JPH06234522A - Electrically conductive material and its production - Google Patents
Electrically conductive material and its productionInfo
- Publication number
- JPH06234522A JPH06234522A JP31508693A JP31508693A JPH06234522A JP H06234522 A JPH06234522 A JP H06234522A JP 31508693 A JP31508693 A JP 31508693A JP 31508693 A JP31508693 A JP 31508693A JP H06234522 A JPH06234522 A JP H06234522A
- Authority
- JP
- Japan
- Prior art keywords
- conductive material
- compound
- precipitate
- powder
- indium
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、樹脂などの帯電防止剤
または静電制御剤、表面導電性付与剤、導電性塗料、ス
パッタリング用のターゲット又は表示装置の透明電極な
どに用いられる導電性材料およびその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent such as resin or an electrostatic control agent, a surface conductivity imparting agent, a conductive coating material, a sputtering target or a conductive material used for a transparent electrode of a display device. And a manufacturing method thereof.
【０００２】[0002]
【従来の技術】透明、白色または淡色の導電性材料とし
ては、酸化錫にアンチモンを添加したもの（ＡＴＯ）、
酸化インジウムに錫を添加したもの（ＩＴＯ）、酸化亜
鉛にアルミニウムを添加したもの等が知られている。こ
れらは、粉末の状態で帯電防止または静電制御のために
合成樹脂などに添加され、樹脂の電気抵抗値を調製する
ために用いられている。また、表面導電性を付与するた
めに用いられる導電性塗料等にも添加されている（例え
ば静電塗装用のプライマーとして）。2. Description of the Related Art As transparent, white or light conductive materials, tin oxide added with antimony (ATO),
It is known that tin is added to indium oxide (ITO), aluminum is added to zinc oxide, and the like. These are added to a synthetic resin or the like in the powder state for antistatic or electrostatic control, and are used for adjusting the electric resistance value of the resin. It is also added to conductive paints and the like used to impart surface conductivity (for example, as a primer for electrostatic coating).
【０００３】また粉末を所定形状に成形し焼結すること
により焼結体を作製し、ターゲット材を得ている。そし
てこの焼結体からなるターゲットを用いて、スパッタ
法、蒸着法、イオンプレーティング法等で表示装置用の
透明電極がガラスや樹脂基板の上に形成されている。Further, a powder is formed into a predetermined shape and sintered to produce a sintered body, and a target material is obtained. A transparent electrode for a display device is formed on a glass or resin substrate by a sputtering method, a vapor deposition method, an ion plating method or the like using the target made of this sintered body.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ＩＴ
Ｏ、ＡＴＯは粉末の状態では耐湿性が比較的低く、湿気
により電気抵抗値が増大するという難点を有している。
またＩＴＯ、ＡＴＯ粉末は還元状態では黒化するため、
樹脂に添加すると樹脂製品の自由な着色が困難になると
いう欠点を有している。またＩＴＯ、ＡＴＯ焼結体から
なるターゲットも還元により黒化し易いため、その特性
の経時変化が問題となっている。[Problems to be Solved by the Invention] However, IT
O and ATO have a relatively low moisture resistance in the powder state, and have the drawback that the electric resistance value increases due to moisture.
Also, since ITO and ATO powder turn black in the reduced state,
When it is added to a resin, it has a drawback that it is difficult to freely color a resin product. Further, a target made of a sintered body of ITO or ATO is also easily blackened by reduction, so that a change in its characteristics with time becomes a problem.
【０００５】本発明の目的は、ＩＴＯ、ＡＴＯよりも耐
湿性に優れ、黒化しにくいとともに、ＩＴＯ、ＡＴＯと
同等の導電性を有する導電性材料およびその製造方法を
提供することにある。An object of the present invention is to provide a conductive material which is superior in moisture resistance to ITO and ATO, is less likely to be blackened, and has the same conductivity as ITO and ATO, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成する本発
明の導電性材料は、ＩｎとＺｎを主成分とし、Ｉｎの原
子比Ｉｎ／（Ｉｎ＋Ｚｎ）が０．１〜０．９である実質
的に非晶質の酸化物からなることを特徴とする導電性材
料（以下、この導電性材料を導電性材料Ｉという）であ
る。また、前記実質的に非晶質の酸化物が、正三価以上
の原子価を有する第３の元素の少なくとも１種を、第３
元素の原子比（全第３元素／（Ｉｎ＋Ｚｎ＋全第３元
素））が２０原子％以下の範囲で含むものであることを
特徴とする導電性材料もまた、上記目的を達成する（以
下、この導電性材料を導電性材料IIという）。A conductive material of the present invention which achieves the above object is composed mainly of In and Zn and has an atomic ratio In / In / (In + Zn) of 0.1 to 0.9. Is a conductive material (hereinafter, this conductive material is referred to as a conductive material I). Further, the substantially amorphous oxide contains at least one kind of a third element having a valence of positive trivalence or more, a third element
A conductive material characterized in that the atomic ratio of the elements (total third element / (In + Zn + total third element)) is contained in a range of 20 atomic% or less also achieves the above object (hereinafter, this conductivity Material is called conductive material II).
【０００７】一方、上記目的を達成する本発明の導電性
材料の製造方法は、インジウム化合物および亜鉛化合物
を用い、これらの少なくとも１種を含む１種以上の溶液
から、沈澱形成剤により形成される沈澱を、固液分離
し、必要により焼成、還元処理して実質的に非晶質の酸
化物を得ることを特徴とする導電性材料の製造方法（以
下、この方法を方法Ｉという）である。さらに、インジ
ウム化合物、亜鉛化合物および正三価以上の原子価を有
する元素の少なくとも１種の化合物を用い、これらの少
なくとも１種を含む１種以上の溶液から、沈澱形成剤に
より形成される沈澱を、固液分離し、必要により焼成、
還元処理して実質的に非晶質の酸化物を得ることを特徴
とする導電性材料の製造方法もまた、上記目的を達成す
る（以下、この方法を方法IIという）。On the other hand, the method for producing a conductive material according to the present invention, which achieves the above-mentioned object, uses an indium compound and a zinc compound and is formed from one or more solutions containing at least one of these by a precipitation forming agent. A method for producing a conductive material (hereinafter, this method is referred to as Method I), which comprises subjecting the precipitate to solid-liquid separation, and if necessary, firing and reduction treatment to obtain a substantially amorphous oxide. . Further, using at least one compound of an indium compound, a zinc compound and an element having a valence of positive trivalence or more, a precipitate formed by a precipitation forming agent is prepared from one or more solutions containing at least one of these compounds, Solid-liquid separation, firing if necessary,
A method for producing a conductive material, which is characterized in that a reduction treatment is performed to obtain a substantially amorphous oxide, also achieves the above object (hereinafter, this method is referred to as Method II).
【０００８】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【０００９】まず、本発明の導電性材料Ｉは、上述した
ようにＩｎとＺｎを主成分とし、Ｉｎの原子比Ｉｎ／
（Ｉｎ＋Ｚｎ）が０．１〜０．９である実質的に非晶質
の酸化物からなることを特徴とする導電性材料からなる
ものである。First, the conductive material I of the present invention is mainly composed of In and Zn as described above, and has an In atomic ratio of In / In.
(In + Zn) is a substantially amorphous oxide having a content of 0.1 to 0.9, and is made of a conductive material.
【００１０】ここに、「実質的に非晶質」とは、Ｘ線回
折測定で、結晶性を示す物質の量を定量し、その残量を
非晶質物質であるとした場合に、所定量の非晶質物質を
含むものをいう。Here, "substantially amorphous" means that when the amount of a substance exhibiting crystallinity is quantified by X-ray diffraction measurement and the remaining amount is an amorphous substance, It refers to a substance containing a fixed amount of an amorphous substance.
【００１１】より具体的には、この実質的に非晶質の酸
化物は、非晶質酸化物を５０重量％以上、より好ましく
は７０重量％以上、特に好ましくは８０重量％以上含
む。More specifically, the substantially amorphous oxide contains 50% by weight or more of the amorphous oxide, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
【００１２】本発明の導電性材料Ｉにおいて、ＩｎとＺ
ｎの原子比（Ｉｎ／（Ｉｎ＋Ｚｎ））は０．１〜０．９
であるのが好ましい。その理由は、０．１未満では導電
性材料の導電性が低くなり、０．９を超えると導電性材
料の耐湿、耐熱性が低下するからである。原子比（Ｉｎ
／（Ｉｎ＋Ｚｎ））は０．５〜０．９がより好ましく、
０．６〜０．７５が特に好ましい。In the conductive material I of the present invention, In and Z
The atomic ratio of n (In / (In + Zn)) is 0.1 to 0.9.
Is preferred. The reason is that if it is less than 0.1, the conductivity of the conductive material is low, and if it exceeds 0.9, the moisture resistance and heat resistance of the conductive material are lowered. Atomic ratio (In
/ (In + Zn)) is more preferably 0.5 to 0.9,
0.6 to 0.75 is particularly preferable.
【００１３】上記のＩｎとＺｎの原子比は沈澱形成時の
インジウム化合物と亜鉛化合物の混合比を調整すること
により得られる。The above atomic ratio of In and Zn can be obtained by adjusting the mixing ratio of the indium compound and the zinc compound during precipitation formation.
【００１４】本発明の導電性材料Ｉは、ＩＴＯ、ＡＴＯ
よりも耐湿性に優れ、還元によっても黒化しにくいとと
もにＩＴＯ、ＡＴＯと同等の導電性を有し、前記した各
種の用途（帯電防止剤、表面導電性付与剤、導電性塗
料、スパッタリング用のターゲット、表示装置の透明電
極など）に用いられる。The conductive material I of the present invention is ITO or ATO.
It has more excellent moisture resistance than that, is less likely to be blackened by reduction, and has the same conductivity as ITO and ATO, and has the various applications described above (antistatic agent, surface conductivity imparting agent, conductive coating, sputtering target). , Transparent electrodes of display devices, etc.).
【００１５】導電性材料Ｉは気相法（ＣＶＤ法）、固相
法（物理混合法）などの種々の方法により製造すること
が可能であるが、後述する本発明の方法Ｉに従って液相
法（共沈法）により製造することが好ましい。The conductive material I can be manufactured by various methods such as a vapor phase method (CVD method) and a solid phase method (physical mixing method), and the liquid phase method is carried out according to the method I of the present invention described later. It is preferable to manufacture by (coprecipitation method).
【００１６】次に、本発明の導電性材料IIについて説明
する。Next, the conductive material II of the present invention will be described.
【００１７】この導電性材料IIは、ＩｎとＺｎ以外に、
正三価以上の原子価を有する元素の少なくとも１種を、
第３元素の原子比（全第３元素／（Ｉｎ＋Ｚｎ＋全第３
元素））が２０原子％以下の範囲で含む実質的に非晶質
の酸化物からなるものである。ここで、正三価以上の原
子価を有する元素としては、Ａｌ，Ｇａ（正三価）、Ｓ
ｉ，Ｇｅ，Ｓｎ（正四価）、Ｓｂ（正五価）の元素が挙
げられるが、導電性改良の効果が大きいＳｎが望まし
い。This conductive material II is, in addition to In and Zn,
At least one element having a valence of positive trivalence or more,
Atomic ratio of third element (all third element / (In + Zn + all third
Element)) is a substantially amorphous oxide containing 20 atomic% or less. Here, as the element having a valence of positive trivalence or more, Al, Ga (positive trivalence), S
Examples of the element include i, Ge, Sn (positive tetravalent) and Sb (positive pentavalent), and Sn having a large effect of improving conductivity is preferable.
【００１８】また、本発明の導電性材料IIにおいて、正
三価以上の原子価を有する元素、例えばＳｎ，Ａｌ，Ｇ
ａ，Ｓｂ，Ｓｉ，Ｇｅ元素を２０原子％を超えて添加す
ると、導電性が低下することがある。In the conductive material II of the present invention, an element having a valence of positive trivalence or more, such as Sn, Al, G
If the elements a, Sb, Si and Ge are added in an amount of more than 20 atomic%, the conductivity may decrease.
【００１９】本発明の導電性材料IIは、ＩＴＯ、ＡＴＯ
よりも耐湿性に優れ、黒化しにくいとともにＩＴＯ、Ａ
ＴＯと同等の導電性を有するので、前記した各種の用途
（帯電防止剤、表面導電性付与剤、導電性塗料、スパッ
タリング用のターゲット、表示装置の透明電極など）に
用いられる。The conductive material II of the present invention is made of ITO or ATO.
Moisture resistance is superior to that of ITO, A
Since it has the same conductivity as TO, it is used for the various applications described above (antistatic agents, surface conductivity imparting agents, conductive coatings, targets for sputtering, transparent electrodes for display devices, etc.).
【００２０】導電性材料IIも気相法（ＣＶＤ法）、固相
法（物理混合法）などの種々の方法により製造すること
が可能であるが、後述する本発明の方法IIに従って溶液
法（共沈法）により製造することが好ましい。The conductive material II can also be produced by various methods such as a vapor phase method (CVD method) and a solid phase method (physical mixing method). However, according to the method II of the present invention described later, the solution method ( Coprecipitation method) is preferred.
【００２１】次に、本発明の方法Ｉおよび方法IIについ
て説明する。Next, the method I and the method II of the present invention will be described.
【００２２】まず本発明の方法Ｉは、前述したようにイ
ンジウム化合物および亜鉛化合物を用い、これらの少な
くとも１種を含む１種以上の溶液から、沈澱形成剤によ
り形成される沈澱を、固液分離し、必要により焼成、還
元処理して実質的に非晶質の酸化物からなる導電性材料
を得ることを特徴とする。First, in the method I of the present invention, as described above, the indium compound and the zinc compound are used, and the precipitate formed by the precipitation forming agent is subjected to solid-liquid separation from one or more solutions containing at least one of them. Then, if necessary, firing and reduction treatments are performed to obtain a conductive material made of a substantially amorphous oxide.
【００２３】方法Ｉで原料として用いるインジウム化合
物および亜鉛化合物は、酸化物または焼成後に酸化物に
なるもの（酸化物前駆体）であれば良い。インジウム酸
化物前駆体、亜鉛酸化物前駆体としては、インジウム、
亜鉛の硫化物、硫酸塩、硝酸塩、ハロゲン化物（塩化
物、臭化物等）、炭酸塩、有機酸塩（酢酸塩、プロピオ
ン酸塩、ナフテン酸塩等）、アルコキシド（メトキシ
ド、エトキシド等）、有機金属錯体（アセチルアセトナ
ート等）等が挙げられる。The indium compound and the zinc compound used as raw materials in Method I may be oxides or compounds that become oxides after firing (oxide precursors). As an indium oxide precursor and a zinc oxide precursor, indium,
Zinc sulfide, sulfate, nitrate, halide (chloride, bromide, etc.), carbonate, organic acid salt (acetate, propionate, naphthenate, etc.), alkoxide (methoxide, ethoxide, etc.), organic metal Examples thereof include complexes (acetylacetonate, etc.).
【００２４】特に、低温で完全に熱分解し、不純物が残
存しないようにするためには、この中でも、硝酸塩、有
機酸塩、アルコキシド、有機金属錯体を用いるのが好ま
しい。Of these, nitrates, organic acid salts, alkoxides, and organic metal complexes are preferably used in order to completely decompose heat at low temperature and prevent impurities from remaining.
【００２５】方法Ｉでは、先ず沈澱を形成するが、沈澱
の形成は、具体的には、以下に示す方法で行なうことが
できる。In Method I, a precipitate is first formed, but the precipitation can be specifically formed by the following method.
【００２６】まず、インジウム化合物と亜鉛化合物を溶
解した溶液、もしくは少なくともインジウム化合物を溶
解した溶液と少なくとも亜鉛化合物を溶解した溶液、お
よび沈澱形成剤を溶解した溶液をそれぞれ調製し、別個
に用意した容器（必要により溶媒を入れておいてもよ
い）に必要により撹拌しながら前述の溶液を同時にある
いは順次添加混合して沈澱を形成することができる。First, a solution in which an indium compound and a zinc compound are dissolved, or a solution in which at least an indium compound is dissolved and a solution in which at least a zinc compound is dissolved, and a solution in which a precipitation-forming agent is dissolved are prepared and prepared separately. A precipitate can be formed by adding and mixing the above-mentioned solutions at the same time or sequentially while stirring (if necessary, a solvent may be added).
【００２７】また、インジウム化合物と亜鉛化合物を溶
解した溶液に沈澱形成剤を溶解した溶液を添加してもよ
いし、またその逆であってもよい。Further, the solution in which the precipitation forming agent is dissolved may be added to the solution in which the indium compound and the zinc compound are dissolved, and vice versa.
【００２８】例えば、インジウム化合物と亜鉛化合物を
溶解した溶液と沈澱形成剤を溶解した溶液をそれぞれ調
製し、別個に溶媒を入れた容器に撹拌しながら両者の溶
液を同時に添加混合して沈澱を形成する場合について以
下詳細に説明する。For example, a solution in which an indium compound and a zinc compound are dissolved and a solution in which a precipitation forming agent is dissolved are prepared, and both solutions are simultaneously added and mixed while stirring in a container containing a solvent to form a precipitate. The case will be described in detail below.
【００２９】先ず、上記インジウム化合物および亜鉛化
合物を、適当な溶媒に溶解させた溶液（以下、溶液Ａと
いう）を準備する。溶媒は、用いるインジウム化合物ま
たは亜鉛化合物の溶解性に応じて適宜選択すればよく、
例えば、水、アルコール、非プロトン性極性溶媒（ＤＭ
ＳＯ、ＮＭＰ、スルホラン、ＴＨＦなど）を用いること
ができ、生成する沈澱の溶解度が低いことから、特に炭
素数１〜５のアルコール（メタノール、エタノール、イ
ソプロパノール、メトキシエタノール、エチレングリコ
ールなど）が好ましい。溶液Ａ中の各金属の濃度は０．
０１〜１０ｍｏｌ／リットルが好ましい。その理由は
０．０１ｍｏｌ／リットル未満では生産性が劣り、１０
ｍｏｌ／リットルを超えると不均一な沈澱が生成するか
らである。さらに、原料の溶解を促進するため、各種溶
媒により適宜、酸（硝酸、塩酸等）やアセチルアセトン
類、多価アルコール（エチレングリコール等）、エタノ
ールアミン類（モノエタノールアミン、ジエタノールア
ミン等）を溶液中の金属量の０．０１〜１０倍程度添加
してもよい。First, a solution (hereinafter referred to as solution A) in which the above indium compound and zinc compound are dissolved in a suitable solvent is prepared. The solvent may be appropriately selected depending on the solubility of the indium compound or zinc compound used,
For example, water, alcohol, aprotic polar solvent (DM
SO, NMP, sulfolane, THF, etc. can be used, and alcohols having 1 to 5 carbon atoms (methanol, ethanol, isopropanol, methoxyethanol, ethylene glycol, etc.) are particularly preferable because of low solubility of the formed precipitate. The concentration of each metal in solution A was 0.
01 to 10 mol / liter is preferable. The reason is that if the amount is less than 0.01 mol / liter, the productivity is inferior, and 10
This is because if it exceeds mol / liter, a non-uniform precipitate is formed. Furthermore, in order to accelerate the dissolution of the raw materials, an acid (nitric acid, hydrochloric acid, etc.), acetylacetones, polyhydric alcohol (ethylene glycol, etc.), ethanolamines (monoethanolamine, diethanolamine, etc.) are appropriately added to the solution by various solvents. You may add about 0.01-10 times the metal amount.
【００３０】方法Ｉにおいて、上記溶液Ａとともに、沈
澱形成剤を溶解させた溶液（以下、溶液Ｂという）をも
準備する。溶液Ｂに溶解させる沈澱形成剤としては、ア
ルカリ（水酸化ナトリウム、水酸化カリウム、炭酸ナト
リウム、炭酸カリウム、重炭酸ナトリウム、重炭酸カリ
ウム、水酸化アンモニウム、炭酸アンモニウム、重炭酸
アンモニウム等）、有機酸（ギ酸、しゅう酸、クエン酸
等）等が用いられるが、不純物の混入を避けるため、有
機酸（特にしゅう酸）を用いることが好ましい。In Method I, a solution in which a precipitation forming agent is dissolved (hereinafter referred to as solution B) is also prepared together with the above solution A. As the precipitation forming agent to be dissolved in the solution B, alkali (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, etc.), organic acid (Formic acid, oxalic acid, citric acid, etc.) is used, but it is preferable to use an organic acid (particularly oxalic acid) in order to avoid mixing of impurities.
【００３１】沈澱は沈澱形成剤により水酸化物、無機酸
塩、有機酸塩となる。The precipitate is converted into a hydroxide, an inorganic acid salt or an organic acid salt by the precipitation forming agent.
【００３２】また沈澱形成剤を溶解するための溶媒及び
沈澱を形成させる容器に入れる溶媒としては、原料を溶
解するために用いる上記した溶媒を用いることができ
る。As the solvent for dissolving the precipitate forming agent and the solvent put in the container for forming the precipitate, the above-mentioned solvents used for dissolving the raw materials can be used.
【００３３】また、各種溶液に用いる溶媒は、操作上同
じものを用いた方がよいが、異なる溶媒を用いてもよ
い。The solvents used for the various solutions should be the same in operation, but different solvents may be used.
【００３４】方法Ｉにおいては、上述のいずれかの手段
で沈澱物を形成させるが、沈澱形成時の温度は、溶媒の
融点以上沸点以下であればよい。また、形成後に熟成を
１〜５０時間行ってもよい。In Method I, a precipitate is formed by any of the above means, and the temperature at the time of forming the precipitate may be above the melting point of the solvent and below its boiling point. Further, aging may be performed for 1 to 50 hours after formation.
【００３５】方法Ｉによれば、上記のようにして得られ
た沈澱物を次に固液分離、乾燥する。沈澱物の固液分離
は、遠心分離、濾過等の常法により行なわれる。固液分
離後、沈澱物から陰イオンやアルカリ金属イオン等を除
去する目的で、溶液Ａ、Ｂに用いた溶媒またはその他の
溶媒で濾別物を十分に洗浄することが望ましい。濾別後
の乾燥は、４０〜２００℃で０．１〜１００時間行うの
が好ましい。低温では、乾燥に時間がかかり過ぎ、高温
では粒子の凝集が起きやすくなる。According to method I, the precipitate obtained as described above is then solid-liquid separated and dried. Solid-liquid separation of the precipitate is carried out by a conventional method such as centrifugation or filtration. After the solid-liquid separation, it is desirable to thoroughly wash the filtered material with the solvent used in the solutions A and B or another solvent for the purpose of removing anions, alkali metal ions and the like from the precipitate. Drying after filtration is preferably carried out at 40 to 200 ° C. for 0.1 to 100 hours. At low temperatures, it takes too long to dry, and at high temperatures, particles tend to agglomerate.
【００３６】方法Ｉによれば、上記固液分離、乾燥後に
焼成、粉砕、還元処理を行なう。According to the method I, the solid-liquid separation and the drying are followed by firing, pulverization and reduction treatment.
【００３７】焼成は、用いるインジウム化合物および亜
鉛化合物にもよるが２００〜６００℃で１〜１００時間
行なうのが好ましい。低温、短時間では、インジウム又
は亜鉛の酸化物前駆体の酸化物への分解が不十分とな
り、また高温、長時間では酸化物が結晶化してくること
がある。The firing is preferably carried out at 200 to 600 ° C. for 1 to 100 hours, depending on the indium compound and zinc compound used. The decomposition of the oxide precursor of indium or zinc into an oxide becomes insufficient at a low temperature for a short time, and the oxide may crystallize at a high temperature for a long time.
【００３８】焼成後の粉砕はボールミル、ロールミル、
ジェットミル、パールミル等によって、粒子径が０．０
１〜１０μｍになるまで行なうのが好ましい。粉砕時間
は、通常１分〜５００時間である。The crushing after firing is performed by a ball mill, a roll mill,
The particle size is 0.0 with a jet mill, pearl mill, etc.
It is preferable to carry out until it becomes 1 to 10 μm. The crushing time is usually 1 minute to 500 hours.
【００３９】還元処理は、還元性ガス（水素、ＣＯ
等）、真空、不活性ガス（窒素、アルゴン）等の雰囲気
で、温度１００〜８００℃で１分〜１００時間行なうの
が好ましい。低温、短時間では、還元が不十分であり、
高温、長時間では粒子の凝集や成分の飛散が起きやす
い。この還元処理は、焼成工程又は粉砕工程の後に行う
ことが好ましい。The reducing treatment is performed by using a reducing gas (hydrogen, CO
Etc.), vacuum, an atmosphere of an inert gas (nitrogen, argon), etc., preferably at a temperature of 100 to 800 ° C. for 1 minute to 100 hours. At low temperature and short time, reduction is insufficient,
Agglomeration of particles and scattering of components easily occur at high temperature for a long time. This reduction treatment is preferably performed after the firing step or the crushing step.
【００４０】方法Ｉによれば、上記の諸工程を行なうこ
とにより、ＩｎとＺｎを主成分とし、実質的に非晶質の
酸化物からなる導電性材料が得られる。この導電性粉末
Ｉは、ＩＴＯ、ＡＴＯよりも耐湿性が優れ、黒化しにく
いとともにＩＴＯ、ＡＴＯと同等の導電性を有してい
る。この粉末の体積固体抵抗（一般に「粉体抵抗」と表
現されることもある）は例えば４０Ω・ｃｍ以下であ
る。According to Method I, by carrying out the above-mentioned steps, a conductive material containing In and Zn as main components and consisting of a substantially amorphous oxide can be obtained. The conductive powder I has a higher moisture resistance than ITO and ATO, is less likely to be blackened, and has the same conductivity as ITO and ATO. The volume solid resistance (generally referred to as “powder resistance”) of this powder is, for example, 40 Ω · cm or less.
【００４１】次に、本発明の方法IIについて説明する。Next, the method II of the present invention will be described.
【００４２】この方法IIは前述したように、インジウム
化合物および亜鉛化合物に正三価以上の原子価を有する
元素（例えば錫化合物，アルミニウム化合物，ガリウム
化合物、アンチモン化合物、ケイ素化合物およびゲルマ
ニウム化合物）から選択される少なくとも１種を加えた
ものを原料として用いる点でのみ上記方法Ｉと異なり、
他は上記方法Ｉと同様に行うものである。As described above, this method II is selected from indium compounds and zinc compounds having elements having a valence of positive trivalence or more (for example, tin compounds, aluminum compounds, gallium compounds, antimony compounds, silicon compounds and germanium compounds). Which differs from the above method I only in that at least one of
Others are the same as in the above method I.
【００４３】方法IIで用いる正三価以上の原子価を有す
る元素（例えば錫化合物、アルミニウム化合物、ガリウ
ム化合物、アンチモン化合物、ケイ素化合物およびゲル
マニウム化合物）は、酸化物または焼成後に酸化物にな
るもの（酸化物前駆体）であれば良い。これらの酸化物
前駆体としては、それぞれの元素（例えばＳｎ，Ａｌ，
Ｇａ，Ａｂ，ＳｉおよびＧｅ）の硫化物、硫酸塩、硝酸
塩、ハロゲン化物（塩化物、臭化物等）、炭酸塩、有機
酸塩（酢酸塩、プロピオン酸塩、ナフテン酸塩等）、ア
ルコキシド（メトキシド、エトキシド等）、有機金属錯
体（アセチルアセトナート等）が挙げられる。The element having a valence of positive trivalence or more (for example, tin compound, aluminum compound, gallium compound, antimony compound, silicon compound and germanium compound) used in the method II is an oxide or one which becomes an oxide after firing (oxidation). Precursor). As these oxide precursors, each element (for example, Sn, Al,
Ga, Ab, Si and Ge) sulfide, sulfate, nitrate, halide (chloride, bromide, etc.), carbonate, organic acid salt (acetate, propionate, naphthenate, etc.), alkoxide (methoxide) , Ethoxide, etc.), and organometallic complexes (acetylacetonate, etc.).
【００４４】低温で完全に熱分解し、不純物が残存しな
いようにするためには、この中でも、硝酸塩、有機酸
塩、アルコキシド、有機金属錯体を用いるのが好まし
い。Of these, nitrates, organic acid salts, alkoxides, and organometallic complexes are preferably used in order to completely decompose thermally at low temperature and prevent impurities from remaining.
【００４５】得られた導電性材料IIはＩＴＯ、ＡＴＯよ
りも耐湿性に優れ、還元によっても黒化しにくく、かつ
ＩＴＯ、ＡＴＯと同等の導電性を有する。The obtained conductive material II is superior in moisture resistance to ITO and ATO, hard to be blackened by reduction, and has the same conductivity as ITO and ATO.
【００４６】本発明の導電性粉末は各種の樹脂と混合す
ることにより帯電防止樹脂組成物として利用することが
できる。The conductive powder of the present invention can be used as an antistatic resin composition by mixing with various resins.
【００４７】使用できる樹脂としては、ポリエチレン、
ポリプロピレン、ポリスチレン、塩化ビニール、酢酸ビ
ニール、ポリビニルアルコール、塩化ビニリデン、ＡＢ
Ｓ樹脂、ポリエステル、メタクリル酸メチル、ポリウレ
タン、ポリアミド、ポリアセタール、ポリカーボネー
ト、ケイ素樹脂、フッ素樹脂などの熱可塑性樹脂；フェ
ノール樹脂、ユリア樹脂、メラミン樹脂、キシレン樹
脂、フラン樹脂、アルキッド樹脂、エポキシ樹脂、ポリ
イミド樹脂などの熱硬化性樹脂が挙げられる。Resins that can be used include polyethylene,
Polypropylene, polystyrene, vinyl chloride, vinyl acetate, polyvinyl alcohol, vinylidene chloride, AB
Thermoplastic resins such as S resin, polyester, methyl methacrylate, polyurethane, polyamide, polyacetal, polycarbonate, silicon resin, fluororesin; phenol resin, urea resin, melamine resin, xylene resin, furan resin, alkyd resin, epoxy resin, polyimide Thermosetting resins such as resins may be mentioned.
【００４８】また導電性粉末は樹脂１００重量部に対し
て１〜６００重量部添加するのが好ましい。添加量が少
ないと導電性が不十分となり、多いと樹脂の物性を損な
うことがある。導電性粉末の分散性を改良するため、導
電性粉末の表面を表面処理剤（シラン系カップリング
剤、チタン系カップリング剤、アルミネート系カップリ
ング剤など）で処理してもよい。Further, it is preferable to add 1 to 600 parts by weight of the conductive powder to 100 parts by weight of the resin. If the added amount is small, the conductivity becomes insufficient, and if the added amount is large, the physical properties of the resin may be impaired. In order to improve the dispersibility of the conductive powder, the surface of the conductive powder may be treated with a surface treatment agent (silane coupling agent, titanium coupling agent, aluminate coupling agent, etc.).
【００４９】またその他各種の添加剤（可塑剤、安定
剤、滑剤、無機フィラー（炭酸カルシウム、マイカ、ガ
ラス、タルクなど）、無機繊維（ガラス繊維、炭素繊維
など）、ウィスカー（チタン酸カリウム、酸化亜鉛ウィ
スカーなど）、界面活性剤などを添加してもよい。Various other additives (plasticizer, stabilizer, lubricant, inorganic filler (calcium carbonate, mica, glass, talc, etc.), inorganic fiber (glass fiber, carbon fiber, etc.), whiskers (potassium titanate, oxidation) Zinc whiskers, etc.), surfactants, etc. may be added.
【００５０】導電性粉末と樹脂の混合方法としては、２
本ロール、３本ロール又は射出成形機を用いて加熱状態
または常温下で練り込む方法、または、樹脂を溶かした
溶液と粉末を混合する方法などの通常の手段を用いるこ
とができる。The method for mixing the conductive powder and the resin is 2
It is possible to use an ordinary means such as a method of kneading using a main roll, a three roll or an injection molding machine in a heated state or at room temperature, or a method of mixing a solution in which a resin is dissolved and a powder.
【００５１】[0051]
【実施例】以下、本発明の実施例について説明するが、
先ず、実施例で得られた物質の物性の測定方法について
説明しておく。EXAMPLES Examples of the present invention will be described below.
First, the method for measuring the physical properties of the substances obtained in the examples will be described.
【００５２】［測定方法］ （１）粒子径と組成の測定 粒子径はＳＥＭ（走査型電子顕微鏡）で、組成はＸＭＡ
（Ｘ線マイクロアナライザー）で測定した。[Measurement method] (1) Measurement of particle size and composition Particle size is SEM (scanning electron microscope), composition is XMA
(X-ray micro analyzer).
【００５３】（２）非晶質酸化物の定量 粉末Ｘ線回折装置を用いて、「セラミックスのキャラク
タリゼーション技術」，社団法人窯業協会発行、１９８
７年、４４〜４５頁に記載の方法により、結晶質物質の
含有量を定量した。次に、その残量を非晶質酸化物であ
るとして非晶質酸化物量を定量した。(2) Quantification of Amorphous Oxide Using a powder X-ray diffractometer, "Ceramics characterization technology", published by The Ceramic Society of Japan, 198
The content of the crystalline substance was quantified by the method described on pages 44 to 45 for 7 years. Next, the amount of the amorphous oxide was quantified assuming that the remaining amount was the amorphous oxide.
【００５４】（３）体積固体抵抗の測定 体積固体抵抗（一般に「粉体抵抗」と表現されることも
ある）は試料１ｇを内径１０ｍｍの樹脂の円筒に入れ、
１００ｋｇ／ｃｍ2 の加圧を行い、テスターで抵抗を測
定し、下記の式により求めた。(3) Measurement of volume solid resistance For volume solid resistance (generally referred to as "powder resistance"), 1 g of a sample is put in a resin cylinder having an inner diameter of 10 mm,
The pressure was applied at 100 kg / cm 2 , the resistance was measured with a tester, and the resistance was determined by the following formula.
【００５５】体積固体抵抗（Ω・ｃｍ）＝［（全抵抗
（Ω）×シリンダーの内面積（ｃｍ2 ）］／試料の厚さ
（ｃｍ）Volume solid resistance (Ω · cm) = [(total resistance (Ω) × inner area of cylinder (cm 2 )] / thickness of sample (cm)
【００５６】実施例１ まず、硝酸インジウム１１８．２８ｇと硝酸亜鉛４９．
５８ｇとを１リットルのイオン交換水に溶解させて、イ
ンジウム塩と亜鉛塩とが溶解した水溶液を調製した。ま
た、アンモニア水（濃度２８％）７８．０ｇを７５０ｃ
ｃのイオン交換水に溶解させて、アルカリ性水溶液を調
製した。Example 1 First, 118.28 g of indium nitrate and 49.
58 g was dissolved in 1 liter of ion-exchanged water to prepare an aqueous solution in which an indium salt and a zinc salt were dissolved. Also, 78.0 g of ammonia water (concentration 28%) is added to 750 c
It was dissolved in ion-exchanged water of c to prepare an alkaline aqueous solution.
【００５７】次いで、イオン交換水１００ｃｃが入った
容積５リットルの容器に、上で得られた水溶液とアルカ
リ性水溶液とを室温下で激しく攪拌しながら同時に滴下
して、両液を反応させた。このとき、反応系のｐＨが
９．０に保たれるように滴下速度を調節した。そして、
滴下終了後も更に１時間攪拌した。このようにして上記
水溶液とアルカリ性水溶液とを反応させることにより沈
殿物が生じ、スラリーが得られた。なお、この反応系に
おける金属（ＩｎおよびＺｎ）濃度は０．３２ mol／リ
ットルであった。Next, the aqueous solution obtained above and the alkaline aqueous solution were simultaneously added dropwise at room temperature to a container having a volume of 5 liters containing 100 cc of ion-exchanged water with vigorous stirring to react the two solutions. At this time, the dropping rate was adjusted so that the pH of the reaction system was maintained at 9.0. And
After the dropping was completed, the mixture was further stirred for 1 hour. In this way, a precipitate was generated by reacting the aqueous solution with the alkaline aqueous solution, and a slurry was obtained. The metal (In and Zn) concentration in this reaction system was 0.32 mol / liter.
【００５８】次に、得られたスラリーを十分に水洗した
後、沈殿物を濾取した。そして、濾取した沈殿物を１２
０℃で一晩乾燥した。Next, the obtained slurry was thoroughly washed with water and the precipitate was collected by filtration. Then, the precipitate collected by filtration is 12
Dry overnight at 0 ° C.
【００５９】この後、得られた乾燥物を６００℃で５時
間焼成した後、焼成物を直径２ｍｍのアルミナボールと
ともに容積８０ｃｃのポリイミド製ポットに入れ、エタ
ノールを加えて、遊星ボールミルで２時間粉砕して粉末
を得た。Thereafter, the dried product obtained was calcined at 600 ° C. for 5 hours, and then the calcined product was put together with alumina balls having a diameter of 2 mm in a polyimide pot having a volume of 80 cc, ethanol was added, and the mixture was pulverized for 2 hours by a planetary ball mill. To obtain a powder.
【００６０】このようにして得られた粉末はＸ線回折測
定の結果から、６０ｗｔ％の非晶質部分を含むこと及び
ＸＭＡ組成分析の結果からＩｎとＺｎの原子比がＩｎ／
（Ｉｎ＋Ｚｎ）＝０．６６の導電性材料Ｉであることが
確認され、その組成は実質的に均一であった。また、Ｓ
ＥＭ（走査型電子顕微鏡）観察の結果、得られた粉末は
平均粒子径が０．１５μｍで、実質的に均一粒径である
ことが確認された。The powder thus obtained was found to contain 60 wt% of an amorphous part from the result of X-ray diffraction measurement, and the atomic ratio of In to Zn was In / Zn from the result of XMA composition analysis.
It was confirmed that the conductive material I was (In + Zn) = 0.66, and its composition was substantially uniform. Also, S
As a result of EM (scanning electron microscope) observation, it was confirmed that the obtained powder had an average particle diameter of 0.15 μm and had a substantially uniform particle diameter.
【００６１】また、得られた粉末の体積固体抵抗は１０
０Ωｃｍであった。そして、この体積固体抵抗は、４０
℃、９０％ＲＨ（相対湿度）の条件での耐湿性試験１０
００時間後でも１０５Ωｃｍと低く、得られた粉末は耐
湿性に優れていることが確認された。The volume solid resistance of the obtained powder is 10
It was 0 Ωcm. And this volume solid resistance is 40
Moisture resistance test under conditions of 90 ° C and 90% RH (relative humidity) 10
Even after 00 hours, it was as low as 105 Ωcm, and it was confirmed that the obtained powder had excellent moisture resistance.
【００６２】実施例２ まず、硝酸インジウム５９．１４ｇと硝酸亜鉛９９．１
６ｇとを１リットルのイオン交換水に溶解させて、イン
ジウム塩と亜鉛塩とが溶解した水溶液を調製し、この水
溶液と実施例１と同様にして調製したアルカリ性水溶液
とを実施例１と同様にして反応させて、スラリーを得
た。なお、この反応系における金属（ＩｎおよびＺｎ）
濃度は０．３ mol／リットルであった。Example 2 First, 59.14 g of indium nitrate and 99.1 of zinc nitrate
6 g was dissolved in 1 liter of ion-exchanged water to prepare an aqueous solution in which an indium salt and a zinc salt were dissolved, and this aqueous solution and an alkaline aqueous solution prepared in the same manner as in Example 1 were treated in the same manner as in Example 1. And reacted to obtain a slurry. The metals (In and Zn) in this reaction system
The concentration was 0.3 mol / liter.
【００６３】次に、得られたスラリーを十分に水洗した
後、沈殿物を濾取した。そして、濾取した沈殿物を１２
０℃で一晩乾燥した。Next, the obtained slurry was thoroughly washed with water and the precipitate was collected by filtration. Then, the precipitate collected by filtration is 12
Dry overnight at 0 ° C.
【００６４】この後、得られた乾燥物を５００℃で５時
間焼成した後、焼成物を実施例１と同様にして粉砕し
て、粉末を得た。Thereafter, the obtained dried product was fired at 500 ° C. for 5 hours, and then the fired product was pulverized in the same manner as in Example 1 to obtain a powder.
【００６５】このようにして得られた粉末はＸ線回折測
定の結果から、７０ｗｔ％の非晶質部分を含むこと及び
ＸＭＡ組成分析の結果からＩｎとＺｎの原子比がＩｎ／
（Ｉｎ＋Ｚｎ）＝０．３３の導電性材料Ｉであることが
確認され、その組成は実質的に均一であった。また、Ｓ
ＥＭ観察の結果、得られた粉末は平均粒子径が０．２３
μｍで、実質的に均一粒径であることが確認された。The powder thus obtained was found to contain 70 wt% of an amorphous portion from the result of X-ray diffraction measurement, and the atomic ratio of In to Zn was In / Zn from the result of XMA composition analysis.
It was confirmed that the conductive material I was (In + Zn) = 0.33, and its composition was substantially uniform. Also, S
As a result of EM observation, the obtained powder had an average particle size of 0.23.
It was confirmed that the particle size was substantially uniform at μm.
【００６６】また、得られた粉末の体積固体抵抗は５５
０Ωｃｍであった。そして、この体積固体抵抗は、４０
℃、９０％ＲＨの条件での耐湿性試験１０００時間後で
も５６０Ωｃｍと低く、得られた粉末は耐湿性に優れて
いることが確認された。The volume solid resistance of the obtained powder is 55.
It was 0 Ωcm. And this volume solid resistance is 40
Even after 1000 hours of humidity resistance test under conditions of ° C and 90% RH, it was as low as 560 Ωcm, and it was confirmed that the obtained powder has excellent humidity resistance.
【００６７】実施例３ 実施例１と同様にしてインジウムと亜鉛の金属塩を溶解
した水溶液を調製した後、更に塩化第二錫７．７ｇを添
加して得た水溶液と、実施例１と同様にして調製したア
ルカリ性水溶液とを実施例１と同様にして反応させてス
ラリーを得た。Example 3 Similar to Example 1, an aqueous solution prepared by dissolving metal salts of indium and zinc was prepared in the same manner as in Example 1, and then 7.7 g of stannic chloride was added, and the same solution as in Example 1. The alkaline aqueous solution prepared as described above was reacted in the same manner as in Example 1 to obtain a slurry.
【００６８】次に、得られたスラリーを十分に水洗した
後、沈殿物を濾取した。そして、濾取した沈殿物を１２
０℃で乾燥した後、６００℃で５時間焼成した。ボール
ミルとともに容積８０ｃｃのポリイミド製のポットに入
れ、エタノールを加えて遊星ボールミルで２時間粉砕し
た。Next, the obtained slurry was thoroughly washed with water and the precipitate was collected by filtration. Then, the precipitate collected by filtration is 12
After drying at 0 ° C, it was baked at 600 ° C for 5 hours. It was put in a polyimide pot having a volume of 80 cc together with a ball mill, ethanol was added, and the mixture was pulverized for 2 hours in a planetary ball mill.
【００６９】この後、得られた焼成物を実施例１と同様
にして粉砕して、粉末を得た。このようにして得られた
粉末はＸ線回折測定の結果から、６０ｗｔ％の非晶質部
分を含むことがわかった。また組成分析からＩｎとＺｎ
の原子比［Ｉｎ／（Ｉｎ＋Ｚｎ）］＝０．６３であり、
Ｓｎを６原子％含むことがわかった。粉末の体積固体抵
抗は９０Ωｃｍであった。そして、この体積固体抵抗
は、４０℃、９０％ＲＨの条件での耐湿性試験１０００
時間後でも１００Ωｃｍと低く、得られた粉末は耐湿性
に優れていることが確認された。Thereafter, the obtained fired product was pulverized in the same manner as in Example 1 to obtain a powder. From the result of X-ray diffraction measurement, it was found that the powder thus obtained contains 60 wt% of an amorphous part. Moreover, from the composition analysis, In and Zn
The atomic ratio [In / (In + Zn)] = 0.63,
It was found to contain 6 atomic% of Sn. The volume solid resistance of the powder was 90 Ωcm. And this volume solid resistance is measured by the humidity resistance test 1000 under the conditions of 40 ° C. and 90% RH.
Even after the lapse of time, it was as low as 100 Ωcm, and it was confirmed that the obtained powder had excellent moisture resistance.
【００７０】実施例４ まず、硝酸インジウム６水和物６８２ｇと硝酸亜鉛６水
和物２４８ｇとを５リットルのエタノールに溶解させ
て、インジウム塩と亜鉛塩とが溶解した溶液を調製し
た。また、しゅう酸２水和物４６２ｇを５リットルのエ
タノールに溶解させて、しゅう酸水溶液を調製した。Example 4 First, 682 g of indium nitrate hexahydrate and 248 g of zinc nitrate hexahydrate were dissolved in 5 liters of ethanol to prepare a solution in which an indium salt and a zinc salt were dissolved. Further, 462 g of oxalic acid dihydrate was dissolved in 5 liters of ethanol to prepare an oxalic acid aqueous solution.
【００７１】室温下、別途容器にエタノール１リットル
をいれてよく撹拌しておき、そこへ同じ流量に制御した
２種の溶液を同時に滴下した。滴下終了後、温度を４０
℃に上げて、４時間熟成した。その後、ろ過し、エタノ
ールでよく洗浄し、１１０℃で１２時間乾燥した。さら
に、３００℃で２時間焼成した。At room temperature, 1 liter of ethanol was separately placed in a separate container and well stirred, and two kinds of solutions controlled to the same flow rate were simultaneously added dropwise thereto. After the dropping is completed, the temperature is set to 40.
The temperature was raised to ℃ and aged for 4 hours. Then, it was filtered, washed well with ethanol, and dried at 110 ° C. for 12 hours. Furthermore, it baked at 300 degreeC for 2 hours.
【００７２】ボールミルでの粉砕（２０時間）の後、粉
末を真空中で２００℃、２時間還元処理したところ、淡
黄色の粉末を得た。After crushing with a ball mill (20 hours), the powder was subjected to reduction treatment in vacuum at 200 ° C. for 2 hours to obtain a pale yellow powder.
【００７３】このようにして得られた粉末のＸ線回折測
定を実施例１と同様に行ったところ、非晶質部分は９０
％であり、実質的に非晶質であることが確認された。ま
た組成分析から、ＩｎとＺｎの原子比［Ｉｎ／（Ｉｎ＋
Ｚｎ）］＝０．６７であった。さらに粉末の体積固体抵
抗を測定したところ、５Ωｃｍであった。そして、この
体積固体抵抗は、６０℃、９５％ＲＨの条件での耐湿性
試験１０００時間後にも６Ωｃｍであり、ほとんど変化
がなく、耐湿性に優れていることがわかった。また、Ｓ
ＥＭとＸＭＡの分析によりこの粉末は平均粒径０．２０
μｍで均一な組成を持つことがわかった。The powder thus obtained was subjected to X-ray diffraction measurement in the same manner as in Example 1. As a result, 90
%, And it was confirmed to be substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [In / (In +
Zn)] = 0.67. Further, the volume solid resistance of the powder was measured and found to be 5 Ωcm. The volume solid resistance was 6 Ωcm even after 1000 hours of the humidity resistance test under the conditions of 60 ° C. and 95% RH, and it was found that there was almost no change and the humidity resistance was excellent. Also, S
EM and XMA analysis showed that the powder had an average particle size of 0.20
It was found to have a uniform composition in μm.
【００７４】実施例５ まず、塩化インジウム４水和物６２３ｇと酢酸亜鉛２水
和物８２ｇとを１リットルのメトキシエタノールに溶解
させて、インジウム塩と亜鉛塩とが溶解した溶液を調製
した。また、しゅう酸２水和物４９４ｇを５リットルの
メトキシエタノールに溶解させて、しゅう酸水溶液を調
製した。Example 5 First, 623 g of indium chloride tetrahydrate and 82 g of zinc acetate dihydrate were dissolved in 1 liter of methoxyethanol to prepare a solution in which an indium salt and a zinc salt were dissolved. Further, 494 g of oxalic acid dihydrate was dissolved in 5 liters of methoxyethanol to prepare an oxalic acid aqueous solution.
【００７５】これらの溶液を用いて、実施例４と同様に
粉末を調製した。但し、焼成温度は３５０℃とした。こ
の粉末も淡黄色であった。Powders were prepared in the same manner as in Example 4 using these solutions. However, the firing temperature was 350 ° C. This powder was also pale yellow.
【００７６】粉末のＸ線回折測定を実施例１と同様に行
ったところ、非晶質部分は８０％であり、実質的に非晶
質であることが確認された。また組成分析からＩｎとＺ
ｎの原子比［Ｉｎ／（Ｉｎ＋Ｚｎ）］＝０．８５であっ
た。さらに粉末の体積固体抵抗を測定したところ、４Ω
ｃｍであった。そして、この体積固体抵抗は、６０℃、
９５％ＲＨの条件での耐湿性試験１０００時間後にも６
Ωｃｍであり、ほとんど変化がなく、耐湿性に優れてい
ることがわかった。When the X-ray diffraction measurement of the powder was carried out in the same manner as in Example 1, it was confirmed that the amorphous portion was 80% and was substantially amorphous. Moreover, from the composition analysis, In and Z
The atomic ratio of n was [In / (In + Zn)] = 0.85. Furthermore, when the volume solid resistance of the powder was measured, it was 4Ω.
It was cm. And this volume solid resistance is 60 ° C,
Moisture resistance test under conditions of 95% RH 6 after 1000 hours
It was found to be excellent in moisture resistance, with almost no change.
【００７７】また、ＳＥＭとＸＭＡの分析によりこの粉
末は平均粒径０．１５μｍで均一な組成を持つことがわ
かった。Further, by SEM and XMA analysis, it was found that this powder had an average particle size of 0.15 μm and a uniform composition.
【００７８】実施例６ まず、硝酸インジウム６水和物６８２ｇと硝酸亜鉛６水
和物２４８ｇとナーセム錫１０８ｇを５リットルのイソ
プロパノールに溶解させて、インジウム塩と亜鉛塩と錫
塩とが溶解した溶液を調製した。また、しゅう酸２水和
物５３２ｇを５リットルのエタノールに溶解させて、し
ゅう酸水溶液を調製した。Example 6 First, a solution in which 682 g of indium nitrate hexahydrate, 248 g of zinc nitrate hexahydrate and 108 g of nasem tin were dissolved in 5 liters of isopropanol to dissolve indium salt, zinc salt and tin salt Was prepared. Also, 532 g of oxalic acid dihydrate was dissolved in 5 liters of ethanol to prepare an oxalic acid aqueous solution.
【００７９】これらの溶液を用いて、実施例４と同様に
粉末を調製した。この粉末も淡黄色であった。Powders were prepared in the same manner as in Example 4 using these solutions. This powder was also pale yellow.
【００８０】粉末のＸ線回折測定を行ったところ、非晶
質部分は９０％であり、実質的に非晶質であることが確
認された。また組成分析から、ＩｎとＺｎの原子比［Ｉ
ｎ／（Ｉｎ＋Ｚｎ）］＝０．６７であり、錫の含有量は
９原子％であった。When X-ray diffraction measurement of the powder was carried out, it was confirmed that the amorphous portion was 90% and was substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [I
n / (In + Zn)] = 0.67, and the tin content was 9 atom%.
【００８１】さらに粉末の体積固体抵抗を測定したとこ
ろ、４Ωｃｍであった。そして、この体積固体抵抗は、
６０℃、９５％ＲＨの条件での耐湿性試験１０００時間
後にも６Ωｃｍであり、ほとんど変化がなく、耐湿性に
優れていることがわかった。また、ＳＥＭとＸＭＡの分
析によりこの粉末は平均粒径０．１７μｍで均一な組成
を持つことがわかった。Further, the volume solid resistance of the powder was measured and found to be 4 Ωcm. And this volume solid resistance is
It was found that even after 1000 hours of humidity resistance test under conditions of 60 ° C. and 95% RH, it was 6 Ωcm, and there was almost no change, and the humidity resistance was excellent. Further, it was found by SEM and XMA analysis that this powder had a uniform composition with an average particle size of 0.17 μm.
【００８２】実施例７ まず、硝酸インジウム６水和物６１３ｇと硝酸亜鉛６水
和物２９８ｇとを５リットルのブタノールに溶解させ
て、インジウム塩と亜鉛塩とが溶解した溶液を調製し
た。また、しゅう酸２水和物４５１ｇを５リットルのブ
タノールに溶解させて、しゅう酸水溶液を調製した。Example 7 First, 613 g of indium nitrate hexahydrate and 298 g of zinc nitrate hexahydrate were dissolved in 5 liters of butanol to prepare a solution in which an indium salt and a zinc salt were dissolved. Further, 451 g of oxalic acid dihydrate was dissolved in 5 liters of butanol to prepare an oxalic acid aqueous solution.
【００８３】これらの溶液を用いて、実施例５と同様に
粉末を調製した。この粉末も淡黄色であった。Powders were prepared in the same manner as in Example 5 using these solutions. This powder was also pale yellow.
【００８４】粉末のＸ線回折測定を行ったところ、非晶
質部分は８０％であり、実質的に非晶質であることが確
認された。また組成分析から、ＩｎとＺｎの原子比［Ｉ
ｎ／（Ｉｎ＋Ｚｎ）］＝０．６０であった。When X-ray diffraction measurement of the powder was carried out, it was confirmed that the amorphous portion was 80% and was substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [I
n / (In + Zn)] = 0.60.
【００８５】さらに粉末の体積固体抵抗を測定したとこ
ろ、２０Ωｃｍであった。そして、この体積固体抵抗
は、６０℃、９５％ＲＨの条件での耐湿性試験１０００
時間後にも２２Ωｃｍであり、ほとんど変化がなく、耐
湿性に優れていることがわかった。Further, the volume solid resistance of the powder was measured and found to be 20 Ωcm. And this volume solid resistance is measured by the humidity resistance test 1000 under the conditions of 60 ° C. and 95% RH.
It was 22 Ωcm even after the lapse of time, and it was found that there was almost no change and the moisture resistance was excellent.
【００８６】また、ＳＥＭとＸＭＡの分析によりこの粉
末は平均粒径０．１９μｍで均一な組成を持つことがわ
かった。Further, by SEM and XMA analysis, it was found that this powder had an average particle size of 0.19 μm and a uniform composition.
【００８７】実施例８ まず、酢酸インジウム６水和物１０２ｇと酢酸亜鉛４２
ｇとを１４０ミリリットルのモノエタノールアミンと８
６０ミリリットルのエタノールの混合物に溶解させて、
溶液を調製した。Example 8 First, 102 g of indium acetate hexahydrate and zinc acetate 42
g and 140 ml of monoethanolamine and 8
Dissolve in a mixture of 60 ml of ethanol,
A solution was prepared.
【００８８】この溶液を、減圧下、８０℃で溶媒を除去
し、４００℃で１時間、焼成し、熱分解させた。次に、
粉末を真空中で２００℃、２時間還元処理したところ、
淡黄色の粉末を得た。The solution was pyrolyzed by removing the solvent at 80 ° C. under reduced pressure and baking at 400 ° C. for 1 hour. next,
When the powder was reduced in a vacuum at 200 ° C. for 2 hours,
A pale yellow powder was obtained.
【００８９】粉末のＸ線回折測定を行ったところ、非晶
質部分は８０％であり、実質的に非晶質であることが確
認された。また組成分析から、ＩｎとＺｎの原子比［Ｉ
ｎ／（Ｉｎ＋Ｚｎ）］＝０．７０であった。さらに粉末
の体積固体抵抗を測定したところ、７Ωｃｍであった。
そして、この体積固体抵抗は、６０℃、９５％ＲＨの条
件での耐湿性試験１０００時間後にも８Ωｃｍであり、
ほとんど変化がなく、耐湿性に優れていることがわかっ
た。When X-ray diffraction measurement of the powder was carried out, it was confirmed that the amorphous portion was 80% and was substantially amorphous. From the composition analysis, the atomic ratio of In and Zn [I
n / (In + Zn)] = 0.70. Further, the volume solid resistance of the powder was measured and found to be 7 Ωcm.
And this volume solid resistance is 8 Ωcm even after 1000 hours of the humidity resistance test under the conditions of 60 ° C. and 95% RH,
It was found that there was almost no change and the moisture resistance was excellent.
【００９０】また、ＳＥＭとＸＭＡの分析によりこの粉
末は平均粒径０．１５μｍで均一な組成を持つことがわ
かった。Further, it was found by SEM and XMA analysis that this powder had an average particle size of 0.15 μm and a uniform composition.
【００９１】[0091]
【発明の効果】本発明によれば、ＩＴＯ、ＡＴＯよりも
耐湿性に優れ、黒化しにくく、かつＩＴＯ、ＡＴＯと同
等の導電性を有する導電性材料およびその製造方法が提
供された。According to the present invention, there is provided a conductive material which is superior in moisture resistance to ITO and ATO, is less likely to be blackened, and has the same conductivity as ITO and ATO, and a method for producing the same.
Claims (7)
Ｉｎ／（Ｉｎ＋Ｚｎ）が０．１〜０．９である実質的に
非晶質の酸化物からなることを特徴とする導電性材料。1. A conductive material comprising In and Zn as a main component and a substantially amorphous oxide having an atomic ratio In / In / (In + Zn) of 0.1 to 0.9. material.
のみからなる請求項１に記載の導電性材料。2. The amorphous oxide is substantially In and Zn.
The conductive material according to claim 1, which is composed of only.
の他に正三価以上の原子価を有する第３の元素の少なく
とも１種を、全第３元素の原子比（全第３元素／（Ｉｎ
＋Ｚｎ＋全第３元素））が２０原子％以下となる割合で
含むものである請求項１に記載の導電性材料。3. The substantially amorphous oxide is In and Zn.
In addition, at least one kind of the third element having a valence of positive trivalence or more is added to the atomic ratio of all the third elements (total third element / (In
The conductive material according to claim 1, wherein the content of + Zn + all third elements) is 20 atomic% or less.
質的に非晶質の酸化物を還元処理してなる導電性材料。4. A conductive material obtained by subjecting the substantially amorphous oxide according to claim 1 to a reduction treatment.
が４０Ω・ｃｍ以下である、請求項１〜４のいずれか一
項に記載の導電性材料。5. The conductive material according to claim 1, wherein the volume solid resistance of the substantially amorphous oxide is 40 Ω · cm or less.
い、これらの少なくとも１種を含む１種以上の溶液か
ら、沈澱形成剤により形成される沈澱を、固液分離し、
必要により焼成、還元処理して実質的に非晶質の酸化物
を得ることを特徴とする請求項１または２に記載の導電
性材料の製造方法。6. An indium compound and a zinc compound are used to perform solid-liquid separation of a precipitate formed by a precipitation forming agent from one or more solutions containing at least one of these compounds,
The method for producing a conductive material according to claim 1 or 2, wherein a substantially amorphous oxide is obtained by firing and reduction treatment if necessary.
三価以上の原子価を有する元素の少なくとも１種の化合
物を用い、これらの少なくとも１種を含む１種以上の溶
液から、沈澱形成剤により形成される沈澱を、固液分離
し、必要により、焼成、還元処理して実質的に非晶質の
酸化物を得ることを特徴とする請求項３に記載の導電性
材料の製造方法。7. A precipitation-forming agent is formed from at least one compound of an indium compound, a zinc compound and an element having a valence of positive trivalence or more, and from at least one solution containing at least one of these compounds. The method for producing a conductive material according to claim 3, wherein the precipitate is subjected to solid-liquid separation, and if necessary, subjected to firing and reduction treatment to obtain a substantially amorphous oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31508693A JPH06234522A (en) | 1992-12-16 | 1993-12-15 | Electrically conductive material and its production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-336406 | 1992-12-16 | ||
| JP33640692 | 1992-12-16 | ||
| JP31508693A JPH06234522A (en) | 1992-12-16 | 1993-12-15 | Electrically conductive material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06234522A true JPH06234522A (en) | 1994-08-23 |
Family
ID=26568175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31508693A Withdrawn JPH06234522A (en) | 1992-12-16 | 1993-12-15 | Electrically conductive material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06234522A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0707320A1 (en) * | 1994-10-13 | 1996-04-17 | AT&T Corp. | Transparent conductors comprising zinc-indium-oxide and methods for making films |
| US6221520B1 (en) | 1996-07-26 | 2001-04-24 | Asahi Glass Company Ltd. | Transparent conductive film and process for forming a transparent electrode |
| WO2013039039A1 (en) | 2011-09-17 | 2013-03-21 | 日本化薬株式会社 | Heat ray shielding adhesive composition, heat ray shielding transparent adhesive sheet, and method for producing same |
| JP2014005165A (en) * | 2012-06-22 | 2014-01-16 | Solar Applied Materials Technology Corp | Indium gallium zinc oxide, production method and application thereof |
| WO2014061279A1 (en) | 2012-10-19 | 2014-04-24 | 日本化薬株式会社 | Heat-ray-shielding sheet |
-
1993
- 1993-12-15 JP JP31508693A patent/JPH06234522A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0707320A1 (en) * | 1994-10-13 | 1996-04-17 | AT&T Corp. | Transparent conductors comprising zinc-indium-oxide and methods for making films |
| US6221520B1 (en) | 1996-07-26 | 2001-04-24 | Asahi Glass Company Ltd. | Transparent conductive film and process for forming a transparent electrode |
| US6465117B2 (en) | 1996-07-26 | 2002-10-15 | Asahi Glass Company Ltd. | Transparent conductive film and process for forming a transparent electrode |
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