JPS59199530A - Electrically conductive titanium oxide powder of low oxidation state and production thereof - Google Patents

Electrically conductive titanium oxide powder of low oxidation state and production thereof

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Publication number
JPS59199530A
JPS59199530A JP7203283A JP7203283A JPS59199530A JP S59199530 A JPS59199530 A JP S59199530A JP 7203283 A JP7203283 A JP 7203283A JP 7203283 A JP7203283 A JP 7203283A JP S59199530 A JPS59199530 A JP S59199530A
Authority
JP
Japan
Prior art keywords
titanium oxide
oxide powder
powder
titanium
conductive
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
JP7203283A
Other languages
Japanese (ja)
Inventor
Masashi Sakamoto
坂本 正志
Haruo Okuda
奥田 晴夫
Hideo Takahashi
英雄 高橋
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.)
Ishihara Sangyo Kaisha Ltd
Original Assignee
Ishihara Sangyo Kaisha Ltd
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Publication date
Application filed by Ishihara Sangyo Kaisha Ltd filed Critical Ishihara Sangyo Kaisha Ltd
Priority to JP7203283A priority Critical patent/JPS59199530A/en
Publication of JPS59199530A publication Critical patent/JPS59199530A/en
Pending legal-status Critical Current

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  • Conductive Materials (AREA)

Abstract

PURPOSE:Electrically conductive titanium oxide powder of low oxidation state, having a specified composition, specific resistance and average particle diameter and improved dispersibility in a base material and useful as an electric conductivity imparting agent. CONSTITUTION:Electrically conductive titanium oxide powder of low oxidation state, expressed by the formula TiOx (x is 1.5-1.9), and having <=100OMEGAcm specific resistance and 0.1-1mu average particle diameter. The above-mentioned titanium oxide powder is formed by treating a mixture of (A) titanium dioxide, e.g. a powdery material obtained by decomposing titanium tetrachloride oxidatively in the vapor phase, with (B) a metallic titanium powder having about <=100 mesh particle size at (2.4:1)-(12:1) molar ratio at about 800-1,000 deg.C in an inert atmosphere for 2-5hr, allowing the resultant powdery product to cool to 100 deg.C or below, and pulverizing the resultant cooled product into fine powder.

Description

【発明の詳細な説明】 本発明は、導電性イτj与拐として有用な導電性低次酸
化チタン粉末及びその製造方法に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a conductive low-order titanium oxide powder useful as a conductive material and a method for producing the same.

ニー、酸化チタンは、紫外線照射又は高温に加熱するこ
とにより、低次酸化物を生成し、このものは灰黒色を帯
び易く、電気伝導度や磁化率か増加することが知られて
いる。近時、この低次酸化チタンの着色性に注目して黒
色顔料としての利用、特に皮膚安全性が高いところから
化粧料への適用が提案されている。
It is known that when titanium oxide is irradiated with ultraviolet rays or heated to high temperatures, it produces lower-order oxides, which tend to take on a grayish-black color and whose electrical conductivity and magnetic susceptibility increase. Recently, attention has been focused on the coloring properties of this low-order titanium oxide, and its use as a black pigment has been proposed, particularly for its application in cosmetics due to its high skin safety.

一方、低次酸化チタンを電子伝導型の導電性(;Iり一
祠として利用をはかることも注目されているか、その実
用化にあたっては解決を要する問題点が少なくない。例
えば゛前記黒色顔料用の低次酸化チタンを導電性付与相
として適用する場合にあっては、このものを高着色力の
ものとするために還元度を比較的大きくする必要がある
ところから還元反応時に粒子の粗大化や粒子焼結が起り
易い。このような前記粗大粒子を含む低次酸化チタン粉
末は、種々の導電性付与基材に対する分散性が良好でな
く、このため十分な導電性付与効果かもたらされないな
どその解決が希求されている。
On the other hand, the use of low-order titanium oxide as an electronically conductive material is attracting attention, and there are many problems that need to be solved for its practical use. When applying low-order titanium oxide as a conductivity-imparting phase, it is necessary to increase the degree of reduction to give it high coloring power, which causes particles to become coarse during the reduction reaction. Low-order titanium oxide powder containing such coarse particles does not have good dispersibility in various conductivity-imparting substrates, and therefore does not provide a sufficient conductivity-imparting effect. A solution is desired.

本発明は、低次酸化チタンのT1:0の割合、比抵抗及
び平均粒子径を特定の範囲に満足せしめることによって
、前記の問題点を11+?決し得ることの知見にもとづ
くものであって、すなわち、本発明の第一は、一般式T
i0x(但し×は酸化度)においてXカ弓、5〜1.9
で示される組成を有し、比抵抗が1. (l OΩcm
以下でかつ平均粒径が0.1〜1μであることを特徴と
する導電性低次酸化チタン粉末であり、また本発明の第
二は二酸化チタンと金属チタンとをモル比h・2.、′
I:I−12:Iになるように混合し、該混合物を不活
性雰囲気中で加熱し、次いで粉砕して、一般式]” i
 (”) X(但しXは酸化度)において が1. 、
5 = 1. 、9で示される111成を有し、比抵抗
力弓(10ΩC1l+以下でがっ平均粒径が()、J〜
1μの粉状生成物を10ることを特徴とする導電性酸化
チタン粉末の製造方法である。
The present invention solves the above problems by satisfying the T1:0 ratio, specific resistance, and average particle diameter of low-order titanium oxide within specific ranges. The first aspect of the present invention is based on the knowledge that the general formula T
i0x (where x is the degree of oxidation), X power, 5 to 1.9
It has a composition shown by, and a specific resistance of 1. (l OΩcm
The second aspect of the present invention is a conductive low-order titanium oxide powder characterized in that the average particle size is 0.1 to 1 μm, and the second aspect of the present invention is a molar ratio of titanium dioxide and metal titanium of h.2. ,′
I:I-12:I, the mixture is heated in an inert atmosphere, and then ground to form the general formula]"i
('') At X (where X is the degree of oxidation), is 1.,
5 = 1. , 9, and the average grain size is (), J~
This is a method for producing conductive titanium oxide powder, which is characterized in that a powdery product of 1 μm is produced at 10 μm.

本発明の導電性低次酸化チタン粉末は、良好な導電性能
を有し、かつ種々の導電性イマ1与基材に対する分散性
が良好であり、また導電性能か環境湿度や長期間の使用
に対して安定であるなど優れた特長を有するものである
The conductive low-order titanium oxide powder of the present invention has good conductive performance and good dispersibility in various conductive materials, and also has good conductive performance in environmental humidity and long-term use. It has excellent features such as being stable against other metals.

本発明の導電性低次酸化チタン粉末は、Ti:○が特定
側合の組成よりなる化合物であって、かつ比抵抗と平均
粒子径か特定範囲にあるものよ1)実質的に構成されて
いるものであるか、(a)前記T1:○の割合は一般式
Ti0x(但しXは酸化度)において、Xは通常1.5
〜1.9、望ましくは1.6〜1.8、特に望ましくは
1 、6−1. 、7である。このような酸化度の範囲
で示される本発明の導電性低次酸化チタン粉末は、例え
ばl’io、Ti2O3、Ti3O5、Tia(L、T
i3O5、i” ; a Ot 1.1’ i 701
3、Tl8015、Ti、0.7、TiHOlgなどの
化合物か前記酸化度の範囲内において実質的に単−第1
1で存在する場合であっても、あるいは前記酸化度の範
囲内においてそれらの化合物か複数相共存している場合
であってもよい。(1〕)前記比抵抗は、通常1(H)
Ωcan以下、望ましくは5()9cm以下、特に望ま
しくは30ΩC+Il以下である。また、(c)平均粒
子径は、通常0.1〜1μであり、望ましくは0.2〜
0.7μ、1、テに望ましくは0.2〜0.5μである
。本発明において、前記の(a)、(1〕)及び(c)
が前記各範囲を−っでも満足しない場合には、導電性能
や分散性能などの特性について少なくとも部分的に欠け
るところがみられ望ましくない。
The conductive low-order titanium oxide powder of the present invention is a compound having a composition in which Ti:○ is on a specific side, and has a specific resistance and an average particle diameter within a specific range. (a) The ratio of T1:○ is the general formula Ti0x (where X is the degree of oxidation), where X is usually 1.5
~1.9, preferably 1.6-1.8, particularly preferably 1, 6-1. , 7. The conductive lower titanium oxide powder of the present invention having such an oxidation degree range is, for example, l'io, Ti2O3, Ti3O5, Tia (L, T
i3O5,i''; a Ot 1.1' i 701
3. Compounds such as Tl8015, Ti, 0.7, TiHOlg, etc. are substantially mono-primary within the range of the above-mentioned oxidation degree.
It may be the case that the compound exists in a single form, or the case that a plurality of these compounds coexist within the range of the above-mentioned oxidation degree. (1) The specific resistance is usually 1 (H)
Ωcan or less, preferably 5()9 cm or less, particularly preferably 30ΩC+Il or less. Further, (c) the average particle diameter is usually 0.1 to 1μ, preferably 0.2 to 1μ.
The thickness is preferably 0.7μ, 1μ, 0.2 to 0.5μ. In the present invention, the above (a), (1]) and (c)
If it does not satisfy each of the above-mentioned ranges, it is undesirable because properties such as conductive performance and dispersion performance are at least partially lacking.

本発明の導電性低次酸化チタン粉末を製造するには、先
ず(1)二酸化チタンと金属チタンとを、生成する低次
酸化チタン化合物のTに〇の割合、加熱処理条件などに
応じて所定のモル比で混合する。前記二酸化チタンと金
属チタンの混合モル比は、通常2.4:1〜12:1、
望ましくは3:1〜6:1、特に望ホしくは3.4:1
〜4:1の範囲である。
In order to produce the conductive low-order titanium oxide powder of the present invention, first, (1) titanium dioxide and metallic titanium are mixed in a predetermined manner according to the ratio of 〇 to T of the low-order titanium oxide compound to be produced, heat treatment conditions, etc. Mix in a molar ratio of The mixing molar ratio of the titanium dioxide and metal titanium is usually 2.4:1 to 12:1,
Preferably 3:1 to 6:1, particularly preferably 3.4:1
~4:1 range.

前記の金属チタンと混合する原料用二酸化チタンとしで
は種々の製法によるものを使用し得るが、例えば次のち
のを挙けることがととる。(a)四塩化チタンを気相酸
化分解してイ:)られる二酸化チタン粉状物、(1〕)
硫酸チタニル溶液や四塩化チタン溶液を必要に応し核形
成用種子の存剤下に加水分解して得られる水和二酸化チ
タンの沈殿に、必要に応しアルカリ性化合物を添加して
中和処理したり、例えば−塩基酸、その塩などの種々の
解膠剤を用いて解膠処理したりして、前記沈殿に吸蔵さ
れている硫酸根や塩素根を脱離して沈殿の凝集をほぐし
た後、550〜700℃で予備焼成してイ11られる二
酸化チタン粉末などを使用することがでべろ。なお、場
合によっては、前記水和二酸化チタンの沈殿に金属チタ
ン粉末を直接混合することもできる。
The raw material titanium dioxide to be mixed with the titanium metal described above can be produced by various methods, and examples include the following. (a) Titanium dioxide powder produced by vapor phase oxidative decomposition of titanium tetrachloride (1)
If necessary, an alkaline compound is added to the precipitate of hydrated titanium dioxide obtained by hydrolyzing a titanyl sulfate solution or a titanium tetrachloride solution in the presence of seeds for nucleation to neutralize it. After removing the sulfuric acid groups and chlorine groups occluded in the precipitate and loosening the agglomeration of the precipitate, It is possible to use titanium dioxide powder which is pre-calcined at 550 to 700°C. In some cases, metallic titanium powder can also be directly mixed into the precipitate of hydrated titanium dioxide.

また、還元反応の際の粒子成長や焼結を抑制したり、生
成物の導電性を高めたりするために、必要に応じ、種々
の焼成処理補助剤、例えばリン、アルカリ金属、アルカ
リ土類金属、アルミニウム、珪素、亜鉛、ニオブ、タン
グステン、タンタルなどの化合物を添加処理することも
で外る。
In addition, in order to suppress particle growth and sintering during the reduction reaction and to increase the conductivity of the product, various calcination processing aids such as phosphorus, alkali metals, alkaline earth metals, etc. may be added as necessary. It is also possible to add compounds such as aluminum, silicon, zinc, niobium, tungsten, and tantalum.

I)η記補助剤の添加量は、二酸化チタンと金属チタン
との混合割合、加熱処理条件によって異なり一層に言え
ないが、ニー酸化チタンの重量基阜に則して、酸化物換
算で通常0.1〜0.5%である。
I) The amount of the auxiliary agent described in η varies depending on the mixing ratio of titanium dioxide and metal titanium, and the heat treatment conditions, but it is difficult to say more, but it is usually 0 in terms of oxide based on the weight of di-titanium oxide. .1 to 0.5%.

本発明方法において前記のように水和二酸化チタンの沈
殿を予備焼成したものを使用したり、還元反応の際に焼
成補助剤を使用したりする場合には、粒子成長や粒子焼
結を抑制することかでき、また比較的低温で還元反応を
行なうことかできるために、分散性や導電性能の一層望
ましい微細粒子の導電性低次酸化チタン粉末を得ること
かできる。
In the method of the present invention, when precalcined hydrated titanium dioxide precipitates are used as described above, or when a calcination aid is used during the reduction reaction, particle growth and particle sintering may be suppressed. Furthermore, since the reduction reaction can be carried out at a relatively low temperature, it is possible to obtain fine particles of conductive low-order titanium oxide powder with more desirable dispersibility and conductivity.

本願発明方法において金属チタン粉末は、微粉状のもの
でも、粉状のものでもいづれのものも使用できるか、粒
度は通常100メンシユ以下、望ましくは200メツシ
ユ以下、特に望ましくは350メツシユ以下である。
In the method of the present invention, the metallic titanium powder may be either fine powder or powder, and the particle size is usually 100 mesh or less, preferably 200 mesh or less, and particularly preferably 350 mesh or less.

次いで(2)、前記(1)で得られ、た酸化チタンと金
属チタンとの混合物の加熱処理は、例えば窒素、アルゴ
ン、ヘリウムなどの気流による不活性雰囲気中で、通常
800〜1.000°C望ましくは850〜900℃で
おこなう。加熱時間は、加熱温度、原料の混合割合、原
料の粒度などにより異なり一4既に言えないが通常2〜
5時間である。前記加熱処理は、種々の型式の加熱炉を
使用して行なうことかて外るが、工業的には回転炉中で
窒素気流下でおこなうのか望ましい。得られた粉状生成
物は、非酸化性雰囲気中で1()0℃以下望ましくは常
温まで放令し、次いで乾式法又は湿式法或はそれらを組
合せて微粉砕して本発明の導電性低次酸化チタン粉末の
製品とする。
Next, (2), the mixture of titanium oxide and metal titanium obtained in the above (1) is heated at a temperature of usually 800 to 1,000° in an inert atmosphere using a gas flow of nitrogen, argon, helium, etc. C: Desirably carried out at 850 to 900°C. The heating time varies depending on the heating temperature, the mixing ratio of raw materials, the particle size of the raw materials, etc.It is difficult to say, but it is usually 2~
It is 5 hours. The heat treatment may be carried out using various types of heating furnaces, but from an industrial perspective it is preferable to carry out the heat treatment in a rotary furnace under a nitrogen stream. The obtained powdered product is allowed to stand at 1()0°C or lower, preferably at room temperature, in a non-oxidizing atmosphere, and then pulverized by a dry method, a wet method, or a combination thereof to obtain the conductive material of the present invention. The product is made of low titanium oxide powder.

実施例1 硫酸法によって製造されたアナタース型二酸化チタン粉
末(平均粒径0.15μ)に、金属チタン粉末(粒度3
25メツシュ全通品、純)999 、1重量%)を、モ
ル比で4=1の割合で均・混合し、この混合物を同転炉
に装入し、窒素ガス気流の不活性雰囲気中で85 (、
’l ”(’、で3時間加熱し、次いで初られた粉状生
成物を同雰囲気中で70°Cまで冷却し、さらに大気中
で常温まで放冷した。しがる後このものをサンドミルで
粉砕後次いでパルベライザーで粉砕して本発明の導電性
低次酸化チタン粉末を得た。
Example 1 Metallic titanium powder (particle size 3
25 mesh (all products, pure) 999, 1% by weight) were homogenized and mixed at a molar ratio of 4=1, and this mixture was charged into the converter and heated in an inert atmosphere of nitrogen gas flow. 85 (,
The powdered product was heated for 3 hours at 'l''('), then cooled to 70°C in the same atmosphere, and then allowed to cool to room temperature in the air. The powder was pulverized with a pulverizer and then pulverized with a pulverizer to obtain the conductive low-order titanium oxide powder of the present invention.

実施例2 実施例1において、二酸化チタンとして塩素法によって
製造されたルチル型二酸化チタン粉末(平均粒子径0.
26μ)を使用し、≦Joo’cで3時間加熱したこと
以外は、同側の場合と同様の方法で処理して本発明の導
電性低次酸化チタン粉末をイ1jた。
Example 2 In Example 1, rutile-type titanium dioxide powder (average particle size 0.
The conductive low-order titanium oxide powder of the present invention was prepared in the same manner as in the case of the same side, except that 26μ) was used and heated for 3 hours at ≦Joo'c.

実施例3〜5・1 実施例2において、二酸化チタンと金属チタンとの混合
割合を表1に示すモル比に代えたこと以外は、同側の場
合と同様の方法で処理して本発明の導電性低次酸化チタ
ン粉末を得た。
Examples 3 to 5/1 In Example 2, except that the mixing ratio of titanium dioxide and metal titanium was changed to the molar ratio shown in Table 1, the treatment of the present invention was carried out in the same manner as in the case of the same side. Conductive low-order titanium oxide powder was obtained.

表1 比較例 実施例2において、二酸化チタンと金属チタンとをモル
比で2:1の割合で混合したこと以外は、同側の場合と
同様の方法で処理した。
Table 1 Comparative Example In Example 2, the treatment was carried out in the same manner as on the same side, except that titanium dioxide and metal titanium were mixed at a molar ratio of 2:1.

実施例5 硫酸チタニル溶液を核形成用種子の存在下で加熱加水分
解しこイ(1−られな水和二酸化チタン(解膠粒子径約
500 A )に、焼成補助剤としてリン酸、水酸化カ
リウム及び炭酸すトリウムをそれぞれ酸性物として0.
2%添加しくいづれち1’ i 02重量基準に刻して
)、このものを650 ’Cで4時間予備焼成した(開
放系)。得られた前記焼成物を実施例1における二酸化
チタン原料に代えて使用したこと以外は、同側の場合と
同様の方法で処理して本発明の導電性酸化チタン粉末を
1(また。
Example 5 A titanyl sulfate solution was heated and hydrolyzed in the presence of seeds for nucleation. Potassium and thorium carbonate were each used as acidic substances with 0.
The product was pre-calcined at 650'C for 4 hours (open system). The conductive titanium oxide powder of the present invention was prepared in the same manner as in Example 1, except that the obtained fired product was used in place of the titanium dioxide raw material in Example 1.

前記の実施例及び比較例で得られた低次酸化チタン粉末
について、組成、比抵抗、粒子径、分散性をそれぞれ次
記のようにして測定した。その結果を表2に示す。
The composition, resistivity, particle size, and dispersibility of the low titanium oxide powders obtained in the Examples and Comparative Examples described above were measured as follows. The results are shown in Table 2.

表2 表2の結果から明らかなように、本発明の導電性低次酸
化チタン粉末は、導電性と分散性とがともに良好なもの
であった。
Table 2 As is clear from the results in Table 2, the conductive low-order titanium oxide powder of the present invention had good conductivity and good dispersibility.

なお表2の比抵抗は、温度20℃で相対湿度50%で測
定したものであるか、本発明の実施例1〜5の低次酸化
チタン粉末試料について、相対湿度90%の雰囲気下で
一定期間放置後測定したところ、いづれのものも湿度変
化にj=Jしてはとんと影響はみられなかった。
The specific resistance in Table 2 was measured at a temperature of 20°C and a relative humidity of 50%, or was measured at a constant temperature of 90% relative humidity for the low titanium oxide powder samples of Examples 1 to 5 of the present invention. When measured after being left for a period of time, no effect was observed on any of the samples when j=J.

糾 成 : 試料粉末におけるT10Xの×(酸化度)
の値は、化学分析により求めた。なお試料粉末のX線回
折をおこなったところ、いっれのものも低次酸化チタン
結晶物であることがみとめられた。
Compilation: × (degree of oxidation) of T10X in sample powder
The value was determined by chemical analysis. When the sample powders were subjected to X-ray diffraction, it was found that all of them were low-order titanium oxide crystals.

比抵抗 : 試料粉末を100 K B/ cm”の圧
力で成型して円型圧粉体(直径18 +n+n、厚3 
nun )とし、その直流抵抗を測定した。
Specific resistance: The sample powder was molded at a pressure of 100 KB/cm" to form a circular powder compact (diameter 18 + n + n, thickness 3
nun), and its DC resistance was measured.

粒子径 : 電子顕微鏡写真法により平均粒子径を測定
した。
Particle size: Average particle size was measured by electron microphotography.

分散性 : 試料粉末をメラミンアルキッドa4脂ワニ
スに混合しく顔料容積濃度20%)、混合物を鋼板パネ
ルに塗布し、乾燥塗膜(膜厚46μ)の光沢度(GO’
−60°)を測定し、分散性の指標とし、下記のA −
Dの四段階表示とした。(光沢度が高いほど分散性が良
好)A:分散性が非常に優れている B:分散性が優れ
ている C:分散性がやや劣るD二分散性が非常に劣る
を表わす、。
Dispersibility: The sample powder was mixed with melamine alkyd A4 fat varnish (pigment volume concentration 20%), the mixture was applied to a steel plate panel, and the glossiness (GO'
-60°) was measured and used as an index of dispersibility, and the following A -
D is displayed in four stages. (The higher the gloss, the better the dispersibility) A: Very good dispersibility B: Excellent dispersibility C: Slightly poor dispersibility D Very poor dispersibility.

111j記の特長を有する本発明の導電性低次酸化チタ
ン粉末は、導電性(=I与祠として広く種々の分野の利
用に好適なものである。例えはプラスチックス成型品や
フィルム、繊m、磁気テープ、塗料などの帯電防止剤と
して、さらに電子写真、静電記録なとの記録H料の支持
体用導電性イ」4材として有用なものである。その具体
例の二、三を挙げる。実施例1の導電性低次酸化チタン
粉末を、塩ビ樹脂フンパウンド100重量部に対し、3
0重量部練込み厚さ0.6mmのシートを成形しtこ。
The conductive low-order titanium oxide powder of the present invention having the characteristics described in Section 111j is suitable for use in a wide variety of fields as a conductive (=I) material.For example, it is suitable for use in a wide variety of fields. It is useful as an antistatic agent for magnetic tapes, paints, etc., and as a conductive material for supports of recording materials such as electrophotography and electrostatic recording. The conductive low-order titanium oxide powder of Example 1 was added in an amount of 3 parts by weight to 100 parts by weight of PVC resin powder.
0 parts by weight was kneaded into a sheet with a thickness of 0.6 mm.

このシートの比抵抗は1.6X107Ωcmであり、防
塵性床材用として十分な帯電防止効果が認められ、従来
の電子伝導型の導電性酸化物の場合に比べて勝るとも劣
らないものであった。また実施例1の導電性低次酸化チ
タン粉末をバインダーに分散させたものを支持体紙上に
塗布した。塗布面の表面抵抗は1..9X107Ωであ
り、この」−に二―酸化チタンを主剤とする感光層を設
けた電子写真感光4・4料は、導電性酸化亜鉛を支持体
に使用する場合よりも画像の連続階調性や鮮明性がとも
に優れたものであった。さらに実施例1の導電性低次酸
化チタン粉末を、磁性酸化鉄粉末(フバルト被着γ−F
e203)とともにバインダーに分散させたもの(該低
次酸化チタンを該酸化鉄重量基準に対して2%、充填固
形分容積濃度50%)をポリxステルテープ」二に塗布
した。この塗布テープは、表面抵抗が3.2X1.09
Ωで、また吸光度0.295/μであり、ビデオ用磁気
テープとしてカーボンブラックを使用する場合に比べで
、磁気特性が良好でかつ帯電防止性及び陰ぺい性とも勝
るとも劣らないものであった。
The specific resistance of this sheet was 1.6 x 107 Ωcm, and it was found to have a sufficient antistatic effect for dust-proof flooring, and was comparable to that of conventional electron-conducting conductive oxides. . Further, the conductive low-order titanium oxide powder of Example 1 dispersed in a binder was applied onto a support paper. The surface resistance of the coated surface is 1. .. 9 x 107 Ω, and the electrophotographic photosensitive material 4.4, which has a photosensitive layer based on titanium dioxide, has better continuous gradation and better image continuity than when conductive zinc oxide is used as a support. Both images were excellent in clarity. Further, the conductive low-order titanium oxide powder of Example 1 was mixed with magnetic iron oxide powder (fuwart-coated γ-F
e203) in a binder (the lower titanium oxide was 2% based on the weight of the iron oxide, and the volume concentration of the filled solids was 50%) was applied to a polyx stell tape. This coating tape has a surface resistance of 3.2X1.09
Ω and an absorbance of 0.295/μ, the magnetic properties were better and the antistatic properties and opacities were comparable to those when carbon black was used as a video magnetic tape. .

特許出願人 石原産業株式会社 手続補正椙、(方式) %式%【0 〕、事件の表示  昭和58年特許願第72032号2
、発明の名称  導電性低次酸化チタン粉末及びその製
造方法3、補正をする者 事件との関係  特許出願人 1]−所   (〒550)大阪市西区江戸堀−下目3
番22号・1.補正σU令のIヨ(=I   昭和58
年7月26日(発送日)5、補正のス・]象  願書及
び明細書全文6、補正の内容  別紙の通り(浄書した
ものであり記載内容に変更なし) 手続補正書 昭和58年8り&4日 特許庁長官 若  杉  和  夫   殿1、事件の
表示  昭和58年特許願第72032号2、 発明の
名称  導電性低次酸化チタン粉末及びその製造方法3
、補正をする者 事件との関係  特許出願人 住所   (〒550)大阪市西区江戸堀−丁目3番2
2号11、補正命令の日刊  自 発 明     細     書 1、発明の名称  導電性低次酸化チタン粉末及びその
製造方法 2、’l、旨′[5、+’を求の範囲 (1)−・般式Ti0x(但しXは酸化度)においてX
が1.5〜1.()で示される組成を有し、比抵抗が1
oOΩcm以下でかつ平均粒径が0.1〜1μであるこ
とを特徴とする導電性低次酸化チタン粉末。
Patent Applicant: Ishihara Sangyo Co., Ltd. Procedural Amendments, (Method) % Formula % [0], Case Indication: 1982 Patent Application No. 72032 2
, Title of the invention Conductive low-order titanium oxide powder and its manufacturing method 3, Relationship with the case of the person making the amendment Patent applicant 1] - Location (550) Edobori, Nishi-ku, Osaka-shi, Shimome 3
No. 22・1. Correction σU Order Iyo (=I 1972
July 26, 2016 (shipment date) 5, Amendments Full text of the application and specification 6, Contents of the amendments As attached (as it has been transcribed and there is no change in the written content) Procedural amendments 1980, 8 & 4th Patent Office Commissioner Kazuo Wakasugi1, Case description 1982 Patent Application No. 720322, Title of invention Electrically conductive low-order titanium oxide powder and its manufacturing method 3
, Relationship with the person making the amendment Patent applicant address (3-2 Edobori-chome, Nishi-ku, Osaka 550)
2 No. 11, Daily Amendment Order Self Invention Specification 1, Title of the Invention Conductive low-order titanium oxide powder and method for producing the same 2, Scope (1) of seeking 'l, effect' [5, +' In the formula Ti0x (where X is the degree of oxidation),
is 1.5-1. It has the composition shown in parentheses and has a specific resistance of 1
1. A conductive low-order titanium oxide powder characterized by having a particle diameter of 0.0Ωcm or less and an average particle size of 0.1 to 1μ.

(2)二酸化チタンと金属チタンとをモル比が2.4:
1〜12:1になるように渭、合し、該混合物を不活性
雰囲気中で加熱処理し、次いで粉砕して、一般式Ti0
x(但しXは酸化度)においてXが1.5へ・1.9で
示される組成を有し、比抵抗が400Ωcm以下でかつ
平均粒径が0.1〜1μの粉状生成物を得ることを特徴
とする導電性低次酸化チタン粉末の製造方法。
(2) The molar ratio of titanium dioxide and metal titanium is 2.4:
1 to 12:1, the mixture was heat treated in an inert atmosphere, and then ground to give the general formula TiO
Obtain a powdery product having a composition where X is 1.5 to 1.9 in x (where X is the degree of oxidation), has a specific resistance of 400 Ωcm or less, and has an average particle size of 0.1 to 1 μm. A method for producing conductive low-order titanium oxide powder, characterized by:

3、発明の詳細な説明 本発明は、導電性付与祠として有用な導電性低次酸化チ
タン粉末及びその製造方法に関する。
3. Detailed Description of the Invention The present invention relates to a conductive low-order titanium oxide powder useful as a conductivity-imparting shrine and a method for producing the same.

二酸化チタンは、紫外線原則又は高温に加熱すること【
こより、低次酸化物を生成し、このものは灰黒色を帯び
易く、電気伝導度や磁化率が増加することが知られてい
る。近時、この低次酸化チタンの着色性に注1」して黒
色顔料としての利用、特に皮膚安全性が高いところから
化粧料、への適用か提案されている。
Titanium dioxide should be heated under ultraviolet rays or at high temperatures [
This produces lower-order oxides, which tend to take on a grayish-black color and are known to have increased electrical conductivity and magnetic susceptibility. Recently, it has been proposed to use low-order titanium oxide as a black pigment due to its coloring properties, particularly in cosmetics due to its high skin safety.

一方、低次酸化チタンを電子伝導型の導電性イτj与材
として利用をはかることも注目されているか、その実用
化にあたっては解決を要する問題点か少なくない。例え
ば前記黒色顔料用の低次酸化チタンを導電性イ」与ヰ4
として適用する場合にあっては、このものを高着色力の
ものとするために還元度を比較的大外くする必要かあ、
るところから還元反応時に粒子の粗大化や粒子焼結が起
り易い。このような前記粗大粒子を含む低次酸化チタン
粉末は、種々の導電性(=I与基利に対する分散性が良
好でなく、このため十分な導電性(=1与効果がもたら
されないなどその解決が希求されている。
On the other hand, the use of low-order titanium oxide as an electron conductive type conductive material τj is also attracting attention, and there are many problems that need to be solved before its practical application. For example, when the lower titanium oxide for the black pigment is given conductivity,
When used as a coloring agent, it is necessary to reduce the degree of reduction to a relatively high degree in order to obtain high coloring power.
Because of this, particle coarsening and particle sintering are likely to occur during the reduction reaction. The low-order titanium oxide powder containing such coarse particles does not have good dispersibility for various conductivity (=I) effects, and therefore does not have sufficient conductivity (=1) effects. A solution is desired.

本発明は、低次酸化チタンのT i:oの割合、比抵抗
及び平均粒子径を特定の範囲に満足せしめることによっ
て、i’+ij記の問題点を解決し得ることの知見にも
とづくものであって、すなわち、本発明の第一は、一般
式Ti0x(但しXは酸化度)においでXが1.5〜1
.9で示される組成を有し、比抵抗か1 (1(,1Ω
Cl+1以下でかつ平均粒径が0.1〜1μであること
を特徴とする導電性低次酸化チタン粉末であり、また本
発明の第二は二酸化チタンと金属チタンとをモル比か2
.=l:1〜12:1になるように混合し、該混合物を
不活性雰囲気中で加熱し、次いで粉砕して、一般式Ti
0x(但しXは酸化度)においてXカ弓、5〜1.9で
示される組成を有し、比抵抗がi (l 99cm以下
でかつ平均粒径が0.1・−・1μの粉状生成物を得る
ことを特徴とする導電性低次酸化チタン粉末の製造方法
である。
The present invention is based on the knowledge that the problems described in i'+ij can be solved by satisfying the T i:o ratio, specific resistance, and average particle diameter of low-order titanium oxide within specific ranges. That is, the first aspect of the present invention is that in the general formula Ti0x (where X is the degree of oxidation), X is 1.5 to 1.
.. It has a composition shown as 9, and has a specific resistance of 1 (1(,1Ω
It is a conductive low-order titanium oxide powder characterized by having Cl+1 or less and an average particle size of 0.1 to 1μ, and the second aspect of the present invention is titanium dioxide and metal titanium in a molar ratio of 2 to 2.
.. = l:1 to 12:1, the mixture is heated in an inert atmosphere, and then ground to obtain the general formula Ti
Powder-like powder having a composition expressed by 5 to 1.9 at 0x (where X is the degree of oxidation), a resistivity of 99cm or less, and an average particle size of 0.1 to 1μ. This is a method for producing a conductive low-order titanium oxide powder, which is characterized in that a product is obtained.

本発明の導電性低次酸化チタン粉末は、良好な導電性能
を有し、かつ種々の導電性付与基材に対する分散性か良
好であり、また導電性能が環境湿度や長期間の使用に対
して安定であるなど優れたb艮を有するものである。
The conductive low-order titanium oxide powder of the present invention has good conductivity and good dispersibility in various conductivity-imparting substrates, and has good conductivity against environmental humidity and long-term use. It has excellent properties such as stability.

本発明の導電性低次酸化チタン粉末は、Ti:Oが特定
割合の組成よりなる化合物であって、かつ比抵抗と平均
粒子径が特定範囲にあるものよ1)実質的に構成されて
いるものであるか、(a)前記”l’i:Oの割合は一
般式Ti0x(但し又は酸化度)において、又は通常1
.5〜1.9、望ましくは1.6〜1.8、特に望まし
くは1.6〜1.7て゛ある。このような酸化度の範囲
で示される本発明の導電性低次酸化チタン粉末は、例え
ばゴio、Tiz○2、Tl309、Ti4O7、T 
i 、05.1’ i G O11、]’ i 701
3、Tl8015、Ti90.。、1゛11゜01.な
どの化合物が前記酸化度の範囲内におし・て実質的に単
−相で存在する場合であっても、あるいは前記酸化度の
範囲内(二おいてそれらの化合物か複数相共存しで(・
る場合であってもよい。(IJ)前記比抵抗は、通常1
00ΩCτ0以下、望ましくは50Ωcm以下、特に望
ましくは30ΩCl1l以下である1、また、(c)平
均粒子径は、通常0.1〜1μであり、望ましくは0.
2〜0.7μ、特に望ましくは0.2〜0.5μである
。本発明において、前記の(a)、(b)及び(c)が
前記各範囲を一つでも714足しない場合には、導電性
能や分散性能などの特性につν・で少なくとも部分的に
欠けるところがみられ望ましく痕・。
The conductive low-order titanium oxide powder of the present invention is a compound consisting of Ti:O in a specific ratio, and has a specific resistance and an average particle size within a specific range. (a) The ratio of l'i:O is in the general formula Ti0x (however, the degree of oxidation), or usually 1
.. 5 to 1.9, preferably 1.6 to 1.8, particularly preferably 1.6 to 1.7. The conductive titanium oxide powder of the present invention having such an oxidation degree range includes, for example, Goio, Tiz○2, Tl309, Ti4O7, T
i , 05.1' i G O11, ]' i 701
3, Tl8015, Ti90. . , 1゛11゜01. Even if compounds such as are present in a substantially single phase within the range of the oxidation degree, or within the range of the oxidation degree (2), those compounds may coexist in multiple phases. (・
This may be the case. (IJ) The specific resistance is usually 1
00ΩCτ0 or less, preferably 50Ωcm or less, particularly preferably 30ΩCl1l or less, and (c) the average particle diameter is usually 0.1 to 1μ, preferably 0.
It is 2-0.7μ, particularly preferably 0.2-0.5μ. In the present invention, if the above-mentioned (a), (b), and (c) do not add at least 714 to each of the above-mentioned ranges, the characteristics such as conductive performance and dispersion performance are at least partially lacking in ν. However, there are visible marks.

本発明の導電性低次酸化チタン粉末を製造するには、先
ず(1)二酸化チタンと金属チタンとを、生成する低次
酸化チタン化合物のTi:Oの割合、加熱処理条件など
(こ応して所定のモル比で混合する。前記二酸化チタン
と金属チタンの混合モル比は、通常2.4:1〜12:
L望ましくは3:1〜6:1、特に望ましくは3.4:
1〜4:1の範囲である。
In order to produce the conductive low-order titanium oxide powder of the present invention, first, (1) titanium dioxide and metallic titanium are mixed, depending on the Ti:O ratio of the low-order titanium oxide compound to be produced, heat treatment conditions, etc. The mixing molar ratio of the titanium dioxide and metal titanium is usually 2.4:1 to 12:
L is preferably 3:1 to 6:1, particularly preferably 3.4:
It is in the range of 1 to 4:1.

前記の金属チタンと混合する原料用二酸化チタンとして
は種々の製法によるものを使用し得るか、例えば次のち
のを挙けることかときる。(、)四塩化チタンを気相酸
化分解してljられるニー酸化チタン粉状物、(1〕)
硫酸チタニル溶液や四塩化チタンlB液を必要に応じ核
形成用種子の存在下に加水分解して1υられる水和二酸
化チタンの沈殿に、必要に応しアルカリ性化合物を添加
して中和処理したり、例えば−・塩基酸、その塩などの
種々の解膠剤を用いて解膠処理したりして、前記沈殿に
吸蔵されている硫酸根や塩素根を脱硼1して沈殿の凝集
をほぐした後、550〜7(月)°Cで予備焼成して得
られる二酸化チタン粉末などを使用することかでbる。
The raw material titanium dioxide to be mixed with the titanium metal may be produced by various methods, including the following. (,) Titanium oxide powder produced by vapor phase oxidative decomposition of titanium tetrachloride, (1)
If necessary, a titanyl sulfate solution or a titanium tetrachloride IB solution is hydrolyzed in the presence of nucleation seeds to precipitate hydrated titanium dioxide, which is then neutralized by adding an alkaline compound as necessary. For example, by peptizing using various peptizing agents such as basic acids and their salts, the sulfate and chlorine groups occluded in the precipitate are removed and the agglomeration of the precipitate is loosened. After that, titanium dioxide powder obtained by pre-calcining at 550 to 7 (months) Celsius is used.

なお、場合によっては、前記水利二酸化チタンの沈殿に
金属チタン粉末を直接混合することもできる。
In some cases, metal titanium powder may be directly mixed into the precipitate of water-containing titanium dioxide.

また、還元反応の際の粒子成長や焼結を抑制したり、生
成物の導電性を高めたりするために、必要に応し、種々
の焼成処理補助剤、例えばリン、アルカリ金属、アルカ
リ土類金属、アルミニウノ1、珪素、亜鉛、二オフ、タ
ングステン、タンクルなどの化合物を添加処理すること
もでトる。
In addition, in order to suppress particle growth and sintering during the reduction reaction and to increase the conductivity of the product, various calcination processing aids, such as phosphorus, alkali metals, alkaline earth It is also possible to add compounds such as metals, aluminum Uno 1, silicon, zinc, diopter, tungsten, and tankle.

1)1j記補助剤の添加量は、二酸化チタンと金属チタ
ンとの混合割合、加熱処理条件によって異なり一層に言
えないか、二酸化チタンの重量基準に対して、酸化物換
算で通常0.1〜0.5%である。
1) The amount of the auxiliary agent described in 1j varies depending on the mixing ratio of titanium dioxide and titanium metal and the heat treatment conditions, and is usually 0.1 to 0.1 to oxide based on the weight of titanium dioxide. It is 0.5%.

本発明方法において前記のように水和二酸化チタンの沈
殿を予備焼成したものを使用したり、還元反応の際に焼
成補助剤を使用したりする場合には、粒子成長や粒子焼
結を抑制することかでき、また比較的低温で還元反応を
行なうことかで外るためしこ、分散性や導電性能の一層
望ましい微細粒子の導電性低次酸化チタン粉末をイυ−
ることかできる。
In the method of the present invention, when precalcined hydrated titanium dioxide precipitates are used as described above, or when a calcination aid is used during the reduction reaction, particle growth and particle sintering may be suppressed. In addition, it is possible to obtain fine particles of conductive low-order titanium oxide powder with more desirable dispersibility and conductive performance by performing a reduction reaction at a relatively low temperature.
I can do that.

本願発明方法において金属チタン粉末、は、微粉状のも
のでも、粉状のものでもいづれのものも使用でとるか、
粒度は通常]00メンシュ以下、望ましくは200メン
シユ以下、特に望ましくは350メツシユリ、下である
In the method of the present invention, the metallic titanium powder may be either fine powder or powder.
The particle size is usually below 00 mesh, preferably below 200 mesh, particularly preferably below 350 mesh.

次いで(2)、前記(1)で得られた酸化チタンと金属
チタンとの混合物の加熱処理は、例えば窒素、アルゴン
、ヘリウムなどの気流による不活性雰囲気中で、通常8
00〜1 、000 ”C望ましくは850〜900℃
でおこなう。加熱時間は、加熱温度、原料の混合割合、
原料の粒度などにより異なり一層に言えな゛いが通常2
〜5時間である。前記加熱処理は、種々の型式の加熱炉
を使用して行なうことかでとるか、工業的には回転炉中
で窒素気流下でおこなうのか望ましい。得られた粉状生
成物は、非酸化性ず囲気中で100°C以下望ましくは
常温主で放冷し、次いで乾式法又は/+++!式法或は
それらを組合せて微粉砕して本発明の導電性低次酸化チ
タン粉末の製品とする。
Next (2), the mixture of titanium oxide and metal titanium obtained in the above (1) is heat-treated in an inert atmosphere using a gas flow of nitrogen, argon, helium, etc., usually for 8 hours.
00~1,000''C desirably 850~900℃
Do it with The heating time depends on the heating temperature, the mixing ratio of raw materials,
It is difficult to say because it depends on the particle size of the raw material, etc., but usually 2
~5 hours. The heat treatment is preferably carried out using various types of heating furnaces, or industrially preferably carried out in a rotary furnace under a nitrogen stream. The obtained powdered product is allowed to cool in a non-oxidizing atmosphere at a temperature below 100°C, preferably at room temperature, and then by a dry method or /+++! The conductive low-order titanium oxide powder product of the present invention is obtained by pulverizing using a formula method or a combination of these methods.

実施例1 硫酸法によって製造されたアナタース型二酸化チタン粉
末(平均粒径0..15μ)に、金属チタン粉末(粒度
325メツシュ令通品、純)z99.1重量%)を、モ
ル比で、−1: 1の劃でやで均一混合し、この混合物
を同転炉に装入腰窒素ガス気流の不活性雰囲気中で85
0°Cで;3時間加熱し、次いで得られた粉状生成物を
同雰囲気中で70’Cまで冷却し、さらに大気中で常温
まで放冷した。しかる後このものをサンドミルで粉砕後
次いでパルベライザーで粉砕して本発明の導電性低次酸
化チタン粉末を得た。
Example 1 Metallic titanium powder (particle size: 325 mesh, regular product, pure) 99.1% by weight) was added to anatase-type titanium dioxide powder (average particle size: 0.15μ) produced by the sulfuric acid method in a molar ratio. -1: Mix uniformly in the 1st bowl and charge this mixture into the same converter in an inert atmosphere of nitrogen gas flow at 85°C.
Heated at 0°C for 3 hours, then cooled the resulting powdered product to 70'C in the same atmosphere, and then allowed to cool to room temperature in the air. Thereafter, this material was pulverized with a sand mill and then pulverized with a pulverizer to obtain a conductive low-order titanium oxide powder of the present invention.

実施例2 実施例1において、二酸化チタンとして塩素法によって
製造されたルチル型二酸化チタン粉末(平均粒子径0.
26μ)を使用し、900 ℃で3時間加熱したこと以
外は、同例の場合と同様の方法で処理して本発明の導電
性低次酸化チタン粉末を代だ。
Example 2 In Example 1, rutile-type titanium dioxide powder (average particle size 0.
The conductive low-order titanium oxide powder of the present invention was treated in the same manner as in the same example, except that 26μ) was used and heated at 900° C. for 3 hours.

実施例3へ、4 実施例2において、二酸化チタンと金属チタンとの混合
割合を表1に示すモル比に代えたこと以外は、同例の場
合と同様の方法で処理して本発明の導電性低次酸化チタ
ン粉末をイ;また。
To Example 3, 4 The conductive material of the present invention was processed in the same manner as in Example 2, except that the mixing ratio of titanium dioxide and metal titanium was changed to the molar ratio shown in Table 1. It also contains low-grade titanium oxide powder.

表1 比較例 実施例2に33いて、二酸化チタンと金属チタンとをモ
ル比で2:1の割合で混合したこと以外は、同例の場合
と同様の方法で処理した。
Table 1 Comparative Example Example 33 was treated in the same manner as in Example 2, except that titanium dioxide and metallic titanium were mixed at a molar ratio of 2:1.

実施例5 硫酸チタニル)H液を核形成用種子の存在下で加熱加水
分解してイ:ノらizだ水和二酸化チタン(解膠粒子径
約5 (10A )に、焼成補助剤としてリン酸、水酸
化カリウム及び炭酸ナトリウ12をそれぞれ酸化物換算
で0.2%添加しくいづれもT i O2重量基準に対
して)、このものを650″Cで11時間予イイ;1焼
成したく開放系)。得られた前記焼成物を実施例]にお
ける二酸化チタン原料に代えて使用したこと以外は、同
例の場合と同様のノJ法て処理して本発明の導電性低次
酸化チタン粉末を得た。
Example 5 Titanyl sulfate) solution H was heated and hydrolyzed in the presence of seeds for nucleation to form hydrated titanium dioxide (peptized particle diameter of about 5 (10A)), and phosphoric acid was added as a calcination aid. , potassium hydroxide and sodium carbonate 12 were added in an amount of 0.2% (calculated as oxides, both based on T i O2 weight), and this was preheated at 650''C for 11 hours; ).The electrically conductive low-order titanium oxide powder of the present invention was produced by the same method as in Example 2, except that the obtained fired product was used in place of the titanium dioxide raw material in Example. Obtained.

111j記の実施例及び比較例で′利られた低次酸化チ
タン粉末について、組成、比抵抗、粒子径、分散性をそ
れぞれ人証のl ウにして測定した。その結果を表2に
示す。
The composition, specific resistance, particle size, and dispersibility of the low-order titanium oxide powders used in the Examples and Comparative Examples described in Section 111j were measured using human testimonials. The results are shown in Table 2.

表 2 表2の結果から明らかなように、本発明の導電性低次酸
化チタン粉末は、導電性と分散性とかともに良好なもの
であった。
Table 2 As is clear from the results in Table 2, the conductive low-order titanium oxide powder of the present invention had good conductivity and dispersibility.

なお表2の比抵抗は、温度20℃で相対湿度50%で測
定したものであるか、本発明の実施例1〜5の導電性低
次酸化チタン粉末試料についで、相対湿度!JO%の雰
囲気下で−・定期間放置後測定したところ、いづれのも
のも湿度変化に対してほとんど影響はみられなかった。
The specific resistance in Table 2 was measured at a temperature of 20° C. and a relative humidity of 50%, or was measured at a relative humidity of 50% relative humidity for the conductive low-order titanium oxide powder samples of Examples 1 to 5 of the present invention. When measured after being left for a certain period of time in an atmosphere of JO%, almost no effect on humidity changes was observed in either case.

組 成 : 試料粉末におけるT10Xの×(酸化度)
の値は、化学分析により求めた。、なお試料粉末のX線
回析をおこなったところ、いづれのちのも低次酸化チタ
ン結晶物であることがみとめられた。
Composition: × (degree of oxidation) of T10X in sample powder
The value was determined by chemical analysis. When the sample powders were subjected to X-ray diffraction, it was found that all of them were low-order titanium oxide crystals.

比抵抗 二 試料粉末を100 Kg/cqn2の圧力
で成型して円型圧粉体(直径1.8111111、厚3
IIII11)とし、その直流抵抗を測定した。
Specific resistance 2 The sample powder was molded at a pressure of 100 Kg/cqn2 to form a circular powder compact (diameter 1.8111111, thickness 3
III11), and its DC resistance was measured.

粒子径 : 電子顕微鏡写真法により平均粒子径を測定
した。
Particle size: Average particle size was measured by electron microphotography.

分散性 : 試料粉末をメラミンアルキッド樹脂ワニス
に混合−顔料容積濃度20%)、混合物を鋼板パネルに
塗布し、乾燥塗膜(膜厚46μ)の光沢度(60°−6
0°)を測定し、分散性の指標と腰下記のA−Dの四段
階表示とした。(光沢度が高いほど分散性が良好)A:
分散性が非常に優れている ■3二分散性か優れている
 C:分散性がやや劣る1〕二分散性が非常に劣るを表
わす。
Dispersibility: The sample powder was mixed with melamine alkyd resin varnish (pigment volume concentration 20%), the mixture was applied to a steel plate panel, and the gloss of the dry coating (film thickness 46μ) was (60°-6).
0°) was measured, and the dispersibility index and waist were expressed in four stages, A to D, as shown below. (The higher the gloss, the better the dispersibility) A:
Very good dispersibility ■3 Excellent bidispersity C: Slightly poor dispersibility 1) Very poor bidispersity.

+iii記の1、r長を有する本発明の導電性低次酸化
チタン粉末は、導電性酸化物4として広く種々の分野の
利用に好適なものである。例えはプラスチ/ラス成型品
やフィルム、繊維、磁気テープ、塗料などの帯電防止剤
として、さらに電子写真、静電記録などの記録祠料の支
持体用導電性(=j−5利として有用なものである。そ
の具体例の二、三を挙げる。実施例]の導電性低次酸化
チタン粉末を、塩ビ樹脂フンパウンド](月)車量部に
対し、30重量部練込み厚さ0 、6 +++mのシー
 l−を成形した。このシートの比抵抗は1..6Xi
O7ΩQ mであり、防塵性床利用として十分な・;1
シ電防止効果が認められ、従来の電子伝導型の導電性酸
化物の場合に比べて勝るとも劣らないものであった。ま
た実施例1の導電性低次酸化チタン粉末をバイングーに
分散させたものを支持体紙」二に塗布した。塗布面の表
面抵抗は]、、9X107Ωであり、この1−に二酸化
チタンを主剤とする感光ノで4を設けた電子写真感光H
料は、導電性酸化亜鉛を支持体に使用する場合よりも画
像の連続階調性や魚工明性がともに優れたものであっt
こ。さらに実施例1の導電性低次酸化チタン粉末を、磁
性酸化鉄粉末(コバルト被着χ−■:″c、O,)とと
もにバイングーに分散させたもの(該底吹酸化チタンを
該酸化鉄重量基樵に対して2%、充填固形分容積濃度5
0%)をポリエステルテープ上に塗布した。この塗布テ
ープは、表面抵抗が3.2X109Ωで、また吸光度(
1,295/μであり、ビデオ用磁気テープとしてカー
ボンフラッフを使用する場合に比べて、磁気特性が良好
でかつ帯電防止性及び陰ぺい性とも勝るとも劣らないも
のであった。
The conductive low-order titanium oxide powder of the present invention having a length of 1 and r in +iii is suitable for use as a conductive oxide 4 in a wide variety of fields. For example, it is useful as an antistatic agent for plastic/lath molded products, films, fibers, magnetic tapes, paints, etc., and as a conductive agent (=j-5) for supports for recording materials such as electrophotography and electrostatic recording. Here are a few specific examples: 30 parts by weight of the conductive low-order titanium oxide powder of Example] was kneaded to a weight of PVC resin (monthly) to a thickness of 0. A sheet l- of 6 +++m was molded.The specific resistance of this sheet was 1..6Xi
O7ΩQ m, which is sufficient for dust-proof floor use.;1
The anti-shock effect was observed, and was comparable to that of conventional electron-conducting conductive oxides. Further, the conductive low-order titanium oxide powder of Example 1 dispersed in bangu was coated on a support paper. The surface resistance of the coated surface is 9 x 107 Ω.
The material is superior in continuous gradation and brightness to images than when conductive zinc oxide is used as a support.
child. Further, the conductive low-order titanium oxide powder of Example 1 was dispersed together with the magnetic iron oxide powder (cobalt-coated 2% based on base wood, filling solids volume concentration 5
0%) was applied onto a polyester tape. This coating tape has a surface resistance of 3.2 x 109Ω and an absorbance (
1,295/μ, and the magnetic properties were better and the antistatic properties and opacities were comparable to those of the case where carbon fluff was used as a video magnetic tape.

特許出願人 石原産業株式会社Patent applicant: Ishihara Sangyo Co., Ltd.

Claims (2)

【特許請求の範囲】[Claims] (1) 一般式Ti0x(但しXは酸化度)において 
力弓、5〜〕、!□Jで示される組成を有し、比抵抗が
1()0ΩCnl以下でかつ平均粒径か0.1〜1μで
あることを特徴とする導電性低次酸化チタン粉末。
(1) In the general formula Ti0x (where X is the degree of oxidation)
Power bow, 5~],! An electrically conductive titanium oxide powder having a composition represented by □J, having a specific resistance of 1()0ΩCnl or less, and an average particle size of 0.1 to 1μ.
(2)二酸化チタンと金属チタンとをモル比が2.4:
1〜12:1になるように混合し、該混合物を不活性雰
囲気中で加熱処理し、次いで粉砕して、一般式Ti0x
(但しXは酸化度)において が1.5〜1.9で示さ
れる組成を有し、比抵抗力弓00Ωam以下でかつ平均
粒径か0.1〜1μの粉状生成物を得ることを特徴とす
る導電性酸化チタン粉末の製造方法。
(2) The molar ratio of titanium dioxide and metal titanium is 2.4:
1 to 12:1, the mixture was heat treated in an inert atmosphere, and then ground to give the general formula TiOx
(where X is the degree of oxidation) has a composition of 1.5 to 1.9, has a resistivity of 00 Ωam or less, and has an average particle size of 0.1 to 1μ. A method for producing characteristically conductive titanium oxide powder.
JP7203283A 1983-04-23 1983-04-23 Electrically conductive titanium oxide powder of low oxidation state and production thereof Pending JPS59199530A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7203283A JPS59199530A (en) 1983-04-23 1983-04-23 Electrically conductive titanium oxide powder of low oxidation state and production thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7203283A JPS59199530A (en) 1983-04-23 1983-04-23 Electrically conductive titanium oxide powder of low oxidation state and production thereof

Publications (1)

Publication Number Publication Date
JPS59199530A true JPS59199530A (en) 1984-11-12

Family

ID=13477659

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7203283A Pending JPS59199530A (en) 1983-04-23 1983-04-23 Electrically conductive titanium oxide powder of low oxidation state and production thereof

Country Status (1)

Country Link
JP (1) JPS59199530A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052786A1 (en) * 2002-12-09 2004-06-24 Tayca Corporation Titanium oxide particles having useful properties and method for production thereof
JP2019219475A (en) * 2018-06-19 2019-12-26 コニカミノルタ株式会社 Intermediate transfer body and image forming apparatus

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052786A1 (en) * 2002-12-09 2004-06-24 Tayca Corporation Titanium oxide particles having useful properties and method for production thereof
JPWO2004052786A1 (en) * 2002-12-09 2006-04-13 テイカ株式会社 Titanium oxide particles having beneficial properties and method for producing the same
JP4546834B2 (en) * 2002-12-09 2010-09-22 テイカ株式会社 Titanium oxide particles having beneficial properties and method for producing the same
JP2019219475A (en) * 2018-06-19 2019-12-26 コニカミノルタ株式会社 Intermediate transfer body and image forming apparatus

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