JPS63157890A - Method for continuously annealing and pickling copper or copper alloy - Google Patents
Method for continuously annealing and pickling copper or copper alloyInfo
- Publication number
- JPS63157890A JPS63157890A JP30377686A JP30377686A JPS63157890A JP S63157890 A JPS63157890 A JP S63157890A JP 30377686 A JP30377686 A JP 30377686A JP 30377686 A JP30377686 A JP 30377686A JP S63157890 A JPS63157890 A JP S63157890A
- Authority
- JP
- Japan
- Prior art keywords
- pickling
- copper
- alloy
- soln
- cupric chloride
- 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.)
- Pending
Links
- 238000005554 pickling Methods 0.000 title claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 title claims abstract description 22
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 16
- 238000000137 annealing Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229960003280 cupric chloride Drugs 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- -1 ammonium ions Chemical class 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000956 alloy Substances 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007664 blowing Methods 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 3
- 229910000906 Bronze Inorganic materials 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010974 bronze Substances 0.000 abstract description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract 5
- 239000010953 base metal Substances 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
- 229940112669 cuprous oxide Drugs 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000317173 Perla Species 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、銅又は銅合金の連続焼鈍酸洗ラインにおける
特に酸洗方法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an improvement in a pickling method, particularly in a continuous annealing and pickling line for copper or copper alloys.
［従来の技術］
従来、一般の銅又は銅合金の連続焼鈍酸洗ラインにおい
ての酸洗液は、硫酸と過酸化水素水との混液（以下混酸
と称する）または硫酸のみが使用されている。しかし、
硫酸のみで酸洗する場合は、硫酸自体に酸化力がないの
で、硫酸と過酸化水素水との混液を使用することが多い
。[Prior Art] Conventionally, a mixed solution of sulfuric acid and hydrogen peroxide (hereinafter referred to as mixed acid) or only sulfuric acid has been used as a pickling solution in a general continuous annealing pickling line for copper or copper alloys. but,
When pickling with sulfuric acid alone, a mixture of sulfuric acid and hydrogen peroxide is often used since sulfuric acid itself has no oxidizing power.
又、他の酸洗液として塩化第２鉄溶液も知られている。Ferric chloride solutions are also known as other pickling solutions.
［発明が解決しようとする問題点］
混酸をつくる場合、硫酸に過酸化水素水を添加するには
、一度に添加すると突沸したり、液温の上昇を伴ない過
酸化水素水の分解等が生じるという不具合があるため、
適宜分けて添加する必要がある。又、液温及び添加量の
違いにより酸洗力の違いが大きく変るので、液温、過酸
化水素水の添加量および酸濃度を精密に調整する必要が
ある。[Problems to be Solved by the Invention] When making a mixed acid, adding hydrogen peroxide to sulfuric acid may cause bumping or decomposition of hydrogen peroxide due to an increase in liquid temperature if added all at once. Due to the problem that occurs,
It is necessary to add it separately as appropriate. Furthermore, since the difference in pickling power varies greatly depending on the temperature of the solution and the amount added, it is necessary to precisely adjust the temperature of the solution, the amount of hydrogen peroxide added, and the acid concentration.
さらに焼鈍時に生ずるスケールの性状に違いが生じる場
合がある。銅を例にとると、酸化第１銅と酸化第２銅の
２種類の酸化物が生成する。Furthermore, there may be differences in the properties of scale produced during annealing. Taking copper as an example, two types of oxides are produced: cuprous oxide and cupric oxide.
酸化第２銅は前記の混酸又は硫酸で十分に除去し得るが
、酸化第１銅は混酸を用いても十分に除去できない場合
がある。そのため、パフ研磨等の機械的手法による研磨
設備の並設が避けられないのが現状である。Cupric oxide can be sufficiently removed with the above-mentioned mixed acid or sulfuric acid, but cuprous oxide may not be sufficiently removed even with the mixed acid. Therefore, the current situation is that parallel installation of polishing equipment using mechanical methods such as puff polishing is unavoidable.
一方、混酸中の過酸化水素水の定量分析法は連続的なも
のはないに等しく、人手による手分析法に頼るしかない
のが現状である。したがって、酸洗液の酸洗力にバラツ
キが生じるのは避けがたいので、機械的研磨を行わない
わけにはいかない。On the other hand, there is no continuous quantitative analysis method for hydrogen peroxide in mixed acids, and the current situation is that the only method available is manual analysis. Therefore, it is inevitable that the pickling power of the pickling liquid will vary, so mechanical polishing cannot be avoided.
機械研磨を施した材料を冷間圧延すると、かさぶたと称
する表面欠陥が生じ、表面処理（主にメッキを指す）を
行った場合に種々の異常（ふくれ、変色、剥離等〉を生
じるか生じやすいと指摘されている。When mechanically polished materials are cold-rolled, surface defects called scabs occur, and various abnormalities (blistering, discoloration, peeling, etc.) occur or tend to occur when surface treatment (mainly refers to plating) is performed. It has been pointed out that.
酸洗で生じた硫酸銅は、濾別分離しても特に用途がない
ので廃棄処分する必要があり、そのための経費が必要で
ある。Copper sulfate produced by pickling has no particular use even if it is separated by filtration, so it needs to be disposed of, which requires expense.
塩化第２鉄溶液は鉄系の材料に対しては非常に良好な結
果を得るが、銅系の材料をこの塩化第２鉄溶液で酸洗す
ると、材料表面に鉄が付着する。この付着した鉄は硫酸
および混酸でも除去し難いで、機械的研磨法を用いなけ
ればならず、使用に耐えない。Ferric chloride solutions give very good results for iron-based materials, but when copper-based materials are pickled with this ferric chloride solution, iron adheres to the surface of the material. This adhered iron is difficult to remove even with sulfuric acid and mixed acids, and mechanical polishing must be used, making it unusable.
［問題点を解決するための手段］
本発明は上記問題点に鑑みなされたもので、その第１発
明は銅又は銅合金の連続焼鈍酸洗ラインにおいて、焼鈍
後の各酸洗槽における酸洗液として塩化第２銅溶液を用
いて酸洗することを特徴とする銅又は銅合金の連続焼鈍
酸洗方法である。[Means for Solving the Problems] The present invention was made in view of the above-mentioned problems, and the first invention is a continuous annealing and pickling line for copper or copper alloys, in which pickling in each pickling tank after annealing is performed. This is a continuous annealing and pickling method for copper or copper alloy, characterized by pickling using a cupric chloride solution as a liquid.
すなわち、銅又は銅合金を大気中で焼鈍（炉内雰囲気温
度７００〜７５０°Ｃ）すると、銅又は銅合金材表面の
焼成酸化物は、酸化第２銅が主で、圧延中層部的に異常
圧下等を受ける部位とか部分的に高温となった時等には
、酸化第１銅が生成されることがある。この酸化第１銅
は、前記混酸のみでもって除去することは難しく、硫酸
のみではほとんど除去てきないが、塩化第２銅液を処理
液として用いることにより簡単に除去できる。That is, when copper or copper alloy is annealed in the air (furnace atmosphere temperature 700 to 750°C), the fired oxide on the surface of the copper or copper alloy material is mainly cupric oxide, and abnormalities occur in the middle layer of the rolling material. Cuprous oxide may be generated when the area is subjected to rolling reduction or the like or when the temperature becomes high. This cuprous oxide is difficult to remove using the mixed acid alone, and is hardly removed using sulfuric acid alone, but it can be easily removed by using a cupric chloride solution as a treatment liquid.
被処理材かりん青銅系の場合には、酸化皮膜は強靭なの
でその除去が少し困難なときがある。When the material to be treated is phosphor bronze, the oxide film is tough, so it is sometimes difficult to remove it.
第２発明はそのような場合に有効である。The second invention is effective in such cases.
すなわち、第２発明は、前記第１発明における酸洗処理
の前処理として、アルカリ又はアルカリ土類金属を含む
アルカリ溶液又はアンモニウムイオンを含む硫酸塩、あ
るいは過１ａ酸塩の内の１種又は２種以上の溶液を用い
て予備洗浄することを特徴とするもので、これにより完
全にスケールを除去することができる。That is, the second invention provides, as a pretreatment for the pickling treatment in the first invention, an alkaline solution containing an alkali or alkaline earth metal, a sulfate containing ammonium ions, or one or two perla salts. This method is characterized by pre-cleaning using a solution of at least 100% of the total amount of scale, thereby making it possible to completely remove scale.
アルカリ溶液としでは、Ｎａ、に、Ｃａ、ＭＱ、Ｂａ等
を含む溶液で、特に苛性ンーダ、苛性カリ等の強アルカ
リ溶液が好適でおり、硫酸塩おるいは過１ａ酸塩として
は、硫酸アンモニウムあるいは過硫酸アンモニウム溶液
が特に有効である。As an alkaline solution, a solution containing Na, Ca, MQ, Ba, etc. is particularly suitable, and a strong alkaline solution such as caustic powder or caustic potash is particularly suitable.As a sulfate or perla salt, ammonium sulfate or Ammonium sulfate solutions are particularly effective.
アルカリ溶液の濃度管理は酸との中和滴定で、アンモニ
ウムを含む溶液の濃度は、遊離のアンモニウムイオン量
によって簡単に定量することができる。The concentration of the alkaline solution is controlled by neutralization titration with an acid, and the concentration of the ammonium-containing solution can be easily determined by the amount of free ammonium ions.
又、塩化第２銅溶液の濃度管理は、酸化還元電位でもっ
て管理できる。そして酸化還元電位が低下した場合には
、塩素を吹き込むこと又は過酸化水素水と塩酸を添加す
ることにより再生することができる。Further, the concentration of the cupric chloride solution can be controlled by the oxidation-reduction potential. If the redox potential decreases, it can be regenerated by blowing in chlorine or adding hydrogen peroxide and hydrochloric acid.
［実施例］ つぎに実施例並びに比較例について説明する。[Example] Next, examples and comparative examples will be described.
３ｎ４．５ｗｔ％、ｐ ０．０５ｗｔ％、Ｆｅ ０．０
４８ｗｔ％、Ｚｎ ０．０２５ｗｔ％、Ｎ ｉ ０．
００３ｗｔ％、残部Ｃｕからなる銅合金の条（０，３ｍ
ｍｔｘ６５０ｍｍＷｘ ９ ）を大気焼鈍（炉内温度７
００〜７５０’Ｃ１炉内０２濃度０、８Ｖ／Ｖ％）した
後酸洗処理をした。3n4.5wt%, p 0.05wt%, Fe 0.0
48wt%, Zn 0.025wt%, Ni 0.
Copper alloy strip (0.3 m
mtx650mmWx9) was annealed in air (furnace temperature 7
00 to 750' C1 furnace 02 concentration 0.8 V/V%) and then pickling treatment.
酸洗処理は２５％塩化第２銅溶液による場合、並びにそ
れに予備処理として１．１０％苛性ソーダ溶液処理を組
合せた場合と、従来の３５％硫酸、おるいはそれに３％
過酸化水素を加えた混酸による処理の場合について、そ
れぞれ通板速度を−〇 −
変えて行った。Pickling treatment is carried out with a 25% cupric chloride solution, in combination with a 1.10% caustic soda solution treatment as a pretreatment, and with a conventional 35% sulfuric acid or 3% in addition.
In the case of treatment with a mixed acid to which hydrogen peroxide was added, the sheet passing speed was changed by −0 − in each case.
その場合の条件とスケール残りの有無についての試験結
果を表に示す。The conditions in that case and the test results regarding the presence or absence of scale residue are shown in the table.
なお、表中◎は適用した酸洗液の種類を示す。Note that ◎ in the table indicates the type of pickling solution used.
又、スケール残りの有無において、Ｑ・・・スケール残
り無し、△・・・スケール残り少し有り、Ｘ・・・スケ
ール残り有り、ｘｘ・・・スケール残り多最に有り、を
それぞれ示す。In addition, regarding the presence or absence of scale remaining, Q: no scale remaining, Δ: a small amount of scale remaining, X: scale remaining, and xx: most scale remaining.
−７＝
上記表に示した結果から明らかなとおり、本発明の実施
例によれば、スケール残りのない銅又は銅合金条が安定
して得られることが判る。-7= As is clear from the results shown in the table above, it can be seen that according to the examples of the present invention, copper or copper alloy strips without scale residue can be stably obtained.
［発明の効果］
本発明によれば、銅又は銅合金の連続焼鈍、酸洗ライン
において、スケール残りのないものが得られるばかりで
なく、塩素を吹き込むことによって、塩化第２銅を簡単
に再生することができるので、廃液の処分等の頻度も少
くてすみ、当然コスト低減が可能となる。また、未酸化
銅へのエツチング力はあまり強くないので過度のエツチ
ングを行うことがなく、製品の減肉量が少くて済むので
経済的である。[Effects of the Invention] According to the present invention, in a continuous annealing and pickling line for copper or copper alloy, not only can a product with no scale residue be obtained, but also cupric chloride can be easily regenerated by blowing in chlorine. Therefore, it is possible to reduce the frequency of disposal of waste liquid, which naturally enables cost reduction. Furthermore, since the etching power for unoxidized copper is not very strong, excessive etching is not performed, and the amount of thickness loss in the product is reduced, which is economical.
Claims (2)
鈍後の各酸洗槽における酸洗液として塩化第２銅溶液を
用いて酸洗することを特徴とする銅又は銅合金の連続焼
鈍酸洗方法。(1) Continuous annealing of copper or copper alloy, characterized in that in a continuous annealing pickling line for copper or copper alloy, pickling is carried out using a cupric chloride solution as the pickling liquid in each pickling tank after annealing. Pickling method.
鈍後、アルカリ又はアルカリ土類金属を含むアルカリ溶
液又はアンモニウムイオンを含む硫酸塩および過硫酸塩
の水溶液の内の１種又は２種以上の溶液で予備洗浄して
から、酸洗液として塩化第２銅溶液を用いて酸洗するこ
とを特徴とする銅又は銅合金の連続焼鈍酸洗方法。(2) In a continuous annealing and pickling line for copper or copper alloys, after annealing, one or more of an alkaline solution containing an alkali or alkaline earth metal or an aqueous solution of sulfate and persulfate containing ammonium ions is used. 1. A method for continuous annealing and pickling of copper or copper alloys, which comprises preliminarily cleaning with a solution of the above, and then pickling using a cupric chloride solution as a pickling solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30377686A JPS63157890A (en) | 1986-12-22 | 1986-12-22 | Method for continuously annealing and pickling copper or copper alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30377686A JPS63157890A (en) | 1986-12-22 | 1986-12-22 | Method for continuously annealing and pickling copper or copper alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63157890A true JPS63157890A (en) | 1988-06-30 |
Family
ID=17925148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30377686A Pending JPS63157890A (en) | 1986-12-22 | 1986-12-22 | Method for continuously annealing and pickling copper or copper alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63157890A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5438344A (en) * | 1990-11-05 | 1995-08-01 | Oliva; Anthony | Portable video book |
| US5914706A (en) * | 1989-03-22 | 1999-06-22 | Seiko Epson Corporation | Compact portable audio-display electronic apparatus with interactive inquirable and inquisitorial interfacing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58213850A (en) * | 1982-06-08 | 1983-12-12 | Kobe Steel Ltd | Manufacture of al-zn-mg-cu alloy material of superior formability |
| JPS60174845A (en) * | 1984-02-18 | 1985-09-09 | Kobe Steel Ltd | Aluminum alloy for forging having superior strength and cold forgeability |
| JPS60251245A (en) * | 1984-05-25 | 1985-12-11 | Kobe Steel Ltd | Al-mg-zn type aluminum alloy plate for blind |
-
1986
- 1986-12-22 JP JP30377686A patent/JPS63157890A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58213850A (en) * | 1982-06-08 | 1983-12-12 | Kobe Steel Ltd | Manufacture of al-zn-mg-cu alloy material of superior formability |
| JPS60174845A (en) * | 1984-02-18 | 1985-09-09 | Kobe Steel Ltd | Aluminum alloy for forging having superior strength and cold forgeability |
| JPS60251245A (en) * | 1984-05-25 | 1985-12-11 | Kobe Steel Ltd | Al-mg-zn type aluminum alloy plate for blind |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5914706A (en) * | 1989-03-22 | 1999-06-22 | Seiko Epson Corporation | Compact portable audio-display electronic apparatus with interactive inquirable and inquisitorial interfacing |
| US5914707A (en) * | 1989-03-22 | 1999-06-22 | Seiko Epson Corporation | Compact portable audio/display electronic apparatus with interactive inquirable and inquisitorial interfacing |
| US5438344A (en) * | 1990-11-05 | 1995-08-01 | Oliva; Anthony | Portable video book |
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