JPH0558797A - Production of copper oxide whisker - Google Patents

Production of copper oxide whisker

Info

Publication number
JPH0558797A
JPH0558797A JP24645291A JP24645291A JPH0558797A JP H0558797 A JPH0558797 A JP H0558797A JP 24645291 A JP24645291 A JP 24645291A JP 24645291 A JP24645291 A JP 24645291A JP H0558797 A JPH0558797 A JP H0558797A
Authority
JP
Japan
Prior art keywords
copper
whiskers
copper oxide
group
oxygen
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
Application number
JP24645291A
Other languages
Japanese (ja)
Inventor
Susumu Kusakaishi
進 日下石
Keiko Yamamoto
恵子 山本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
INTERNATL SOFTWARE KK
Original Assignee
INTERNATL SOFTWARE KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by INTERNATL SOFTWARE KK filed Critical INTERNATL SOFTWARE KK
Priority to JP24645291A priority Critical patent/JPH0558797A/en
Priority to EP92107989A priority patent/EP0530440A1/en
Priority to CA002068437A priority patent/CA2068437A1/en
Publication of JPH0558797A publication Critical patent/JPH0558797A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To efficiently obtain copper oxide whiskers by heating metallic copper to above the melting temp. and then heating the copper at a prescribed temp. in an oxygen-contg. atmosphere. CONSTITUTION:Metallic copper contg. <0.2wt.% impurities other than group IIIb elements, e.g. electrolytic copper or chemical copper is heated to above the melting temp. (at about 1,470 deg.C) and then heated at 250-750 deg.C for 0.5-30hr in an oxygen-contg. atmosphere having more than several% oxygen concn. Copper oxide whiskers can be efficiently and reasonably obtd. even from chemical copper or electrolytic copper from which copper oxide whiskers are difficult to form by the conventional method.

Description

【発明の詳細な説明】Detailed Description of the Invention

【産業上の利用分野】本発明は、プラスチックの充填材
もしくは強化材、その他各種用途に利用することができ
る酸化銅ウイスカーの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a copper oxide whisker which can be used as a filler or reinforcing material for plastics and various other purposes.

【従来の技術】金属酸化物は板状、針状、ブムック状等
々各種形状を示し、中にはウイスカーと呼ばれる針状単
結晶を生成するものもある。ウイスカーを形成する金属
酸化物としては、酸化アルミニウム、酸化ベリリウム、
酸化亜鉛、酸化マグネシウム等が知られている。これら
のウイスカーは、それぞれの形状をもっており、現在、
プラスチックのフイラーとして有望視されているが、高
価であったり、毒性があったり、製造に多大な労力を要
したりして、必ずしも満足のいくものではなかった。こ
のように各種の金属酸化物のウイスカーが知られていた
が、酸化銅がウイスカーとして生成することは未だ知ら
れていなかった。2. Description of the Related Art Metal oxides have various shapes such as a plate shape, a needle shape, a Bumook shape, and some of them form a needle-shaped single crystal called whiskers. Aluminum oxide, beryllium oxide, metal oxides forming whiskers,
Zinc oxide, magnesium oxide and the like are known. These whiskers have their respective shapes and are currently
Although it is regarded as a promising plastic filler, it is not always satisfactory because it is expensive, toxic, and requires a great deal of labor to manufacture. Thus, whiskers of various metal oxides have been known, but it has not yet been known that copper oxide is produced as whiskers.

【発明の目的】本発明は、新規な酸化銅ウイスカーを、
比較的簡単な方法で効率よく製造する方法を提供するこ
とを目的とする。さらに、本発明は、安価な金属銅を原
料とすることにより、経済性に富む酸化銅ウイスカーを
提供することを目的とする。OBJECT OF THE INVENTION The present invention provides a novel copper oxide whisker,
It is an object of the present invention to provide a method for efficiently manufacturing a relatively simple method. A further object of the present invention is to provide a highly economical copper oxide whisker by using inexpensive metallic copper as a raw material.

【課題を解決するための手段】本発明は、金属銅をその
溶融温度以上の温度に加熱し、次いで酸素含有雰囲気下
で２５０乃至７５０℃の温度に加熱することを特徴とす
る酸化銅ウイスカーの製造方法を提供する。金属銅を、
酸素含有雰囲気下で加熱する前に、一旦溶融せしめるな
らば、効率よく酸化銅ウイスカーが得られることを見出
したのである。溶融した銅を室温まで冷却し、その後あ
らためて２５０乃至７００℃の温度に加熱してもよい。
この場合は、冷却した銅をヤスリやグラインダー等の機
械的手段で粉末にするのが有利である。表面積が大きく
なり収量が多くなるからである。或いは、溶融した銅を
２５０乃至７００℃の温度範囲にまで冷却し酸素を含む
雰囲気下で加熱を続けてもよい。この場合は、酸化銅ウ
イスカーは金属銅の表面に生成するので、未反応物とウ
イスカーの分別がしやすいという利点がある。従って目
的に応じていずれかの手段を選択することができる。な
お、金属銅の溶融は、酸化を防止するために不活性雰囲
気下で行なうのが好ましい。本発明の方法により、化学
的手法により得られた銅（以下これを化学銅という）、
例えば硫酸水溶液中に亜鉛などを投入し、イオン交換を
して還元析出した銅、或いは電解銅と呼ばれる銅の精錬
工程で産出される銅を出発原料として効率よく酸化銅ウ
イスカーを製造することができる。かかる化学銅又は電
解銅を単に酸素含有雰囲気下で２５０乃至７００℃の温
度に加熱した場合には、ウイスカーは生成するもののそ
の量は微量であった。ところが、化学銅又は電解銅を一
旦溶融した後前記加熱を実施した場合には、酸化銅ウイ
スカーの生成量が飛躍的に向上することが分ったのであ
る。その理由は十分明らかではないが、金属銅を溶融し
冷却すると結晶構造がより密になり、酸化銅ウイスカー
を生成すると時銅元素が連続して供給されるということ
が推測される。本発明において使用する金属銅は、ホウ
素、アルミニウム、ガリウム、インジウム、タリウム等
の三族ｂ亜属金属元素以外の不純物を実質的に含まない
こと、具体的にはかかる不純物含量が０.２重量％より
も少ないこと、が好ましい。本発明者らの鋭意研究をし
た結果によると、酸化銅を生成させる為には２.６重量
％以内であれば三族ｂ亜属元素の含有はむしろ好ましい
ものであるが、この三族ｂ亜属元素以外の元素が含まれ
ることは、酸化銅ウイスカーは生成しなかったりしても
わずかであったりして、好ましくない。この場合、三族
ｂ亜属以外の元素といっても、水素やヘリウムや窒素や
酸素、フッ素、ネオン、アルゴン、塩素、臭素、クリプ
トン等の鋼精錬工程において蒸発し、あるいは気散する
元素は対象とせず、あくまで銅の精錬工程中において、
残存するであろうと予想される三族ｂ亜属以外の一族、
二族、三族ａ亜属、四族、五族、六族、七族ａ亜属、八
族の半導体、半金属、金属を示すことはいうまでもな
い。これらの三族ｂ亜属以外の元素を１種又はそれ以上
の種類の合計が０.２重量％を越えるとウイスカーの生
成は困難になる。一方、三族ｂ亜属の元素は、最大で
２.６重量％まで加えても酸化銅ウイスカーの生成に全
く問題ないか、又は加えた方が好ましいという結果を得
ている。本発明において酸素含有雰囲気は、酸素濃度が
１００％に近い雰囲気、あるいは空気のような窒素等々
と混合された雰囲気でもよく、さらには、空気よりも酸
素含有量が小さい数％の酸素濃度を有する、窒素または
その他の気体との混合された雰囲気でもよい。酸素濃度
が数％以上であればよいが、５０％以上であれば一層好
ましい。酸素含有雰囲気下での加熱のための温度条件
は、２５０℃以下の場合ではウイスカーが生成しない
か、または、ウイスカーが生成しても極く微量であった
り、極めて細かいウイスカーであったりして、好ましく
ない。また、７００℃を越えるとウイスカーが溶融状態
となり、好ましくない。上記のような雰囲気及び温度条
件下で金属銅を０.５〜３０時間加熱する。さらに、詳
しくは以下の実施例をもって明らかになるだろう。SUMMARY OF THE INVENTION The present invention is a copper oxide whisker characterized by heating metallic copper to a temperature above its melting temperature and then to a temperature of 250 to 750 ° C. in an oxygen-containing atmosphere. A manufacturing method is provided. Metal copper,
It has been found that a copper oxide whisker can be efficiently obtained if it is once melted before being heated in an oxygen-containing atmosphere. The molten copper may be cooled to room temperature and then reheated to a temperature of 250 to 700 ° C.
In this case, it is advantageous to powder the cooled copper by mechanical means such as a file or a grinder. This is because the surface area increases and the yield increases. Alternatively, the molten copper may be cooled to a temperature range of 250 to 700 ° C. and heating may be continued in an atmosphere containing oxygen. In this case, since the copper oxide whiskers are formed on the surface of the metallic copper, there is an advantage that the unreacted substances and the whiskers can be easily separated. Therefore, either means can be selected according to the purpose. The melting of metallic copper is preferably performed in an inert atmosphere to prevent oxidation. By the method of the present invention, copper obtained by a chemical method (hereinafter referred to as chemical copper),
For example, it is possible to efficiently produce copper oxide whiskers by introducing zinc or the like into a sulfuric acid aqueous solution and performing ion exchange to reduce and precipitate copper, or copper produced in a refining process of copper called electrolytic copper as a starting material. .. When such chemical copper or electrolytic copper was simply heated to a temperature of 250 to 700 ° C. in an oxygen-containing atmosphere, whiskers were formed, but the amount thereof was very small. However, it has been found that when the chemical copper or electrolytic copper is once melted and then the heating is performed, the amount of copper oxide whiskers produced is dramatically improved. The reason for this is not fully clear, but it is speculated that when the metallic copper is melted and cooled, the crystal structure becomes denser, and when the copper oxide whiskers are formed, the copper element is continuously supplied. The metallic copper used in the present invention is substantially free of impurities other than Group III group b metal elements such as boron, aluminum, gallium, indium, and thallium. Specifically, the content of such impurities is 0.2% by weight. % Is preferable. According to the results of earnest studies by the present inventors, it is preferable that the content of the Group IIIb subgroup element is 2.6% by weight or less in order to form copper oxide. The inclusion of an element other than the sub-genus element is not preferable since copper oxide whiskers are not produced or are present in a small amount. In this case, elements other than Group 3 b subgenus, such as hydrogen, helium, nitrogen, oxygen, fluorine, neon, argon, chlorine, bromine, and krypton, which evaporate or diffuse in the steel refining process, In the refining process of copper without targeting,
A family other than the subgroup of the 3rd family, which is expected to remain,
It goes without saying that the semiconductors, semimetals, and metals of Group 2, Group 3 a, Subgroup 4, Group 5, Group 5, Group 6, Group 7 a, and Group 8 are shown. If the total of one or more elements other than Group 3 b subgenus exceeds 0.2% by weight, it becomes difficult to form whiskers. On the other hand, it has been obtained that even if the element of Group 3 subgroup b is added up to 2.6% by weight at most, there is no problem in forming copper oxide whiskers, or it is preferable to add it. In the present invention, the oxygen-containing atmosphere may be an atmosphere having an oxygen concentration close to 100% or an atmosphere mixed with nitrogen such as air, and further has an oxygen concentration of several% which is smaller than that of air. It may be an atmosphere mixed with nitrogen or other gas. The oxygen concentration may be several% or more, but it is more preferably 50% or more. The temperature condition for heating in an oxygen-containing atmosphere is that whiskers do not form in the case of 250 ° C. or lower, or even if the whiskers form, there is an extremely small amount or extremely fine whiskers, Not preferable. Further, if the temperature exceeds 700 ° C., the whiskers are in a molten state, which is not preferable. The metallic copper is heated for 0.5 to 30 hours under the above atmosphere and temperature conditions. Further details will be made clear by the following examples.

【実施例】【Example】

実施例１ 電解銅板（同和鉱業（株）小坂鉱山、黒鉱より精錬）を
約１cm角位の大きさにブリキバサミを使って切断した。
この銅板は、品質検査によると９９.９８％の銅であ
る。これを２０ｇ用意し、ルツボ（ＴＯＰ，ＳＳＡ−
Ｈ，Ｃ型）に入れ高周波炉（イタリア製ＭＵＬＴＩＨＥ
ＲＴＺ ＡＵＲＵＭ０５／０Ｃ）に装着し、ルツボの開
口部にはアルゴンガスを２０ｌ／ｍｉｎの流量で流し、
不活性雰囲気として３００秒加熱し銅を溶融した。溶融
温度は ℃であった。中の金属銅が固化したのを肉眼
で確かめ室内に放置し、冷却した。このルツボを削り、
中の銅塊を取り出し、ヤスリで削り粉末を約１ｇ得た。
この銅粉末を５mg採取し、示差熱分析計（真空理工
（株）製ＴＧＤ−７０００）を電気炉として酸素を８０
ｍｌ／ｍｉｎを流した環境の中で５５０℃で３時間加熱
後、走査型電子型顕微鏡（日本電子（株）製Ｔ−２０
型）を用いて観察した結果、図１に示すように銅の表面
に明らかにウイスカーが生成していた。この時のウイス
カーは一辺が０.２〜０.３μｍ、長さ３.０〜４.０μｍ
の角柱形状であり、重量計算から生成量を求めると３
８.８％であった。 実施例２ 銅板を電解銅粉（福田箔粉工業（株）製ＣＥ−１１５）
に替えた以外は実施例１と全く同様にして酸化銅ウイス
カーの生成を試みた結果、一辺が０.２〜０.３μｍの角
柱形状のウイスカーが得られ、生成量は３７.３２％で
あった。 比較例１ 実施例１の中で金属銅の加熱溶融操作を行なわず電解銅
板をそのままヤスリで削り、粉末を得、以下、全く同様
の操作を行ったところ、酸化銅ウイスカーは全く生成し
なかった。 比較例２ 実施例２で使用した電解銅粉を加熱溶融を行わずそのま
ま実施例１と同様に示差熱分析計で加熱し、以下の工程
を同様に行ったが全く酸化銅ウイスカーの生成はなかっ
た。 実施例３ 硫酸銅（和光純薬工業（株）製試薬一級ＣｕＳＯ4・５
Ｈ2Ｏ）約５０ｇを３００ｍｌの純水に溶かし、これに
粒状亜鉛（和光純薬工業（株）製試薬一級）２０ｇを投
入し、室温で時々撹拌しながら約４０分放置し、デカン
テーシヨンを用いて粒状の亜鉛を析出した化学銅と分別
した。硫酸銅の青色は、やや緑色がかっており、まだ析
出されない銅イオンが残っていると思われたが、このま
ま東洋ろ紙Ｎo.５Ａを用いて洗浄・ろ過・乾燥し、化学
銅粉３ｇを得た。実施例１の中で、銅板２０ｇをここで
得た化学還元銅１.５ｇに替えた以外は全く実施例１と
同様に行った結果、一辺が０.２〜０.３μｍ、長さ２.
０〜５.０μｍ角柱形状を有する酸化銅ウイスカーを収
率３５.１％で得た。 比較例３ 実施例３で得た化学銅を使用した以外は比較例２と全く
同様の操作を行ったが酸化銅ウイスカーの生成は確認出
来なかった。 比較例４ 実施例１で使用した銅に表−１に示す様な一族、二族、
三族ａ亜属、四族、五族、六族、七族ａ亜属、八族の各
代表的な元素を１重量％に相当する量を加え、実施例１
と全く同様の操作を行った。結果を表−１に記載したが
全く酸化銅ウイスカーの生成は認められなかった。Example 1 An electrolytic copper plate (refined from Kuroko ore, Kosaka mine, Dowa Mining Co., Ltd.) was cut into about 1 cm square pieces using tinplate scissors.
This copper plate is 99.98% copper according to quality inspection. Prepare 20g of this, and use the crucible (TOP, SSA-
Put in H, C type and high frequency furnace (MULTIHE made in Italy)
RTZ AURUM05 / 0C), and flow argon gas through the opening of the crucible at a flow rate of 20 l / min.
The copper was melted by heating for 300 seconds in an inert atmosphere. The melting temperature was ° C. It was confirmed with naked eyes that the metallic copper inside had solidified, and it was left in the room and cooled. Sharpen this crucible,
The copper ingot was taken out and sanded with a file to obtain about 1 g of powder.
5 mg of this copper powder was sampled and oxygen was adjusted to 80 by using a differential thermal analyzer (TGD-7000 manufactured by Vacuum Riko Co., Ltd.) as an electric furnace.
After heating at 550 ° C. for 3 hours in an environment of flowing ml / min, a scanning electron microscope (T-20 manufactured by JEOL Ltd.) was used.
As a result of observation using a mold, whiskers were clearly formed on the copper surface as shown in FIG. The whiskers at this time are 0.2-0.3 μm on a side and 3.0-4.0 μm in length.
It is a prismatic shape of, and if the amount generated is calculated from the weight calculation,
It was 8.8%. Example 2 A copper plate was an electrolytic copper powder (CE-115 manufactured by Fukuda Foil & Powder Co., Ltd.)
The production of copper oxide whiskers was attempted in exactly the same manner as in Example 1 except that the whiskers having a prism shape with one side of 0.2 to 0.3 μm were obtained, and the production amount was 37.32%. It was Comparative Example 1 In Example 1, the heating and melting operation of metallic copper was not performed, and the electrolytic copper plate was directly ground with a file to obtain a powder. Thereafter, the same operation was performed, but no copper oxide whiskers were formed at all. .. Comparative Example 2 The electrolytic copper powder used in Example 2 was heated as it was by a differential thermal analyzer in the same manner as in Example 1 without heating and melting, and the following steps were performed in the same manner, but no copper oxide whiskers were formed. It was Example 3 Copper sulfate (Wako Pure Chemical Industries, Ltd. reagent first-grade CuSO 4.5 )
Approximately 50 g of H 2 O) is dissolved in 300 ml of pure water, 20 g of granular zinc (Wako Pure Chemical Industries, Ltd. first-grade reagent) is added, and the mixture is left at room temperature for about 40 minutes with occasional stirring, followed by decantation. Was used to separate granular zinc from the deposited chemical copper. The blue color of copper sulphate was slightly greenish, and it was thought that copper ions that had not been deposited still remained, but this was washed, filtered, and dried using Toyo Filter Paper No. 5A to obtain 3 g of chemical copper powder. .. In Example 1, except that the copper plate 20 g was replaced by the chemically reduced copper 1.5 g obtained here, the result was the same as in Example 1, and as a result, one side was 0.2 to 0.3 μm and the length was 2.
Copper oxide whiskers having a prismatic shape of 0 to 5.0 μm were obtained with a yield of 35.1%. Comparative Example 3 The same operation as in Comparative Example 2 was performed except that the chemical copper obtained in Example 3 was used, but formation of copper oxide whiskers could not be confirmed. Comparative Example 4 The copper used in Example 1 was classified into the groups 1 and 2 as shown in Table-1.
Example 1 was added with each of the representative elements of Group 3 a sub-genus, group 4, group 5, group 6, group 7 sub-genus a, group 8 added in an amount corresponding to 1% by weight.
The same operation was performed. The results are shown in Table 1, but no formation of copper oxide whiskers was observed.

【表１】 但し、表−１中、 ×・・・生成を確認出来ず △・・・生成を認めるが明らかにウイスカーとは断定出
来ない 実施例４ 実施例１で使用した銅板１９.８ｇに亜鉛（和光純薬工
業（株）製試薬一級）を表−２に示すような割合で加え
た銅合金を使用し、実施例１と同じ操作をしてウイスカ
ーを生成せしめた。結果を表−２に合わせて示す。[Table 1] However, in Table 1, x ... generation was not confirmed, and Δ ... generation was recognized, but it could not be clearly determined as whiskers. Example 4 19.8 g of the copper plate used in Example 1 had zinc (Wako Pure Co., Ltd.). Whiskers were produced in the same manner as in Example 1, using a copper alloy containing the chemicals of the first-class reagent manufactured by Yakuhin Kogyo Co., Ltd. in the proportions shown in Table 2. The results are shown in Table 2 together.

【表２】 但し、表−２中、 ×・・・生成を確認出来ず △・・・生成を認めるが明らかにウイスカーとは断定出
来ない 〇・・・明らかにウイスカーが生成している[Table 2] However, in Table 2, x: generation cannot be confirmed. △: generation is recognized, but it cannot be clearly determined to be whiskers. 〇: clearly whiskers are generated.

【発明の効果】以上、説明した様に本発明によれば酸化
銅ウイスカーを効率よく、かつ従来生成が困難であった
化学銅や電解銅からも合理的に得ることが出来る。この
ウイスカーはプラスチツクの充填材や強化材をはじめと
して、酸化銅ウイスカーが導電性であることに着目し、
ＥＭＩ対策用材料として極めて有効である。酸化銅ウイ
スカーの特性を利用した他の様々な応用が期待出来る。As described above, according to the present invention, the copper oxide whiskers can be efficiently obtained rationally from chemical copper or electrolytic copper, which has been difficult to produce conventionally. This whisker focuses on the fact that copper oxide whiskers are conductive, including plastic fillers and reinforcing materials,
It is extremely effective as an EMI countermeasure material. Various other applications can be expected utilizing the characteristics of copper oxide whiskers.

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

【図１】図１は、本発明の実施例１によって得られた酸
化銅ウイスカー（繊維）の形状を示す電子顕微鏡写真で
ある。FIG. 1 is an electron micrograph showing the shape of a copper oxide whisker (fiber) obtained according to Example 1 of the present invention.

─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成３年１０月３１日[Submission date] October 31, 1991

【手続補正１】[Procedure Amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、プラスチックの充填材
もしくは強化材、その他各種用途に利用することができ
る酸化銅ウイスカーの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a copper oxide whisker which can be used as a filler or reinforcing material for plastics and various other purposes.

【０００２】[0002]

【従来の技術】金属酸化物は板状、針状、ブムック状等
々各種形状を示し、中にはウイスカーと呼ばれる針状単
結晶を生成するものもある。ウイスカーを形成する金属
酸化物としては、酸化アルミニウム、酸化ベリリウム、
酸化亜鉛、酸化マグネシウム等が知られている。これら
のウイスカーは、それぞれの形状をもっており、現在、
プラスチックのフイラーとして有望視されているが、高
価であったり、毒性があったり、製造に多大な労力を要
したりして、必ずしも満足のいくものではなかった。2. Description of the Related Art Metal oxides have various shapes such as a plate shape, a needle shape, a Bumook shape, and some of them form a needle-shaped single crystal called whiskers. Aluminum oxide, beryllium oxide, metal oxides forming whiskers,
Zinc oxide, magnesium oxide and the like are known. These whiskers have their respective shapes and are currently
Although it is regarded as a promising plastic filler, it is not always satisfactory because it is expensive, toxic, and requires a great deal of labor to manufacture.

【０００３】このように各種の金属酸化物のウイスカー
が知られていたが、酸化銅がウイスカーとして生成する
ことは未だ知られていなかった。As described above, whiskers of various metal oxides have been known, but it has not yet been known that copper oxide forms whiskers.

【０００４】[0004]

【発明の目的】本発明は、新規な酸化銅ウイスカーを、
比較的簡単な方法で効率よく製造する方法を提供するこ
とを目的とする。OBJECT OF THE INVENTION The present invention provides a novel copper oxide whisker,
It is an object of the present invention to provide a method for efficiently manufacturing a relatively simple method.

【０００５】さらに、本発明は、安価な金属銅を原料と
することにより、経済性に富む酸化銅ウイスカーを提供
することを目的とする。A further object of the present invention is to provide an economical copper oxide whisker by using inexpensive metallic copper as a raw material.

【０００６】[0006]

【課題を解決するための手段】本発明は、金属銅をその
溶融温度以上の温度に加熱し、次いで酸素含有雰囲気下
で２５０乃至７５０℃の温度に加熱することを特徴とす
る酸化銅ウイスカーの製造方法を提供する。金属銅を、
酸素含有雰囲気下で加熱する前に、一旦溶融せしめるな
らば、効率よく酸化銅ウイスカーが得られることを見出
したのである。SUMMARY OF THE INVENTION The present invention is a copper oxide whisker characterized by heating metallic copper to a temperature above its melting temperature and then to a temperature of 250 to 750 ° C. in an oxygen-containing atmosphere. A manufacturing method is provided. Metal copper,
It has been found that a copper oxide whisker can be efficiently obtained if it is once melted before being heated in an oxygen-containing atmosphere.

【０００７】溶融した銅を室温まで冷却し、その後あら
ためて２５０乃至７００℃の温度に加熱してもよい。こ
の場合は、冷却した銅をヤスリやグラインダー等の機械
的手段で粉末にするのが有利である。表面積が大きくな
り収量が多くなるからである。或いは、溶融した銅を２
５０乃至７００℃の温度範囲にまで冷却し酸素を含む雰
囲気下で加熱を続けてもよい。この場合は、酸化銅ウイ
スカーは金属銅の表面に生成するので、未反応物とウイ
スカーの分別がしやすいという利点がある。従って目的
に応じていずれかの手段を選択することができる。な
お、金属銅の溶融は、酸化を防止するために不活性雰囲
気下で行なうのが好ましい。The molten copper may be cooled to room temperature and then reheated to a temperature of 250 to 700 ° C. In this case, it is advantageous to powder the cooled copper by mechanical means such as a file or a grinder. This is because the surface area increases and the yield increases. Alternatively, melted copper 2
The heating may be continued in an atmosphere containing oxygen after cooling to a temperature range of 50 to 700 ° C. In this case, since the copper oxide whiskers are formed on the surface of the metallic copper, there is an advantage that the unreacted substances and the whiskers can be easily separated. Therefore, either means can be selected according to the purpose. The melting of metallic copper is preferably performed in an inert atmosphere to prevent oxidation.

【０００８】本発明の方法により、化学的手法により得
られた銅（以下これを化学銅という）、例えば硫酸水溶
液中に亜鉛などを投入し、イオン交換をして還元析出し
た銅、或いは電解銅と呼ばれる銅の精錬工程で産出され
る銅を出発原料として効率よく酸化銅ウイスカーを製造
することができる。かかる化学銅又は電解銅を単に酸素
含有雰囲気下で２５０乃至７００℃の温度に加熱した場
合には、ウイスカーは生成するもののその量は微量であ
った。ところが、化学銅又は電解銅を一旦溶融した後前
記加熱を実施した場合には、酸化銅ウイスカーの生成量
が飛躍的に向上することが分ったのである。その理由は
十分明らかではないが、金属銅を溶融し冷却すると結晶
構造がより密になり、酸化銅ウイスカーを生成すると時
銅元素が連続して供給されるということが推測される。Copper obtained by a chemical method by the method of the present invention (hereinafter referred to as chemical copper), for example, zinc or the like is put into an aqueous solution of sulfuric acid and ion-exchanged to reduce and precipitate, or electrolytic copper. It is possible to efficiently produce copper oxide whiskers by using copper produced in a copper refining process called as a starting material. When such chemical copper or electrolytic copper was simply heated to a temperature of 250 to 700 ° C. in an oxygen-containing atmosphere, whiskers were formed, but the amount thereof was very small. However, it has been found that when the chemical copper or electrolytic copper is once melted and then the heating is performed, the amount of copper oxide whiskers produced is dramatically improved. The reason for this is not fully clear, but it is speculated that when the metallic copper is melted and cooled, the crystal structure becomes denser, and when the copper oxide whiskers are formed, the copper element is continuously supplied.

【０００９】本発明において使用する金属銅は、ホウ
素、アルミニウム、ガリウム、インジウム、タリウム等
の三族ｂ亜属金属元素以外の不純物を実質的に含まない
こと、具体的にはかかる不純物含量が０．２重量％より
も少ないこと、が好ましい。The metallic copper used in the present invention is substantially free of impurities other than the Group 3 subgroup b metal elements such as boron, aluminum, gallium, indium and thallium, and specifically, the content of such impurities is 0. It is preferably less than 0.2% by weight.

【００１０】本発明者らの鋭意研究をした結果による
と、酸化銅を生成させる為には２．６重量％以内であれ
ば三族ｂ亜属元素の含有はむしろ好ましいものである
が、この三族ｂ亜属元素以外の元素が含まれることは、
酸化銅ウイスカーは生成しなかったりしてもわずかであ
ったりして、好ましくない。According to the results of earnest studies by the present inventors, it is rather preferable that the content of the Group 3b subgroup element is 2.6% by weight or less in order to form copper oxide. The inclusion of elements other than Group IIIb subgroup elements
Copper oxide whiskers are not preferable because they are not produced or are present in a small amount.

【００１１】この場合、三族ｂ亜属以外の元素といって
も、水素やヘリウムや窒素や酸素、フッ素、ネオン、ア
ルゴン、塩素、臭素、クリプトン等の鋼精錬工程におい
て蒸発し、あるいは気散する元素は対象とせず、あくま
で銅の精錬工程中において、残存するであろうと予想さ
れる三族ｂ亜属以外の一族、二族、三族ａ亜属、四族、
五族、六族、七族ａ亜属、八族の半導体、半金属、金属
を示すことはいうまでもない。これらの三族ｂ亜属以外
の元素を１種又はそれ以上の種類の合計が０．２重量％
を越えるとウイスカーの生成は困難になる。In this case, elements other than Group IIIb subgenus are vaporized or vaporized in the steel refining process such as hydrogen, helium, nitrogen, oxygen, fluorine, neon, argon, chlorine, bromine and krypton. Elements other than the subgroups of Group 3 and b, which are expected to remain during the refining process of copper, are not included in the target group, Group 2, Group a, Subgroup 3a, and Group 4,
It goes without saying that it refers to semiconductors, metalloids, and metals belonging to Group V, Group 6, Group 7 a, and Group 8 a. 0.2% by weight of the total of one or more kinds of elements other than Group 3 b subgenus
If it exceeds, it becomes difficult to generate whiskers.

【００１２】一方、三族ｂ亜属の元素は、最大で２．６
重量％まで加えても酸化銅ウイスカーの生成に全く問題
ないか、又は加えた方が好ましいという結果を得てい
る。On the other hand, the maximum amount of elements of Group 3 b subgroup is 2.6.
It has been obtained that there is no problem in forming copper oxide whiskers even if it is added up to the weight%, or that it is preferable to add it.

【００１３】本発明において酸素含有雰囲気は、酸素濃
度が１００％に近い雰囲気、あるいは空気のような窒素
等々と混合された雰囲気でもよく、さらには、空気より
も酸素含有量が小さい数％の酸素濃度を有する、窒素ま
たはその他の気体との混合された雰囲気でもよい。酸素
濃度が数％以上であればよいが、５０％以上であれば一
層好ましい。In the present invention, the oxygen-containing atmosphere may be an atmosphere in which the oxygen concentration is close to 100% or an atmosphere mixed with nitrogen such as air. It may be a mixed atmosphere with nitrogen or other gas having a concentration. The oxygen concentration may be several% or more, but it is more preferably 50% or more.

【００１４】酸素含有雰囲気下での加熱のための温度条
件は、２５０℃以下の場合ではウイスカーが生成しない
か、または、ウイスカーが生成しても極く微量であった
り、極めて細かいウイスカーであったりして、好ましく
ない。また、７００℃を越えるとウイスカーが溶融状態
となり、好ましくない。The temperature condition for heating in an oxygen-containing atmosphere is that whiskers do not form when the temperature is 250 ° C. or lower, or even if whiskers are formed, the amount is extremely small or extremely fine whiskers. It is not preferable. Further, if the temperature exceeds 700 ° C., the whiskers are in a molten state, which is not preferable.

【００１５】上記のような雰囲気及び温度条件下で金属
銅を０．５〜３０時間加熱する。Metallic copper is heated for 0.5 to 30 hours under the above atmosphere and temperature conditions.

【００１６】さらに、詳しくは以下の実施例をもって明
らかになるだろう。Further details will be made clear by the following embodiments.

【００１７】[0017]

【実施例】 実施例１ 電解銅板（同和鉱業（株）小坂鉱山、黒鉱より精錬）を
約１ｃｍ角位の大きさにブリキバサミを使って切断し
た。この銅板は、品質検査によると９９．９８％の銅で
ある。これを２０ｇ用意し、ルツボ（ＴＯＰ，ＳＳＡ−
Ｈ，Ｃ型）に入れ高周波炉（イタリア製ＭＵＬＴＩＨＥ
ＲＴＺ ＡＵＲＵＭ０５／０Ｃ）に装着し、ルツボの開
口部にはアルゴンガスを２０１／ｍｉｎの流量で流し、
不活性雰囲気として３００秒加熱し銅を溶融した。溶融
温度は１４７０℃であった。中の金属銅が固化したのを
肉眼で確かめ室内に放置し、冷却した。Example 1 An electrolytic copper plate (refined from Kuroka, Kosaka mine, Dowa Mining Co., Ltd.) was cut into about 1 cm square pieces using tin scissors. This copper plate is 99.98% copper according to quality inspection. Prepare 20g of this, and use the crucible (TOP, SSA-
Put in H, C type and high frequency furnace (MULTIHE made in Italy)
RTZ AURUM05 / 0C), and flow argon gas at a flow rate of 201 / min through the opening of the crucible,
The copper was melted by heating for 300 seconds in an inert atmosphere. The melting temperature was 1470 ° C. It was confirmed with naked eyes that the metallic copper inside had solidified, and it was left in the room and cooled.

【００１８】このルツボを削り、中の銅塊を取り出し、
ヤスリで削り粉末を約１ｇ得た。この銅粉末を５ｍｇ採
取し、示差熱分析計（真空理工（株）製ＴＧＤ−７００
０）を電気炉として酸素を８０ｍｌ／ｍｉｎを流した環
境の中で５５０℃で３時間加熱後、走査型電子型顕微鏡
（日本電子（株）製Ｔ−２０型）を用いて観察した結
果、図１に示すように銅の表面に明らかにウイスカーが
生成していた。The crucible was ground to remove the copper ingot,
About 1 g of shaving powder was obtained with a file. 5 mg of this copper powder was sampled and analyzed with a differential thermal analyzer (manufactured by Vacuum Riko Co., Ltd. TGD-700).
0) as an electric furnace and heated at 550 ° C. for 3 hours in an environment of flowing oxygen of 80 ml / min, and then observed with a scanning electron microscope (T-20 type manufactured by JEOL Ltd.), As shown in FIG. 1, whiskers were clearly formed on the copper surface.

【００１９】この時のウイスカーは一辺が０．２〜０．
３μｍ、長さ３．０〜４．０μｍの角柱形状であり、重
量計算から生成量を求めると３８．８％であった。At this time, the whisker has a side of 0.2 to 0.
The prismatic shape was 3 μm and the length was 3.0 to 4.0 μm, and the production amount was calculated from the weight calculation to be 38.8%.

【００２０】実施例２ 銅板を電解銅粉（福田箔粉工業（株）製ＣＥ−１１５）
に替えた以外は実施例１と全く同様にして酸化銅ウイス
カーの生成を試みた結果、一辺が０．２〜０．３μｍの
角柱形状のウイスカーが得られ、生成量は３７．３２％
であった。Example 2 A copper plate was electrolytic copper powder (CE-115 manufactured by Fukuda Foil & Powder Co., Ltd.)
The production of copper oxide whiskers was tried in exactly the same manner as in Example 1 except that the whiskers were prismatic whiskers having a side of 0.2 to 0.3 μm, and the production amount was 37.32%.
Met.

【００２１】比較例１ 実施例１の中で金属銅の加熱溶融操作を行なわず電解銅
板をそのままヤスリで削り、粉末を得、以下、全く同様
の操作を行ったところ、酸化銅ウイスカーは全く生成し
なかった。Comparative Example 1 In Example 1, the electrolytic copper plate was directly ground with a file without performing the heating and melting operation of metallic copper to obtain a powder, and the same operation was carried out. Copper oxide whiskers were formed at all. I didn't.

【００２２】比較例２ 実施例２で使用した電解銅粉を加熱溶融を行わずそのま
ま実施例１と同様に示差熱分析計で加熱し、以下の工程
を同様に行ったが全く酸化銅ウイスカーの生成はなかっ
た。Comparative Example 2 The electrolytic copper powder used in Example 2 was heated by a differential thermal analyzer in the same manner as in Example 1 without heating and melting, and the following steps were performed in the same manner, but no copper oxide whiskers were obtained. There was no generation.

【００２３】実施例３ 硫酸銅（和光純薬工業（株）製試薬一級ＣｕＳＯ４・５
Ｈ２Ｏ）約５０ｇを３００ｍｌの純水に溶かし、これに
粒状亜鉛（和光純薬工業（株）製試薬一級）２０ｇを投
入し、室温で時々撹拌しながら約４０分放置し、デカン
テーションを用いて粒状の亜鉛を析出した化学銅と分別
した。硫酸銅の青色は、やや緑色がかっており、まだ析
出されない銅イオンが残っていると思われたが、このま
ま東洋ろ紙Ｎｏ．５Ａを用いて洗浄・ろ過・乾燥し、化
学銅粉３ｇを得た。Example 3 Copper sulfate (Wako Pure Chemical Industries, Ltd. reagent first-grade CuSO 4.5 )
About 50 g of H 2 O) is dissolved in 300 ml of pure water, 20 g of granular zinc (Wako Pure Chemical Industries, Ltd. reagent first grade) is added, and the mixture is left at room temperature for about 40 minutes with occasional stirring to perform decantation. It was used to separate granular zinc from the deposited chemical copper. The blue color of copper sulfate was slightly greenish, and it was thought that copper ions that had not yet been deposited remained. It was washed, filtered and dried using 5A to obtain 3 g of chemical copper powder.

【００２４】実施例１の中で、銅板２０ｇをここで得た
化学還元銅１．５ｇに替えた以外は全く実施例１と同様
に行った結果、一辺が０．２〜０．３μｍ、長さ２．０
〜５．０μｍ角柱形状を有する酸化銅ウイスカーを収率
３５．１％で得た。In Example 1, except that the copper plate 20 g was replaced by the chemically reduced copper 1.5 g obtained here, the same procedure as in Example 1 was performed. As a result, one side was 0.2 to 0.3 μm and the length was long. 2.0
Copper oxide whiskers having a prism shape of ˜5.0 μm were obtained with a yield of 35.1%.

【００２５】比較例３ 実施例３で得た化学銅を使用した以外は比較例２と全く
同様の操作を行ったが酸化銅ウイスカーの生成は確認出
来なかった。Comparative Example 3 The same operation as in Comparative Example 2 was carried out except that the chemical copper obtained in Example 3 was used, but formation of copper oxide whiskers could not be confirmed.

【００２６】比較例４ 実施例１で使用した銅に表−１に示す様な一族、二族、
三族ａ亜属、四族、五族、六族、七族ａ亜属、八族の各
代表的な元素を１重量％に相当する量を加え、実施例１
と全く同様の操作を行った。Comparative Example 4 The copper used in Example 1 was classified into the groups 1 and 2 as shown in Table 1.
Example 1 was added with each of the representative elements of Group 3 a sub-genus, group 4, group 5, group 6, group 7 sub-genus a, group 8 added in an amount corresponding to 1% by weight.
The same operation was performed.

【００２７】結果を表−１に記載したが全く酸化銅ウイ
スカーの生成は認められなかった。The results are shown in Table 1, but no formation of copper oxide whiskers was observed.

【００２８】[0028]

【表１】 [Table 1]

【００２９】実施例４ 実施例１で使用した銅板１９．８ｇに亜鉛（和光純薬工
業（株）製試薬一級）を表−２に示すような割合で加え
た銅合金を使用し、実施例１と同じ操作をしてウイスカ
ーを生成せしめた。結果を表−２に合わせて示す。Example 4 A copper alloy prepared by adding 19.8 g of the copper plate used in Example 1 with zinc (Wako Pure Chemical Industries, Ltd. first-grade reagent) in the proportion shown in Table 2 was used. The same operation as in 1 was performed to generate whiskers. The results are shown in Table 2 together.

【００３０】[0030]

【表２】 [Table 2]

【００３１】[0031]

【発明の効果】以上、説明した様に本発明によれば酸化
銅ウイスカーを効率よく、かつ従来生成が困難であった
化学銅や電解銅からも合理的に得ることが出来る。As described above, according to the present invention, the copper oxide whiskers can be efficiently obtained rationally from chemical copper or electrolytic copper, which has been difficult to produce conventionally.

【００３２】このウイスカーはプラスチツクの充填材や
強化材をはじめとして、酸化銅ウイスカーが導電性であ
ることに着目し、ＥＭＩ対策用材料として極めて有効で
ある。酸化銅ウイスカーの特性を利用した他の様々な応
用が期待出来る。This whisker is extremely effective as an EMI countermeasure material, paying attention to the fact that copper oxide whiskers are conductive, including plastic fillers and reinforcing materials. Various other applications can be expected utilizing the characteristics of copper oxide whiskers.

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 金属銅をその溶融温度以上の温度に加熱
し、次いで酸素含有雰囲気下で２５０乃至７５０℃の温
度に加熱することを特徴とする酸化銅ウイスカーの製造
方法。1. A method for producing a copper oxide whisker, which comprises heating metallic copper to a temperature equal to or higher than its melting temperature and then heating it to a temperature of 250 to 750 ° C. in an oxygen-containing atmosphere. 【請求項２】 該金属銅が電解銅である、請求項１に記
載の酸化銅ウイスカーの製造方法。2. The method for producing a copper oxide whisker according to claim 1, wherein the metallic copper is electrolytic copper. 【請求項３】 該金属銅が化学的方法によって製造され
たものである、請求項１に記載の酸化銅ウイスカーの製
造方法。3. The method for producing a copper oxide whisker according to claim 1, wherein the metallic copper is produced by a chemical method. 【請求項４】 該金属銅が三族ｂ亜属元素以外の不純物
を実質的に含まない、請求項１に記載の酸化銅ウイスカ
ーの製造方法。4. The method for producing a copper oxide whisker according to claim 1, wherein the metallic copper is substantially free of impurities other than Group 3 b subgroup elements. 【請求項５】 該金属銅の三族ｂ亜属以外の不純物が
０.２重量％よりも少ない、請求項１に記載の酸化銅ウ
イスカーの製造方法。5. The method for producing a copper oxide whisker according to claim 1, wherein the amount of impurities other than Group 3 b subgroup of the metallic copper is less than 0.2% by weight.
JP24645291A 1991-09-02 1991-09-02 Production of copper oxide whisker Pending JPH0558797A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP24645291A JPH0558797A (en) 1991-09-02 1991-09-02 Production of copper oxide whisker
EP92107989A EP0530440A1 (en) 1991-09-02 1992-05-12 Copper oxide whiskers and process for producing the same
CA002068437A CA2068437A1 (en) 1991-09-02 1992-05-12 Copper oxide whiskers and process for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP24645291A JPH0558797A (en) 1991-09-02 1991-09-02 Production of copper oxide whisker

Publications (1)

Publication Number Publication Date
JPH0558797A true JPH0558797A (en) 1993-03-09

Family

ID=17148647

Family Applications (1)

Application Number Title Priority Date Filing Date
JP24645291A Pending JPH0558797A (en) 1991-09-02 1991-09-02 Production of copper oxide whisker

Country Status (1)

Country Link
JP (1) JPH0558797A (en)

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