and the like are used.
A 4% Si alloy and an Al-Fe-Mn-Mg alloy are common.
【０００３】[0003]
【発明が解決しようとする課題】最近では建築外装材、
内装材等の用途においては、デザイン上の要請から色調
の多様化、個性化を求められることが多くなっている。
陽極酸化処理を施して用いられるアルミニウム合金につ
いても、これらの用途では種々の色調が求められること
が多くなっており、その例としてピンクないし赤紫色の
色調がある。SUMMARY OF THE INVENTION Recently, building exterior materials,
In applications such as interior materials, diversification and individualization of color tone are often required due to design requirements.
For an aluminum alloy to be subjected to anodizing treatment, various colors are often required for these uses, and examples thereof include a pink to purple-red color.
【０００４】また建材等においては、単に色調のみなら
ず、デザイン的な観点から個性的な外観模様を有するこ
とも求められるようになっており、その一つとして横縞
模様がある。[0004] Building materials and the like are required not only to have a simple color tone but also to have a unique appearance from the viewpoint of design, and one of them is a horizontal stripe pattern.
【０００５】アルミニウム合金の陽極酸化処理材に各種
の色調や模様を与える方法としては、二次電解法や染色
法、その他の塗装法などもあるが、これらの方法では退
色の問題があるほか、耐食性やコスト等の問題がある。
したがって陽極酸化処理のままでピンクないし赤紫色の
色調や横縞模様を得ることが望まれる。また陽極酸化処
理には、シュウ酸電解浴等を用いることもあるが、一般
には硫酸電解浴を用いることが多く、実際硫酸電解浴に
よる陽極酸化処理は、シュウ酸電解浴等による陽極酸化
処理と比較して、電解条件や電解浴管理に厳密さが要求
されず、また皮膜特性も優れるとともにコストも低いこ
とから、硫酸電解浴による陽極酸化処理のままでピンク
〜赤紫色の色調や所定の横縞模様を得ることが望まれ
る。Methods for imparting various colors and patterns to the aluminum alloy anodized material include a secondary electrolytic method, a dyeing method, and other coating methods. These methods have a problem of fading. There are problems such as corrosion resistance and cost.
Therefore, it is desired to obtain a pink or purplish red color tone or a horizontal stripe pattern while the anodizing treatment is performed. Although an oxalic acid electrolytic bath may be used for the anodic oxidation treatment, a sulfuric acid electrolytic bath is generally used in many cases.In practice, the anodic oxidation treatment with the sulfuric acid electrolytic bath is the same as the anodic oxidation treatment with the oxalic acid electrolytic bath. In comparison, strict requirements are not required for the electrolysis conditions and electrolysis bath management, and the film properties are excellent and the cost is low. It is desired to obtain a pattern.
【０００６】しかしながら、従来は硫酸電解浴による陽
極酸化処理のままでピンク〜赤紫色の色調を得る手法は
確立されておらず、またもちろん硫酸電解浴による陽極
酸化処理のままでこれらの色調の横縞模様を得る手法も
知られていなかったのが実情である。特に板連続鋳造法
（連続鋳造圧延法）によって５〜５０mm程度の板を直接
鋳造する方法を適用した場合に、硫酸電解浴による陽極
酸化処理のままでピンク〜赤紫色の色調の横縞模様を得
るための手法は知られていなかったのが実情である。However, a method of obtaining a pink to purple-red color tone with the anodic oxidation treatment in a sulfuric acid electrolytic bath has not been established, and, of course, horizontal stripes of these colors with an anodic oxidation treatment in a sulfuric acid electrolytic bath have not been established. The fact is that no technique for obtaining patterns has been known. In particular, when a method of directly casting a plate of about 5 to 50 mm by a plate continuous casting method (continuous casting and rolling method) is applied, a horizontal stripe pattern having a pink to reddish purple color tone is obtained with anodizing treatment using a sulfuric acid electrolytic bath. It is the fact that the method for this was not known.
【０００７】この発明は以上の事情を背景としてなされ
たもので、硫酸電解浴による陽極酸化処理のままで、ピ
ンク〜赤紫色の色調を有しかつ鋳造方向もしくは圧延方
向に対して直交する方向の横縞模様を有するアルミニウ
ム合金板を確実かつ安定して得る方法を提供することを
目的とするものである。The present invention has been made in view of the above circumstances, and has a pink to purplish red color tone and a direction perpendicular to the casting direction or the rolling direction while being subjected to anodic oxidation treatment in a sulfuric acid electrolytic bath. It is an object of the present invention to provide a method for reliably and stably obtaining an aluminum alloy plate having a horizontal stripe pattern.
【０００８】[0008]
【課題を解決するための手段】この発明の陽極酸化処理
用アルミニウム合金板の製造方法は、基本的には、合金
の成分系を、比較的多量のＭｎを含有するＡｌ−Ｍｎ系
とするとともに所定量のＦｅ、Ｔｉ（およびＢ）を添加
したものとし、さらに直接的に板を鋳造する板連続鋳造
法の特性を有効に利用して、硫酸電解浴による陽極酸化
処理後の表面に横縞を発生させると同時に、その硫酸電
解浴による陽極酸化処理のままの色調としてピンク〜赤
紫色を発色させるようにしている。そしてまた、板連続
鋳造のままの板、あるいは板連続鋳造の後、冷間圧延を
施して板厚を減じた板を提供することとしている。According to the method for producing an aluminum alloy plate for anodizing treatment of the present invention, basically, the component system of the alloy is an Al-Mn system containing a relatively large amount of Mn. A predetermined amount of Fe, Ti (and B) is added, and horizontal stripes are formed on the surface after the anodizing treatment with a sulfuric acid electrolytic bath by effectively utilizing the characteristics of the continuous plate casting method of directly casting a plate. Simultaneously with the generation, pink to reddish purple is developed as the color tone of the anodic oxidation treatment by the sulfuric acid electrolytic bath. Further, it is intended to provide a plate as it is in continuous plate casting, or a plate having a reduced thickness by cold rolling after continuous plate casting.
【０００９】[0009]
【００１０】[0010]
【００１１】具体的には、請求項１の発明の方法は、Ｍ
ｎ０．８〜３．５wt％、Ｆｅ０．０５wt％以上１．０wt
％未満、Ｓｉ０．５wt％以下を含有するとともに、結晶
粒微細化剤としてＴｉ０．００５〜０．１５wt％を単独
でまたはＢ０．０００１〜０．０５００wt％と組合せて
含有し、残部がＡｌおよびその他の不可避的不純物より
なる合金の溶湯を、板連続鋳造法によって５℃／sec 以
上の冷却速度で鋳造することを特徴とするものである。Specifically, the method of the first aspect of the present invention
n0.8-3.5wt%, Fe0.05wt% or more 1.0wt
%, Less than 0.5 wt% of Si, 0.005 to 0.15 wt% of Ti alone or in combination with 0.0001 to 0.0500 wt% of B as a grain refiner, the balance being Al and other A molten metal of an alloy comprising unavoidable impurities is cast at a cooling rate of 5 ° C./sec or more by a continuous plate casting method.
【００１２】さらに請求項２の発明の方法は前記同様の
成分組成の合金の溶湯を、板連続鋳造法によって５℃／
sec 以上の冷却速度で鋳造した後、もしくはさらにその
鋳造の後に２５０〜３５０℃で０．５〜２４時間加熱し
た後、冷間圧延することを特徴とするものである。Further, according to a second aspect of the present invention, a molten alloy having the same composition as described above is melted at 5 ° C. /
After casting at a cooling rate of sec or more, or after the casting, heating is performed at 250 to 350 ° C. for 0.5 to 24 hours, and then cold rolling is performed.
【００１３】[0013]
【作用】先ずこの発明の方法において使用されるアルミ
ニウム合金の成分組成限定理由を説明する。First, the reasons for limiting the composition of the aluminum alloy used in the method of the present invention will be described.
【００１４】Ｍｎ：Ｍｎが固溶状態で存在すれば、陽極
酸化処理後の色調としてピンク〜赤紫色を発色させるこ
とができ、Ｍｎの固溶量が多いほどピンク〜赤紫色は強
くなる。したがってＭｎは、この発明においてピンク〜
赤紫色の色調を得るために基本的に重要な合金元素であ
る。Ｍｎの固溶量が多いほどピンク〜赤紫色は強くなる
が、充分なピンク〜赤紫色の色調を得るためには通常は
０．８wt％以上のＭｎが必要である。但し、ＤＣ鋳造法
等の通常の冷却速度が遅い鋳造方法では、Ｍｎが０．８
wt％以上ではＭｎを強制的に固溶できないために、ピン
ク〜赤紫色を明瞭に発色できず、さらにＭｎが１．５wt
％を越えれば粗大なＭｎ系の初晶金属間化合物が生じ
て、表面欠陥を招く。これに対し板連続鋳造法によって
５℃／sec 以上の冷却速度で急冷凝固させれば、粗大な
Ｍｎ系の金属間化合物を生成させないＭｎ添加量範囲を
３．５wt％にまで上げることができ、しかも板連続鋳造
法の如き急冷凝固では、添加したＭｎの大部分を強制的
に固溶でき、そのため充分に強いピンク〜赤紫色を発色
させることができる。但しＭｎが３．５wt％を越えれ
ば、板連続鋳造法を適用しても初晶の粗大化合物が晶出
し、しかもＭｎの強制固溶量も限界に達するからそれ以
上添加しても意味がない。したがってＭｎ量は０．８〜
３．５wt％の範囲内とした。Mn: If Mn exists in a solid solution state, pink to reddish purple can be developed as a color tone after the anodizing treatment, and the more solid solution amount of Mn, the stronger pink to reddish purple. Therefore, Mn is pink in the present invention.
It is a fundamentally important alloying element for obtaining a red-purple color tone. As the amount of solid solution of Mn increases, the pink-red-purple color becomes stronger. However, in order to obtain a sufficient pink-red-purple color tone, Mn of 0.8 wt% or more is usually required. However, in a casting method with a normal slow cooling rate such as a DC casting method, Mn is 0.8%.
If the content of Mn is more than wt%, Mn cannot be solid-dissolved, so that pink to reddish purple cannot be clearly formed.
%, Coarse Mn-based primary intermetallic compounds are generated, leading to surface defects. In contrast, rapid solidification at a cooling rate of 5 ° C./sec or more by the continuous plate casting method can increase the Mn addition range in which coarse Mn-based intermetallic compounds are not formed to 3.5 wt%. In addition, in rapid solidification such as the continuous plate casting method, most of the added Mn can be forcibly dissolved in a solid solution, so that a sufficiently strong pink to reddish purple color can be developed. However, if Mn exceeds 3.5 wt%, a coarse compound of primary crystals is crystallized even when the continuous casting method is applied, and the amount of forced solid solution of Mn reaches a limit, so that it is meaningless to add more. . Therefore, the Mn content is 0.8 to
It was within the range of 3.5 wt%.
【００１５】Ｆｅ：Ｆｅはこの発明において陽極酸化処
理後に横縞模様を呈するに寄与する。すなわち、Ｆｅが
含有されれば、Ａｌ−Ｆｅ（−Ｍｎ−Ｓｉ）系の晶出物
が晶出するが、このＡｌ−Ｆｅ（−Ｍｎ−Ｓｉ）系の晶
出物はピンク〜赤紫色の色調を若干濁らせる。特にＡｌ
−Ｆｅ−Ｍｎ（−Ｓｉ）系の晶出物が大きくて、粗く分
布すれば、その粗く分布した部分が他の部分とやや異な
る色調を呈することになる。一対の回転冷却ロールやキ
ャタピラー、ベルト等の間に給湯して鋳造する板連続鋳
造法では、後に改めて説明するように鋳造時の冷却速度
に脈動が生じるが、Ｆｅ量が０．０５wt％以上となれば
上述の鋳造時の冷却速度の脈動によって、Ａｌ−Ｆｅ
（−Ｍｎ−Ｓｉ）系の晶出物が鋳造方向に交互に疎密に
分布することになり、その結果、陽極酸化処理後の板表
面に鋳造方向に直交する特有の横縞模様を生じさせるこ
とができる。ここで、Ｆｅ量が０．０５wt％未満であれ
ば、Ａｌ−Ｆｅ（−Ｍｎ−Ｓｉ）系の晶出物の晶出量が
不足し、横縞模様を得ることが困難となり、一方Ｆｅ量
が１．０wt％以上となれば、鋳造が困難となる。したが
ってＦｅ量は０．０５wt％以上、１．０wt％未満とする
必要がある。Fe: Fe contributes to exhibiting a horizontal stripe pattern after the anodic oxidation treatment in the present invention. That is, if Fe is contained, an Al-Fe (-Mn-Si) -based crystallized product is crystallized, but the Al-Fe (-Mn-Si) -based crystallized product has a pink to purple-red color. The color tone is slightly muddy. Especially Al
If the -Fe-Mn (-Si) crystallized substance is large and coarsely distributed, the coarsely distributed portion will exhibit a slightly different color tone from the other portions. In the continuous plate casting method in which hot water is cast between a pair of rotating cooling rolls, caterpillars, belts, and the like, a pulsation occurs in the cooling rate during casting, as will be described later, but the Fe content is 0.05 wt% or more. If possible, the pulsation of the cooling rate during the casting described above causes Al-Fe
The (-Mn-Si) crystallized material is alternately and densely distributed in the casting direction, and as a result, a specific horizontal stripe pattern perpendicular to the casting direction is formed on the plate surface after the anodizing treatment. it can. Here, if the amount of Fe is less than 0.05 wt%, the amount of Al-Fe (-Mn-Si) -based crystallization becomes insufficient, and it becomes difficult to obtain a horizontal stripe pattern. If it exceeds 1.0 wt%, casting becomes difficult. Therefore, the amount of Fe needs to be 0.05 wt% or more and less than 1.0 wt%.
【００１６】Ｓｉ：ＳｉがＦｅとともに含有されれば、
Ａｌ−Ｆｅ−Ｓｉ（−Ｍｎ）系の晶出物が晶出し、この
Ａｌ−Ｆｅ−Ｓｉ（−Ｍｎ）系の晶出物は、Ｆｅの項で
Ａｌ−Ｆｅ（−Ｍｎ−Ｓｉ）系晶出物として述べたよう
に、ピンク〜赤紫色の色調を若干濁らせ、かつ連続鋳造
時の冷却速度の脈動によって鋳造方向に交互に疎密に分
布し、横縞模様を発生させる。したがってＳｉは、横縞
模様の現出を助長させる効果がある。但し、Ｓｉ量が
０．５wt％を越えれば鋳造が困難となるから、Ｓｉ量は
０．５wt％以下とする必要がある。Si: If Si is contained together with Fe,
An Al—Fe—Si (—Mn) crystallized product is crystallized, and the Al—Fe—Si (—Mn) crystallized product is an Al—Fe (—Mn—Si) crystal in the Fe term. As described above, the color tone of pink to magenta becomes slightly turbid, and is distributed alternately and sparsely in the casting direction due to the pulsation of the cooling rate during continuous casting, thereby generating a horizontal stripe pattern. Therefore, Si has the effect of promoting the appearance of horizontal stripes. However, if the Si content exceeds 0.5 wt%, casting becomes difficult, so the Si content must be 0.5 wt% or less.
【００１７】Ｔｉ，Ｂ：少量のＴｉを単独で、あるいは
少量のＴｉを微量のＢと組合せて添加することは、鋳塊
結晶粒微細化のために有効である。特にこの発明で適用
する板連続鋳造法では、鋳塊結晶粒微細化は、偏析やそ
れに起因する溶質元素のしみだし、およびその溶質元素
の酸化等の鋳造欠陥を防止する効果がある。また鋳造法
にかかわらず、鋳塊結晶粒微細化は晶出化合物の均一微
細な分散をもたらすため、模様以外の色むらの発生を防
止でき、その結果安定な横縞模様を発現する効果をもた
らす。Ｔｉが０．００５wt％未満では鋳塊結晶粒微細化
の効果が得られず、Ｔｉが０．１５wt％を越えれば初晶
ＴｉＡｌ3を晶出して表面特性を害するから、Ｔｉは
０．００５〜０．１５wt％の範囲内とした。またＴｉと
ともにＢを添加する場合、Ｂ量が０．０００１wt％未満
ではＢ添加の効果が得られず、一方Ｂ量が０．０５００
wt％を越えればＴｉＢ2 の粗大粒子が混入して表面欠陥
を招くから、Ｂは０．０００１〜０．０５００wt％の範
囲内とした。Ti, B: Adding a small amount of Ti alone or combining a small amount of Ti with a small amount of B is effective for refining ingot crystal grains. In particular, in the continuous plate casting method applied in the present invention, the refinement of ingot crystal grains has an effect of preventing casting defects such as segregation and exudation of a solute element due to the segregation and oxidation of the solute element. Regardless of the casting method, the refinement of the ingot crystal grains results in uniform and fine dispersion of the crystallized compound, so that it is possible to prevent the occurrence of color unevenness other than the pattern, and as a result, it has the effect of developing a stable horizontal stripe pattern. If Ti is less than 0.005 wt%, the effect of refining ingot crystal grains cannot be obtained, and if Ti exceeds 0.15 wt%, primary crystal TiAl 3 is crystallized and surface properties are impaired. It was within the range of 0.15 wt%. When B is added together with Ti, if the B content is less than 0.0001 wt%, the effect of B addition cannot be obtained, while the B content is 0.0500 wt%.
Since lead to surface defects if exceeds the wt% of coarse particles of TiB 2 is mixed, B was in the range of 0.0001~0.0500wt%.
【００１８】以上の各成分のほかは、基本的にはＡｌ
と、不可避的不純物とすれば良い。但し、通常のアルミ
ニウム合金においては、鋳造時の溶湯の酸化を防止する
ため微量のＢｅを添加することがあるが、この発明の合
金の場合にも、微量のＢｅを添加しても良く、Ｂｅ量が
５００ppm 程度以下であれば特に他の性能を劣化させる
ことはない。またそのほか、強度向上を目的としてＣ
ｕ，Ｚｎ，Ｍｇ，Ｃｒのうちのいずれか一種または二種
以上が含有されてていも良く、Ｃｕは１．０wt％以下、
Ｚｎは２．０wt％以下、Ｍｇは２．０wt％以下、Ｃｒは
０．５wt％以下であれば特に他の性能を損なうことな
く、この発明の目的を達成することができる。ただし、
Ｃｕ，Ｚｎ，Ｃｒは耐食性の観点から各々０．１wt％未
満とすることが好ましく、またＭｇは酸化物を生成しや
すく、これに起因する介在物が表面処理後の表面品質に
悪影響を及ぼすから、Ｍｇも０．１wt％未満が好まし
い。In addition to the above components, Al
And unavoidable impurities. However, in a normal aluminum alloy, a small amount of Be may be added in order to prevent oxidation of the molten metal during casting. However, in the case of the alloy of the present invention, a small amount of Be may be added. If the amount is less than about 500 ppm, no other performance is degraded. In addition, for the purpose of improving strength, C
Any one or more of u, Zn, Mg, and Cr may be contained.
If the Zn content is 2.0 wt% or less, the Mg content is 2.0 wt% or less, and the Cr content is 0.5 wt% or less, the object of the present invention can be achieved without impairing other performances. However,
Cu, Zn, and Cr are each preferably less than 0.1 wt% from the viewpoint of corrosion resistance, and Mg easily forms oxides, and inclusions resulting therefrom adversely affect the surface quality after surface treatment. , Mg is also preferably less than 0.1 wt%.
【００１９】次にこの発明のアルミニウム合金の製造方
法について説明する。Next, a method for producing the aluminum alloy of the present invention will be described.
【００２０】この発明の方法では、合金溶湯の鋳造法と
して、一対の回転冷却ロールやキャタピラー、ベルト等
の間に溶湯を供給することによって板を直接鋳造する、
板連続鋳造法を適用する。これは、例えば３Ｃ法あるい
はハンター法、キャスターII、ハザレー法として知られ
ており、またロールキャストあるいはストリップキャス
トとも称されている。このような板連続鋳造法では、溶
湯が回転冷却ロールに接する際に表面張力の影響で溶湯
が例えば回転冷却ロール表面に接する位置が周期的に変
動し、この結果冷却速度も周期的に変動する。そのため
リップルマークと称される模様が生じやすいが、この発
明ではむしろこの冷却速度の周期的変動（脈動）を有効
利用し、適切な合金成分組成と組合せることによって安
定な横縞模様を発現させ得たのである。In the method of the present invention, as a method of casting a molten alloy, a plate is directly cast by supplying the molten metal between a pair of rotary cooling rolls, caterpillars, belts, and the like.
Apply the continuous plate casting method. This is known as, for example, the 3C method, the Hunter method, the caster II, or the Hatherley method, and is also called a roll cast or a strip cast. In such a continuous plate casting method, when the molten metal comes into contact with the rotary cooling roll, the position where the molten metal comes into contact with, for example, the surface of the rotary cooling roll fluctuates periodically due to the effect of surface tension, and as a result, the cooling rate also fluctuates periodically. . For this reason, a pattern called a ripple mark is likely to occur. However, in the present invention, a stable horizontal stripe pattern can be developed by effectively utilizing the periodic fluctuation (pulsation) of the cooling rate and combining it with an appropriate alloy component composition. It was.
【００２１】この発明の方法において、前述のような成
分組成の合金溶湯を鋳造するにあたって、陽極酸化処理
によるピンク色の発色に寄与する固溶Ｍｎを充分に確保
するべく、Ｍｎを強制的に固溶させ、かつ１．５wt％以
上のＭｎ量でも粗大な金属間化合物を生成させないため
には、５℃／sec 以上の冷却速度が必要である。このよ
うな５℃／sec 以上の鋳造時冷却速度を、工業的に大き
な板で得ることは、前述のような一対の冷却ロールやキ
ャタピラー、ベルト等の間に溶湯を供給して５〜５０mm
程度の板を直接鋳造する、板連続鋳造法（連続鋳造圧延
法）で達成できる。In the method of the present invention, when casting a molten alloy having the above-described composition, Mn is forcibly solidified in order to sufficiently secure solid Mn that contributes to the development of pink color by anodic oxidation. A cooling rate of 5 ° C./sec or more is necessary in order to dissolve and not to form a coarse intermetallic compound even if the amount of Mn is 1.5 wt% or more. To obtain such a cooling rate of 5 ° C./sec or more at the time of casting with an industrially large plate, it is necessary to supply a molten metal between a pair of cooling rolls, caterpillars, belts, and the like as described above to obtain a cooling rate of 5 to 50 mm.
It can be achieved by a continuous plate casting method (continuous casting and rolling method) in which a certain degree of plate is directly cast.
【００２２】このようにして板連続鋳造法により得られ
た鋳造板は、そのままの板厚で陽極酸化処理に供しても
良く、あるいは冷間圧延を施して所要の板厚としてから
陽極酸化処理に供しても良い。熱処理は必須条件ではな
いが、鋳造板均質化の目的、あるいは冷間圧延を容易に
する目的、さらには強度調整の目的などから、鋳造直
後、あるいは冷間圧延の中途や冷間圧延の後に熱処理
（焼鈍）を施しても良い。但し、熱処理によってＡｌ−
Ｆｅ（−Ｍｎ−Ｓｉ）系の微細析出物が生じれば、色調
が濁ってピンク〜赤紫の色調から逸脱し、灰色〜黒色と
なってしまうから、熱処理はこのような微細析出物が生
じないように、比較的低温で行なう必要がある。また鋳
造板の段階で熱処理する場合と、冷間圧延中途もしくは
後に熱処理する場合とでは、次のように若干条件が異な
る。The cast sheet obtained by the continuous casting method as described above may be subjected to anodizing treatment with the same thickness, or may be subjected to cold rolling to a required thickness and then subjected to anodizing treatment. May be served. Although heat treatment is not an essential condition, heat treatment is performed immediately after casting, after cold rolling, or after cold rolling for the purpose of homogenizing cast plates, facilitating cold rolling, and adjusting strength. (Annealing) may be performed. However, Al-
If Fe (-Mn-Si) -based fine precipitates are formed, the color tone becomes turbid and deviates from the pink to red-purple color to gray to black. It must be done at a relatively low temperature so that it does not occur. Further, the condition is slightly different between the case where the heat treatment is performed at the stage of the cast plate and the case where the heat treatment is performed during or after the cold rolling as follows.
【００２３】先ず鋳造板の段階で行なう加熱は、鋳造時
の偏析を緩和して均質化する目的で、またその後に冷間
圧延を行なう場合は以降の冷間圧延を容易にする目的で
行なうが、この場合温度が２５０℃未満では鋳造時の偏
析を緩和できず、一方３５０℃を越えればＡｌ−Ｆｅ
（−Ｍｎ−Ｓｉ）系の微細析出物が生じて陽極酸化処理
後の色調が灰色〜黒色となってしまう。また時間は、
０．５時間未満では熱処理の効果がなく、一方２４時間
を越えれば効果が飽和し、経済性を損なうだけである。
したがって鋳造板の段階で行なう加熱は、２５０〜３５
０℃の範囲内で０．５〜２４時間とする。First, the heating performed at the stage of the cast plate is carried out for the purpose of relaxing segregation at the time of casting and homogenizing it, and when performing cold rolling thereafter, for the purpose of facilitating subsequent cold rolling. In this case, if the temperature is lower than 250 ° C., segregation during casting cannot be alleviated, while if it exceeds 350 ° C., Al—Fe
(-Mn-Si) -based fine precipitates are generated, and the color tone after anodizing becomes gray to black. The time is
If the time is less than 0.5 hour, the effect of the heat treatment is not obtained, while if it exceeds 24 hours, the effect is saturated and the economic efficiency is only impaired.
Therefore, the heating performed at the stage of the cast plate is 250-35.
0.5 to 24 hours within the range of 0 ° C.
【００２４】冷間圧延の中途もしくは後に行なう熱処理
（中間焼鈍もしくは最終焼鈍）は、以後の冷間圧延を容
易にしたり温度調整したりする目的で行なう。この場合
の熱処理には、バッチ式の焼鈍と連続焼鈍とのいずれを
用いても良い。The heat treatment (intermediate annealing or final annealing) performed during or after cold rolling is performed for the purpose of facilitating the subsequent cold rolling or adjusting the temperature. For the heat treatment in this case, either batch annealing or continuous annealing may be used.
【００２５】バッチ式焼鈍の場合、目的とする強度に応
じて温度が選択されるが、２００℃未満では焼鈍の効果
が得られず、一方３５０℃を越える高温ではＡｌ−Ｆｅ
（−Ｍｎ−Ｓｉ）系の微細析出物が生じてピンク赤紫色
の色調が得られなくなってしまい、また加熱保持時間が
０．５時間未満では焼鈍の効果が得られず、一方１２時
間を越えれば３５０℃以下でもＡｌ−Ｆｅ（−Ｍｎ−Ｓ
ｉ）系の微細析出物が生じるおそれがある。したがって
冷間圧延の中途もしくは後に行なう焼鈍にバッチ式焼鈍
を適用する場合には、２００〜３５０℃の範囲内の温度
で０．５〜１２時間の加熱保持とする。In the case of batch annealing, the temperature is selected in accordance with the desired strength. However, the effect of annealing cannot be obtained at a temperature lower than 200 ° C., whereas at a high temperature exceeding 350 ° C., Al—Fe
(-Mn-Si) -based fine precipitates are formed, so that a pink-red-purple color tone cannot be obtained. Further, if the heating holding time is less than 0.5 hour, the effect of annealing cannot be obtained, while the heating holding time exceeds 12 hours. Al-Fe (-Mn-S)
i) Fine precipitates of the system may be generated. Therefore, when applying the batch annealing to the annealing performed during or after the cold rolling, the heating is performed at a temperature in the range of 200 to 350 ° C. for 0.5 to 12 hours.
【００２６】一方連続式焼鈍の場合は、コイルを連続的
に巻戻しながら焼鈍するため、一般的にバッチ式焼鈍と
比較して、高温短時間の処理となる。そしてこの場合、
高温でも加熱は短時間であるため、実質上Ａｌ−Ｆｅ
（−Ｍｎ−Ｓｉ）系の微細析出物は生じない。したがっ
て加熱到達温度は、色調の点からは制約されず、強度調
整等の目的から選択すれば良いが、３００℃未満では焼
鈍の効果が得られず、５００℃を越えれば共晶融解の発
生のおそれがあり、また保持時間が３分を越えれば高温
では結晶粒粗大化のおそれがある。したがって冷間圧延
の中途もしくは後に連続焼鈍により行なう焼鈍は、３０
０〜５００℃の温度で保持なしもしくは３分以下の保持
とする。On the other hand, in the case of continuous annealing, since the coil is annealed while being continuously unwound, the treatment is generally performed at a higher temperature and in a shorter time than in batch annealing. And in this case,
Since heating is performed for a short time even at a high temperature, Al-Fe
No fine precipitate of (-Mn-Si) system is generated. Therefore, the heating temperature is not limited from the point of color tone and may be selected for the purpose of strength adjustment or the like. However, the effect of annealing cannot be obtained below 300 ° C., and if it exceeds 500 ° C., eutectic melting may occur. If the holding time exceeds 3 minutes, the crystal grains may be coarsened at a high temperature. Therefore, annealing performed during or after cold rolling by continuous annealing is 30
No holding at a temperature of 0 to 500 ° C or holding for 3 minutes or less.
【００２７】次に上述のような方法で得られたアルミニ
ウム合金（鋳造板もしくは圧延板）に対して、陽極酸化
処理を施して実際にピンク〜赤紫色の色調で横縞模様を
有する板を得るためのプロセスを説明する。Next, the aluminum alloy (cast plate or rolled plate) obtained by the above-described method is subjected to anodizing treatment to obtain a plate having a horizontal stripe pattern in a pink to magenta color tone. The process will be described.
【００２８】陽極酸化処理にあたっては、予め表面の汚
れおよび表面の欠陥を除去しておくため、脱脂およびエ
ッチングを行なうのが一般的である。エッチングは、苛
性ソーダ系のアルカリエッチングを行なうのが通常であ
る。そして陽極酸化処理自体は、Ｈ2 ＳＯ4 濃度が１０
〜２５ vol％の硫酸浴を用い、浴温度１０〜３０℃、電
流密度１．５Ａ／dm2 以上、２．５Ａ／dm2 未満で行な
い、膜厚１０〜３０μｍの陽極酸化皮膜を生成させる。In the anodic oxidation treatment, degreasing and etching are generally performed in order to remove surface dirt and surface defects in advance. Usually, caustic soda-based alkaline etching is performed. Then, the anodic oxidation treatment itself is performed when the H 2 SO 4 concentration is 10%.
An anodic oxide film having a film thickness of 10 to 30 μm is formed by using a sulfuric acid bath having a bath temperature of 10 to 30 ° C., a current density of 1.5 A / dm 2 or more and less than 2.5 A / dm 2 using a sulfuric acid bath of 25 vol%.
【００２９】ここで、硫酸浴のＨ2 ＳＯ4 濃度が１０ v
ol％未満では生成される陽極酸化皮膜の多孔度が減少し
て浴電圧が高くなる。一方Ｈ2 ＳＯ4 濃度が２５ vol％
を越えれば、表面が荒れて陽極酸化皮膜が柔らかくな
る。また浴温度が１０℃未満では所要の膜厚を得るため
に長時間の処理を要して不経済となり、一方３０℃を越
えれば陽極酸化処理後の耐食性が低下してしまう。さら
に電流密度は、２．５Ａ／dm2 以上では処理に多大な電
力を要し、実用的でなく、一方１．５Ａ／dm2 未満で
は、陽極酸化処理後の色調が薄くなって強いピンク〜赤
紫色が得られなくなる。また生成される陽極酸化皮膜の
膜厚が１０μｍ未満では充分な耐食性が得られず、一方
３０μｍを越えるまで厚くすることは経済的でない。Here, the H 2 SO 4 concentration of the sulfuric acid bath is 10 v
If the amount is less than ol%, the porosity of the formed anodic oxide film decreases, and the bath voltage increases. On the other hand, the H 2 SO 4 concentration was 25 vol%
If it exceeds, the surface becomes rough and the anodic oxide film becomes soft. If the bath temperature is lower than 10 ° C., it takes a long time to obtain a required film thickness, which is uneconomical. On the other hand, if the bath temperature is higher than 30 ° C., the corrosion resistance after the anodic oxidation treatment is reduced. Further, when the current density is 2.5 A / dm 2 or more, a large amount of electric power is required for the treatment, which is not practical. On the other hand, when the current density is less than 1.5 A / dm 2 , the color tone after anodizing becomes lighter and becomes stronger. The purplish red color cannot be obtained. If the thickness of the anodic oxide film formed is less than 10 μm, sufficient corrosion resistance cannot be obtained. On the other hand, increasing the thickness to more than 30 μm is not economical.
【００３０】以上のような硫酸浴による陽極酸化処理に
よって、ピンク〜赤紫色の色調の横縞模様を得ることが
できる。By the anodic oxidation treatment in the sulfuric acid bath as described above, a horizontal stripe pattern having a pink to purple-red color tone can be obtained.
【００３１】なおこの発明で得られる横縞模様は、図１
に示すように、鋳造方向、圧延方向に直交する方向の縞
模様であって、比較的薄い色の地の部分１に、直線状も
しくは直線に近い波状、曲線状の比較的濃色の縞状部分
２が鋳造方向、圧延方向に対しほぼ直角に存在する縞模
様である。またその横縞の幅（縞状部分２の中心間距
離）Ｗは鋳造板では通常は幅１〜２mm程度であり、圧延
板ではその圧下量に応じて広い幅に引き延ばされた横縞
模様となる。The horizontal stripe pattern obtained by the present invention is shown in FIG.
As shown in the figure, a striped pattern in a direction perpendicular to the casting direction and the rolling direction, and a relatively dark colored striped portion on a relatively light-colored ground portion 1 in a straight or wavy or curved shape. Portion 2 is a striped pattern that exists substantially perpendicular to the casting direction and the rolling direction. The width (width between centers of the striped portions 2) W of the horizontal stripes is usually about 1 to 2 mm in the width of a cast plate, and the width of the horizontal stripes is widened in a rolled plate according to the amount of reduction. Become.
【００３２】[0032]
実施例１ 表１の合金番号１〜４に示す成分組成のアルミニウム合
金を常法にしたがって溶製し、一対のロール間に給湯す
る方式の板連続鋳造法によって板厚７mmの鋳造板を得
た。凝固時の冷却速度はいずれも２００〜３００℃／se
c であった。得られた各合金に対して、そのまま（鋳造
のまま）で陽極酸化処理を施すか、または５５０℃×１
０時間の加熱を行なってから陽極酸化処理を施した。Example 1 An aluminum alloy having a component composition shown in alloy numbers 1 to 4 in Table 1 was melted according to a conventional method, and a cast plate having a thickness of 7 mm was obtained by a continuous plate casting method in which hot water was supplied between a pair of rolls. . The cooling rate during solidification is 200 to 300 ° C / se
c. Each of the obtained alloys is subjected to an anodic oxidation treatment as it is (as cast) or at 550 ° C. × 1
After heating for 0 hour, an anodic oxidation treatment was performed.
【００３３】上記のいずれの場合においても陽極酸化処
理は次の条件で行なった。すなわち、先ず１０％ＮａＯ
Ｈ水溶液でエッチングした後、水洗して硝酸でデスマッ
ト処理を施し、次いで１５ vol％濃度の硫酸浴を用いて
浴温２０℃、電流密度１．５Ａ／dm2 で陽極酸化処理を
行ない、膜厚２０μｍの陽極酸化皮膜を生成させた。In each of the above cases, the anodic oxidation treatment was performed under the following conditions. That is, first, 10% NaO
After etching with H aqueous solution, washing with water and desmutting with nitric acid are performed, and then anodizing treatment is performed using a 15 vol% sulfuric acid bath at a bath temperature of 20 ° C. and a current density of 1.5 A / dm 2 , An anodized film of 20 μm was formed.
【００３４】以上のようにして陽極酸化処理が施された
各板の表面の色調と横縞模様の状況を目視により観察、
判定した結果を表２に示す。なお表２において、横縞模
様の欄の○印は明瞭に横縞模様が発現した場合を、△印
は不鮮明に横縞模様が生じていた場合を、×印は横縞模
様が生じていなかった場合をそれぞれあらわす。The color tone and the state of the horizontal stripes on the surface of each plate anodized as described above are visually observed.
Table 2 shows the results of the determination. In Table 2, a circle in the horizontal stripe pattern column indicates a case where the horizontal stripe pattern clearly appeared, a mark Δ indicates a case where the horizontal stripe pattern was blurred, and a cross mark indicates the case where the horizontal stripe pattern did not occur. It represents.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】表２から明らかなように、成分組成が本発
明範囲内の合金（合金番号１，２）を用いた鋳造板（製
造符号Ａ〜Ｃ）のうち、鋳造のままの板（製造符号Ａ，
Ｃ）は、いずれも陽極酸化処理によってピンク〜赤紫色
の色調の横縞模様を発現させることができたが、５５０
℃×１０時間の加熱を行なった板（製造符号Ｂ）は、陽
極酸化処理後の色調が黒色となり、また横縞模様も鮮明
ではなかった。またＭｎ量、Ｆｅ量がともに少ない比較
合金（合金番号３）を用いた鋳造板（製造符号Ｄ）は、
充分に濃いピンク〜赤紫色の色調は得られず、また横縞
模様も発現しなかった。またＦｅ量が著しく少ない比較
合金（合金番号４）を用いた鋳造板（製造符号Ｅ）は、
ピンク〜赤紫色の色調は得られたが、横縞模様が発現し
なかった。As is apparent from Table 2, among the cast plates (product codes A to C) using alloys (alloy Nos. 1 and 2) whose component compositions fall within the range of the present invention, the as-cast plate (product code) A,
C) was able to develop a horizontal stripe pattern of pink to reddish purple tone by anodic oxidation treatment, but 550
The plate heated to 10 ° C. for 10 hours (Production code B) had a black color after anodizing, and the horizontal stripes were not clear. Further, a cast plate (manufacturing code D) using a comparative alloy (alloy No. 3) having a small amount of both Mn and Fe,
Sufficient pink to reddish purple color tone was not obtained, and no horizontal stripes appeared. Further, a cast plate (manufacturing code E) using a comparative alloy (alloy No. 4) having an extremely small amount of Fe,
Pink to reddish purple color tone was obtained, but no horizontal stripes appeared.
【００３８】実施例２ 実施例１の合金番号１，２の各合金について前記同様に
板連続鋳造により板厚７mmの鋳造板とし、各鋳造板（但
し鋳造のままのもの）について、板厚１．５mmまで冷間
圧延した。冷間圧延後の各板の一部はそのままま陽極酸
化処理を施し、他のものは、バッチ炉による２５０℃×
５時間もしくは４００℃×５時間、あるいは連続焼鈍を
想定したソルトバスによる３５０℃×１０sec の焼鈍を
施してから陽極酸化処理を施した。陽極酸化処理の条件
は実施例１の場合と同じである。Example 2 Each of the alloys Nos. 1 and 2 of Example 1 was cast into a cast plate having a thickness of 7 mm by continuous continuous casting in the same manner as described above. Cold rolled to 0.5 mm. A part of each plate after cold rolling is subjected to anodic oxidation treatment as it is, and the others are subjected to a batch furnace at 250 ° C. ×
Annealing was performed for 5 hours, 400 ° C. × 5 hours, or 350 ° C. × 10 sec using a salt bath assuming continuous annealing, and then anodizing was performed. The conditions of the anodizing treatment are the same as those in the first embodiment.
【００３９】陽極酸化処理後の表面の色調および横縞模
様を目視により観察、判定した。その結果を表３に示
す。The color tone and the horizontal stripe pattern on the surface after the anodizing treatment were visually observed and judged. Table 3 shows the results.
【００４０】[0040]
【表３】 [Table 3]
【００４１】表３から明らかなように、本発明成分範囲
内の合金からなる鋳造のままの板に対し冷間圧延を行な
った場合にも、特に焼鈍を行なわなかった板（製造符号
Ｆ，Ｈ）、２５０℃×５時間のバッチ炉焼鈍を行なった
板（製造符号Ｇ）、および連続焼鈍を想定した短時間の
焼鈍を行なった板（製造符号Ｉ）は、いずれも濃いピン
ク〜赤紫色の横縞模様が得られた。これに対し４００℃
×５時間のバッチ炉焼鈍を行なった場合（製造符号Ｊ）
には、陽極酸化処理後の色調が黒色となってしまった。As is evident from Table 3, when the as-cast sheet made of the alloy within the composition range of the present invention was subjected to cold rolling, the sheet which was not particularly annealed (manufacturing code F, H ), A plate subjected to batch furnace annealing at 250 ° C. × 5 hours (manufacturing code G), and a plate subjected to short-time annealing assuming continuous annealing (manufacturing code I) have dark pink to magenta colors. A horizontal stripe pattern was obtained. 400 ° C
× 5 hours batch furnace annealing (Product code J)
In, the color tone after the anodizing treatment was black.
【００４２】[0042]
【発明の効果】前述の実施例からも明らかなように、こ
の発明のアルミニウム合金板の製造方法によれば、板連
続鋳造法を適用することによって、比較的多量のＭｎを
含有するＡｌ−Ｍｎ系合金を用いて硫酸浴による陽極酸
化処理後にピンク〜赤紫色の色調を有しかつ安定かつ鮮
明な横縞模様を有する板を確実に製造することができ
る。As is apparent from the above-described embodiment, according to the method for manufacturing an aluminum alloy sheet of the present invention, Al-Mn containing a relatively large amount of Mn can be obtained by applying the continuous casting method. A plate having a pink to reddish purple color tone and a stable and clear horizontal stripe pattern can be reliably produced after the anodizing treatment in a sulfuric acid bath using the base alloy.
【００４３】[0043]
【００４４】したがってこの発明は、外観の多様化、個
性化が求められる各種建材材料や銘板、各種器物、容器
等の製造に適用して有益なものである。Accordingly, the present invention is useful when applied to the production of various building materials, nameplates, various objects, containers, and the like, which require diversification and individualization of the appearance.
【図１】この発明によるアルミニウム合金板の陽極酸化
処理後の横縞模様を説明するための模式図である。FIG. 1 is a schematic diagram for explaining a horizontal stripe pattern after an anodizing treatment of an aluminum alloy plate according to the present invention.
１ 地の部分 ２ 縞状部分 1 Part of the ground 2 Striped part
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−100144（ＪＰ，Ａ) 特開 昭53−43016（ＪＰ，Ａ) 特開 昭62−275546（ＪＰ，Ａ) 特開 平１−111897（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 11/04 - 11/24 C22C 21/00 - 21/18 C22F 1/04 - 1/057 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-100144 (JP, A) JP-A-53-43016 (JP, A) JP-A-62-275546 (JP, A) JP-A-1- 111897 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C25D 11/04-11/24 C22C 21/00-21/18 C22F 1/04-1/057
Claims (2)
wt％以上１．０wt％未満、Ｓｉ０．５wt％以下を含有す
るとともに、結晶粒微細化剤としてＴｉ０．００５〜
０．１５wt％を単独でまたはＢ０．０００１〜０．０５
００wt％と組合せて含有し、残部がＡｌおよびその他の
不可避的不純物よりなる合金の溶湯を、板連続鋳造法に
よって５℃／sec 以上の冷却速度で鋳造することを特徴
とする、陽極酸化処理後にピンク〜赤紫色の色調を有し
かつ横縞模様を有する陽極酸化処理用アルミニウム合金
板の製造方法。1. Mn 0.8 to 3.5 wt%, Fe 0.05
wt% or more and less than 1.0 wt%, Si 0.5 wt% or less, and Ti 0.005-
0.15wt% alone or B 0.0001-0.05
After the anodizing treatment, the molten metal of the alloy containing in combination with Al and other inevitable impurities is cast at a cooling rate of 5 ° C./sec or more by the continuous casting method. A method for producing an anodized aluminum alloy plate having a pink to red-purple color tone and having a horizontal stripe pattern.
wt％以上１．０wt％未満、Ｓｉ０．５wt％以下を含有す
るとともに、結晶粒微細化剤としてＴｉ０．００５〜
０．１５wt％を単独でまたはＢ０．０００１〜０．０５
００wt％と組合せて含有し、残部がＡｌおよびその他の
不可避的不純物よりなる合金の溶湯を、板連続鋳造法に
よって５℃／sec 以上の冷却速度で鋳造した後、もしく
はさらにその鋳造の後に２５０〜３５０℃で０．５〜２
４時間加熱した後、冷間圧延することを特徴とする、陽
極酸化処理後にピンク〜赤紫色の色調を有しかつ横縞模
様を有する陽極酸化処理用アルミニウム合金板の製造方
法。2. Mn 0.8 to 3.5 wt%, Fe 0.05
wt% or more and less than 1.0 wt%, Si 0.5 wt% or less, and Ti 0.005-
0.15wt% alone or B 0.0001-0.05
After the molten alloy of the alloy containing Al and other unavoidable impurities is cast at a cooling rate of 5 ° C./sec or more by the continuous plate casting method, or after the casting, 250 to 0.5 to 2 at 350 ° C
A method for producing an anodized aluminum alloy plate having a color tone of pink to reddish purple and having a horizontal stripe pattern after anodizing, comprising heating for 4 hours and then cold rolling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03197117A JP3142152B2 (en) | 1991-07-10 | 1991-07-10 | Manufacturing method of aluminum alloy plate for anodizing treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03197117A JP3142152B2 (en) | 1991-07-10 | 1991-07-10 | Manufacturing method of aluminum alloy plate for anodizing treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0517842A JPH0517842A (en) | 1993-01-26 |
| JP3142152B2 true JP3142152B2 (en) | 2001-03-07 |
Family
ID=16369018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03197117A Expired - Fee Related JP3142152B2 (en) | 1991-07-10 | 1991-07-10 | Manufacturing method of aluminum alloy plate for anodizing treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3142152B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5929745A (en) * | 1996-03-29 | 1999-07-27 | Hokuriku Electric Industry Co., Ltd. | High-voltage electric component |
-
1991
- 1991-07-10 JP JP03197117A patent/JP3142152B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0517842A (en) | 1993-01-26 |
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