JP2612884B2 - Titanium oxynitride fiber and its manufacturing method - Google Patents
Titanium oxynitride fiber and its manufacturing methodInfo
- Publication number
- JP2612884B2 JP2612884B2 JP63039579A JP3957988A JP2612884B2 JP 2612884 B2 JP2612884 B2 JP 2612884B2 JP 63039579 A JP63039579 A JP 63039579A JP 3957988 A JP3957988 A JP 3957988A JP 2612884 B2 JP2612884 B2 JP 2612884B2
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- titanium oxide
- titanium oxynitride
- fibrous
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0821—Oxynitrides of metals, boron or silicon
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は繊維状酸窒化チタンとその製造方法に関す
る。The present invention relates to fibrous titanium oxynitride and a method for producing the same.
このものは補強性をもった導電性の繊維であり、プラ
スチック、特にエンジニアリングプラスチックやゴム、
紙、その他無機材料に添加し導電性を付与することが出
来、帯電防止材、発熱体、電波吸収体、静電記録層等に
用いられるばかりでなくプラスチックに添加した場合は
機械的性質例えば補強性、耐摩耗性、表面平滑性、加工
性、寸法安定性に優れる導電性プラスチック複合体が得
られる。This is a conductive fiber with reinforcement properties, plastics, especially engineering plastics and rubber,
Can be added to paper and other inorganic materials to impart conductivity, and used not only for antistatic materials, heating elements, radio wave absorbers, electrostatic recording layers, etc., but also for mechanical properties such as reinforcement when added to plastics A conductive plastic composite having excellent properties, abrasion resistance, surface smoothness, workability, and dimensional stability can be obtained.
更に加熱反応の程度によって青色、黒色、茶色等の種
々の色を呈するため顔料としての用途も考えられる。Further, since it exhibits various colors such as blue, black, and brown depending on the degree of the heating reaction, it may be used as a pigment.
（従来の技術と問題点） 導電性を示す繊維状の粉末としては、カーボン（炭素
繊維、ケッチェンブラック）、本発明者らが開発したチ
タン酸カリウムを還元した粉末（特開昭59−141425）、
チタン酸アルカリをカーボンで還元した粉末（特公昭62
−3767）及びチタン酸カリウムにアンチモンをドープし
た酸化スズをコーティングした粉末などが知られてい
る。カーボンやカーボンで還元したチタン酸カリウムは
表面が炭素質であるため、一般の無機フィラーに比べて
疎水性を示し、プラスチックに添加した場合、他の顔料
等となじみにくく、混合時の分散性、成形体での色別れ
や脱離が問題となる。また本発明者らが開発した六チタ
ン酸カリウムを還元した粉末については800℃を越える
還元では元の繊維が折れやすくなる。導電性物質をコー
ティングしたチタン酸カリウム繊維については導電性物
質と基体との密着性が問題とされる。更にチタン酸アル
カリ繊維を母材とした導電材はポリカーボネートや難燃
剤を添加したエンジニアリングプラスチックや半導体関
連の帯電防止用途のようなアルカリの混在をきらう用途
には使用出来ないという問題がある。(Conventional technology and problems) Examples of the fibrous powder exhibiting conductivity include carbon (carbon fiber, Ketjen black) and a powder obtained by reducing potassium titanate developed by the present inventors (Japanese Patent Application Laid-Open No. Sho 59-141425). ),
Powder obtained by reducing alkali titanate with carbon (Japanese Patent Publication No. Sho 62
-3767) and a powder coated with tin oxide obtained by doping antimony into potassium titanate. Since carbon and potassium titanate reduced with carbon have a carbonaceous surface, they show hydrophobicity compared to general inorganic fillers, and when added to plastic, are less compatible with other pigments and the like, dispersibility when mixed, Color separation and desorption in the molded body pose a problem. Also, with respect to the powder obtained by reducing the potassium hexatitanate developed by the present inventors, the original fiber is likely to be broken when the temperature exceeds 800 ° C. For potassium titanate fibers coated with a conductive substance, adhesion between the conductive substance and the substrate is problematic. Further, there is a problem that a conductive material using alkali titanate fiber as a base material cannot be used for applications in which alkalis are not mixed, such as polycarbonate, engineering plastics to which a flame retardant is added, and semiconductor-related antistatic applications.
本発明者らは繊維状の酸化チタンもしくは水和酸化チ
タン粉末をアンモニアを含む還元雰囲気下で加熱還元す
ることにより、元の繊維状を保持した導電性の酸窒化チ
タン繊維が容易に得られることを見出し、先に出願し
た。出発原料となる水和酸化チタン繊維は、針状のチタ
ン酸アルカリ（一般には焼成法やフラックス法によって
得られる四チタン酸カリウム繊維）を水または酸溶液で
水熱処理し、アルカリを除去する方法〔柳田、清水、繊
維学会誌、34（1978）,319〕、板状のチタン酸アルカリ
（一般にはメルト法で得た二チタン酸カリウム繊維）を
酸水溶液で処理しアルカリを除去する方法〔藤木、大
坂、窯業協会誌、90（1982）、19〕、または三塩化チタ
ン水溶液を空気で酸化する方法〔粉体粉末治金協会、昭
和55年度秋季大会講演概要集２−６、p86〕、によって
得られることが既に知られている。The inventors of the present invention can easily obtain conductive titanium oxynitride fibers retaining the original fibrous state by heating and reducing fibrous titanium oxide or hydrated titanium oxide powder in a reducing atmosphere containing ammonia. And filed earlier. A hydrated titanium oxide fiber as a starting material is obtained by subjecting a needle-like alkali titanate (generally, a potassium tetratitanate fiber obtained by a firing method or a flux method) to hydrothermal treatment with water or an acid solution to remove the alkali [ Yanagida, Shimizu, Journal of the Textile Society of Japan, 34 (1978), 319], a method of removing alkali by treating a plate-like alkali titanate (generally potassium dititanate fiber obtained by a melt method) with an aqueous acid solution [Fujiki, Osaka, Journal of the Ceramics Society of Japan, 90 (1982), 19], or a method of oxidizing an aqueous solution of titanium trichloride with air [Powder and Powder Metallurgy Association, Abstracts of Autumn Meeting, 1980, 2-6, p86]. It is already known that
また酸化チタン繊維は水和酸化チタン繊維を数百℃以
上で加熱脱水することにより得られ、また四塩化チタン
を含有する塩化物溶融塩中で空気により酸化する方法に
よっても容易に得ることが出来る。（U.S.P.3,012,857,
U.S.P.3,030,183） （問題解決に係る知見） 本発明者らは以上の既知の事項により繊維状の導電性
酸窒化チタン粉末が酸化チタン繊維もしくは水和酸化チ
タン繊維をアンモニアを含む還元雰囲気下で加熱還元す
ることにより、効率よくえられることを見出して本発明
を完成した。The titanium oxide fiber is obtained by heating and dehydrating the hydrated titanium oxide fiber at a temperature of several hundred degrees Celsius or higher, and can also be easily obtained by a method of oxidizing with air in a chloride molten salt containing titanium tetrachloride. . (USP3,012,857,
(USP 3,030,183) (Knowledge for solving the problem) According to the above-mentioned known facts, the present inventors heated the fibrous conductive titanium oxynitride powder in a reducing atmosphere containing ammonia or titanium oxide fiber or hydrated titanium oxide fiber. The present inventors have found that the compound can be obtained efficiently by reduction and completed the present invention.
（発明の構成） 本発明は、一般式TiOxNy（１＜ｘ＋ｙ＜２）なる組成
を有し、酸素を４〜39wt％、窒素を１〜20wt％（O/N重
量比39〜0.2）含有した平均長0.3μｍ〜2000μｍ（アス
ペクト比（長径／短径）３〜200）の酸窒化チタン繊維
を提供する。本発明はまた、繊維状の酸化チタンもしく
は水和酸化チタンをアンモニアを含む還元雰囲気下で50
0〜1000℃に加熱して還元することからなる導電性酸窒
化チタン繊維の製造方法を提供する。(Constitution of the Invention) The present invention has a composition represented by the general formula TiOxNy (1 <x + y <2), and contains 4 to 39 wt% of oxygen and 1 to 20 wt% of nitrogen (O / N weight ratio 39 to 0.2). Provided is a titanium oxynitride fiber having an average length of 0.3 μm to 2000 μm (aspect ratio (major axis / minor axis) of 3 to 200). The present invention also provides fibrous titanium oxide or hydrated titanium oxide under a reducing atmosphere containing ammonia.
Provided is a method for producing a conductive titanium oxynitride fiber, which comprises heating to reduce the temperature to 0 to 1000 ° C.
本発明に用いる繊維状の酸化チタンもしくは水和酸化
チタンは無定型及びアナターゼ型、ルチル型の正方晶系
のいずれの結晶型でもよく、平均長さ0.3μｍから2000
μｍ、アスペクト比（長径／短径）３〜200の粉末で、
アルカリ含有量が1wt％以下のものである。平均長さが
0.3μｍ未満であると導電性複合体への添加量が多くな
る。平均長さが2000μｍを越えると繊維同士がからまり
複合体中での分散が悪くなる。またアスペクト比につい
ては、３未満であると添加量が増し、補強性などの機械
的性質の向上がみられなくなる。200を越えると複合化
の際折損し易くなり、分散性も低下する。カリウム、ナ
トリウムなどのアルカリ含有量については1wt％を越え
ると加熱還元時に折れ易くなるし、本発明の繊維状の導
電性酸窒化チタンがアルカリをきらう用途に使用出来な
くなる。The fibrous titanium oxide or hydrated titanium oxide used in the present invention may be any of amorphous and anatase-type or rutile-type tetragonal crystal forms, and has an average length of 0.3 μm to 2000 μm.
μm, powder with aspect ratio (major axis / minor axis) 3 to 200,
It has an alkali content of 1% by weight or less. Average length
If it is less than 0.3 μm, the amount added to the conductive composite increases. If the average length exceeds 2000 μm, the fibers become entangled with each other and the dispersion in the composite becomes worse. When the aspect ratio is less than 3, the amount of addition increases, and no improvement in mechanical properties such as reinforcing properties is observed. If it exceeds 200, breakage is liable to occur during compounding, and dispersibility is also reduced. If the content of alkali such as potassium and sodium exceeds 1% by weight, it tends to be broken during heat reduction, and the fibrous conductive titanium oxynitride of the present invention cannot be used for applications that do not use alkali.
繊維状の酸化チタンもしくは水和酸化チタンをアンモ
ニアを含む還元雰囲気下で還元する場合、元の形状を維
持し、導電性を出すためには加熱温度が重要である。こ
の温度範囲は500〜1000℃で、好ましくは、600〜900℃
である。500℃未満では長時間還元雰囲気下において
も、反応が進行せず、1000℃を越える温度では繊維同士
の焼結が進み元の形状が維持出来ず、補強性を失う。こ
の温度範囲において反応時間は0.5〜６時間の比較的短
時間で良い。アンモニアを含む還元性ガスの流量につい
ては、キャリーオーバーが抑えられる範囲で炉内線速度
が大きいほど均一な粉末が得られるが少なくとも0.5cm/
sec以上の炉内線速度がないと反応は均一に進行しな
い。このようにして得られる酸窒化チタン繊維は反応温
度、時間、還元性ガスの流量を変えることにより10-2Ω
・cmから105Ω・cmの広範囲の導電性をもった有色の補
強性粉末が得られる。またこの繊維はTiOxNy（１＜ｘ＋
ｙ＜２）なる組成を有し、酸素を４〜39wt％、窒素を１
〜20wt％（O/N重量比39〜0.2）を含有する。酸素39wt％
を越え、窒素1wt％未満であると導電性を示さず、また
酸素4wt％未満、窒素20wt％を越えると元の形状が維持
出来なくなる。以上のプロセスにより得られた粉末は絶
縁性材料（プラスチックス、紙、無機物等）と複合化さ
せることにより少ない添加量で導電性を付与することが
出来る。更に、プラスチックに添加した場合、機械的強
度、寸法安定性等の向上を示す。When fibrous titanium oxide or hydrated titanium oxide is reduced in a reducing atmosphere containing ammonia, the heating temperature is important for maintaining the original shape and providing conductivity. This temperature range is 500-1000 ° C, preferably 600-900 ° C
It is. If the temperature is lower than 500 ° C., the reaction does not proceed even in a reducing atmosphere for a long time, and if the temperature exceeds 1000 ° C., sintering of the fibers progresses, the original shape cannot be maintained, and the reinforcing property is lost. In this temperature range, the reaction time may be a relatively short time of 0.5 to 6 hours. Regarding the flow rate of the reducing gas containing ammonia, a uniform powder can be obtained as the furnace linear velocity is increased within a range where carryover is suppressed, but at least 0.5 cm /
The reaction does not proceed uniformly unless the linear velocity in the furnace is longer than sec. The titanium oxynitride fiber obtained in this way is 10 -2 Ω by changing the reaction temperature, time, and reducing gas flow rate.
A colored reinforcing powder with a wide range of conductivity from cm to 10 5 Ω · cm is obtained. This fiber is made of TiOxNy (1 <x +
y <2), containing 4 to 39% by weight of oxygen and 1% of nitrogen.
-20% by weight (O / N weight ratio 39-0.2). Oxygen 39wt%
If less than 1% by weight of nitrogen, no conductivity is exhibited. If less than 4% by weight of oxygen and more than 20% by weight of nitrogen, the original shape cannot be maintained. The powder obtained by the above process can impart conductivity with a small amount of addition by being compounded with an insulating material (plastics, paper, inorganic substance, etc.). Furthermore, when added to plastics, it shows improvements in mechanical strength, dimensional stability, and the like.
以下に実施例により本発明を具体的に示す。 Hereinafter, the present invention will be specifically described with reference to Examples.
実施例１〜４ 四チタン酸カリウム繊維より製造した平均繊維長さ10
μｍ、アスペクト比30の水和酸化チタン繊維（カリウム
含有量0.7wt％）20gをボートに入れて、反応温度、反応
時間、反応ガスの組成と炉内線速度を変化させて繊維状
の酸窒化チタンを製造し、組成、比抵抗、色、形状を測
定した。結果を第１表に示す。Examples 1-4 Average fiber length 10 produced from potassium tetratitanate fiber
20 g of hydrated titanium oxide fiber (potassium content 0.7 wt%) with a thickness of 30 μm and an aspect ratio of 30 was placed in a boat and the reaction temperature, reaction time, reaction gas composition and furnace linear velocity were changed to obtain a fibrous titanium oxynitride. Was manufactured, and the composition, specific resistance, color, and shape were measured. The results are shown in Table 1.
実施例５〜７ 三塩化チタン水溶液より製造した平均繊維長さ0.6μ
ｍ、アスペクト比７のルチル型酸化チタン繊維を20gボ
ートに入れて反応条件を変えて処理を行った結果を第１
表に示す。Examples 5 to 7 Average fiber length 0.6 μm produced from titanium trichloride aqueous solution
The results obtained by placing 20 g of rutile type titanium oxide fiber having a m and aspect ratio of 7 in a boat and changing the reaction conditions were used as the first results.
It is shown in the table.
実施例８ 板状の二チタン酸カリウム繊維から製造した平均繊維
長さ400μｍ、アスペクト比30のアナターゼ型酸化チタ
ン繊維を20gボートに入れてNH3ガスを2cm/secの炉内線
速度で、900℃、1hrの処理を行った。結果を第１表に示
す。Example 8 20 g of an anatase type titanium oxide fiber having an average fiber length of 400 μm and an aspect ratio of 30 produced from plate-like potassium dititanate fiber was put into a 20 g boat, and NH 3 gas was supplied at a furnace linear speed of 2 cm / sec at 900 ° C. For 1 hour. The results are shown in Table 1.
比較例１ 実施例１と同形状のチタン酸カリウムを用い同様の反
応条件を行なって製造した。Comparative Example 1 The same reaction conditions were produced using potassium titanate having the same shape as that of Example 1 to produce the same.
比較例２〜３ 実施例１の反応条件を還元温度450℃、1050℃以外は
同一にし処理を行った結果を表１に示す。Comparative Examples 2 and 3 Table 1 shows the results of the treatment performed in the same manner as in Example 1 except that the reduction conditions were 450 ° C. and 1050 ° C.
実施例９ 実施例３の繊維状酸窒化チタン粉末をポリプロピン
（三菱油化BC−４）に混合し、二本ロールを用い混練し
た後、シート状に成形した。該シートについて表面抵
抗、引張強度を測定した結果を第２表に示す。 Example 9 The fibrous titanium oxynitride powder of Example 3 was mixed with polypropyne (Mitsubishi Yuka BC-4), kneaded using two rolls, and formed into a sheet. Table 2 shows the results of measuring the surface resistance and tensile strength of the sheet.
フロントページの続き (72)発明者 坂井 洋一 埼玉県大宮市北袋町１―297 三菱金属 株式会社中央研究所内 (72)発明者 小林 勇 兵庫県尼崎市浜１丁目１番１号 久保田 鉄工株式会社技術開発研究所内 (72)発明者 牧戸 勲 兵庫県尼崎市浜１丁目１番１号 久保田 鉄工株式会社技術開発研究所内Continued on the front page (72) Inventor Yoichi Sakai 1-27 Kitabukuro-cho, Omiya-shi, Saitama Mitsubishi Metals Central Research Laboratory (72) Inventor Isamu 1-1-1 Hama, Amagasaki-shi, Hyogo Kubota Tekko Co., Ltd. (72) Inventor Isao Makito 1-1-1 Hama, Amagasaki-shi, Hyogo Kubota Iron Works Co., Ltd.
Claims (2)
を有し、酸素を４〜39wt％、窒素を１〜20wt％（O/N重
量比39〜0.2）を含有した平均長0.3μｍ〜2000μｍ、ア
スペクト比（長径／短径）３〜200の酸窒化チタンの繊
維。An average length of 0.3 to 3 wt% of oxygen and 4 to 39 wt% of nitrogen and 1 to 20 wt% of nitrogen (O / N weight ratio of 39 to 0.2). Titanium oxynitride fibers having a diameter of 3 to 200 μm to 2000 μm and an aspect ratio (major axis / minor axis) of 3 to 200 μm.
ンをアンモニアを含む還元雰囲気下で、500〜1000℃に
して加熱して還元することからなる導電性酸窒化チタン
繊維の製造法。2. A method for producing a conductive titanium oxynitride fiber, comprising reducing fibrous titanium oxide or hydrated titanium oxide by reducing the temperature of the fibrous titanium oxide or hydrated titanium oxide by heating at 500 to 1000 ° C. in an atmosphere containing ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63039579A JP2612884B2 (en) | 1988-02-24 | 1988-02-24 | Titanium oxynitride fiber and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63039579A JP2612884B2 (en) | 1988-02-24 | 1988-02-24 | Titanium oxynitride fiber and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01215718A JPH01215718A (en) | 1989-08-29 |
| JP2612884B2 true JP2612884B2 (en) | 1997-05-21 |
Family
ID=12556994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63039579A Expired - Lifetime JP2612884B2 (en) | 1988-02-24 | 1988-02-24 | Titanium oxynitride fiber and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2612884B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1205245A4 (en) * | 1999-08-05 | 2005-01-19 | Toyoda Chuo Kenkyusho Kk | Photocatalytic material and photocatalytic article |
| DE60107991T2 (en) * | 2000-03-31 | 2005-12-15 | Sumitomo Chemical Co., Ltd. | Process for producing titanium oxide |
| JP4106434B2 (en) * | 2003-05-02 | 2008-06-25 | 国立大学法人 千葉大学 | Method for producing metal oxide semiconductor |
| CZ2008278A3 (en) * | 2008-05-06 | 2009-12-30 | Elmarco S.R.O. | Method for production of inorganic nanofibers and/or nanofibrous structures comprising TiN, inorganic nanofibers and/or nanofibrous structures comprising TiN and use of such nanofibrous structures |
| JP2009298601A (en) * | 2008-06-10 | 2009-12-24 | Sumitomo Chemical Co Ltd | Method for producing metal oxynitride |
| TWI404811B (en) * | 2009-05-07 | 2013-08-11 | Atomic Energy Council | Method of fabricating metal nitrogen oxide thin film structure |
-
1988
- 1988-02-24 JP JP63039579A patent/JP2612884B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01215718A (en) | 1989-08-29 |
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