JPS62230644A - Production of electrically conductive fiber - Google Patents
Production of electrically conductive fiberInfo
- Publication number
- JPS62230644A JPS62230644A JP7182786A JP7182786A JPS62230644A JP S62230644 A JPS62230644 A JP S62230644A JP 7182786 A JP7182786 A JP 7182786A JP 7182786 A JP7182786 A JP 7182786A JP S62230644 A JPS62230644 A JP S62230644A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- gel
- aqueous solution
- substituted
- metal alkoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 3
- -1 metal complex ions Chemical class 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- GOOXRYWLNNXLFL-UHFFFAOYSA-H azane oxygen(2-) ruthenium(3+) ruthenium(4+) hexachloride Chemical compound N.N.N.N.N.N.N.N.N.N.N.N.N.N.[O--].[O--].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ru+3].[Ru+3].[Ru+4] GOOXRYWLNNXLFL-UHFFFAOYSA-H 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/011—Manufacture of glass fibres or filaments starting from a liquid phase reaction process, e.g. through a gel phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/003—Conducting or semi-conducting fibres
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Glass Melting And Manufacturing (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
この発明は導電性繊維の製造方法に関する。さらに詳し
くは、電磁波、雑音等の遮断用に用いられるセラミック
、ガラス等の繊維からなる導電性繊維の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to a method for producing conductive fibers. More specifically, the present invention relates to a method for manufacturing conductive fibers made of ceramic, glass, etc. fibers used for shielding electromagnetic waves, noise, etc.
（ロ）従来の技術
従来、ガラスまたはセラミックからなる繊維で電気伝導
性を有するセラミック繊維としては、炭素繊維および炭
化ケイ素にアルミニウム等を蒸着被覆した繊維等が知ら
れている。(B) Prior Art Conventionally, as ceramic fibers made of glass or ceramic and having electrical conductivity, carbon fibers and fibers made of silicon carbide coated with aluminum or the like are known.
（ハ）発明が解決しようとする問題点
しかじな力くら、炭素繊維は高価であり、また大気中で
は３００℃以上で酸化されてしまうので耐熱性がない。(c) Problems to be Solved by the Invention On the other hand, carbon fibers are expensive and have no heat resistance since they are oxidized at temperatures of 300° C. or higher in the atmosphere.
また繊維体に金属膜を蒸着形成したものでは蒸着にコス
トや時間がかかりまた繊維体と蒸着膜との熱膨張の違い
から蒸着膜が剥がれやすく耐熱性や耐久性に問題があっ
た。Further, in the case where a metal film is deposited on a fibrous body, the deposition process is costly and time-consuming, and due to the difference in thermal expansion between the fibrous body and the deposited film, the deposited film tends to peel off easily, causing problems in heat resistance and durability.
この発明はかかる状況に鑑み為されたものであり、こと
に耐熱性を有しかつ簡便に得られる導電性繊維の製造方
法を提供しようとするものである。The present invention has been made in view of the above situation, and it is an object of the present invention to provide a method for producing conductive fibers that are particularly heat resistant and easily obtainable.
（ニ）問題点を解決するための手段
かくしてこの発明によれば、金属アルコキシドと、金属
アルコキシドの少なくとも１つのアルコキシ基が脂肪族
もしくは芳香族の炭化水素基、アミノ基またはアルキル
アミノ基で置換された置換金属アルコキシドとの混合物
からなる水性溶液に、加水分解触媒を添加して加水分解
してゾルとし、これを濃縮し、この濃縮ゾルを紡糸して
繊維状ゲルとし、これを導電性金属酸化物を形成しうる
金属イオンまたは金属錯イオンを含有する水溶液に浸漬
して該金属イオンまたは金属錯イオンを上記ゲル体中に
含浸させ、次いでこの含浸処理繊維状ゲルを空気中で高
温で熱処理して導電性繊維を得ることを特徴とする導電
性繊維の製造方法が提供される。(d) Means for Solving the Problems According to the present invention, the metal alkoxide and at least one alkoxy group of the metal alkoxide are substituted with an aliphatic or aromatic hydrocarbon group, an amino group, or an alkylamino group. A hydrolysis catalyst is added to an aqueous solution consisting of a mixture of a substituted metal alkoxide and a substituted metal alkoxide, which is hydrolyzed to form a sol, which is concentrated, and this concentrated sol is spun to form a fibrous gel. The gel body is impregnated with the metal ions or metal complex ions by immersion in an aqueous solution containing metal ions or metal complex ions capable of forming a substance, and then the impregnated fibrous gel is heat-treated in air at a high temperature. Provided is a method for producing conductive fibers, characterized in that the conductive fibers are obtained by
この発明の最も特徴とする点は、金属アルコキシドと置
換金属アルコキシドとの混合物からなる水性溶液を加水
分解して得られる濃縮ゾルの曳糸性を利用して紡糸し、
この結果得られる多孔質繊維状ゲルに導電性物質を含浸
して熱処理することにより導電性繊維を得ることにある
。The most distinctive feature of this invention is that spinning takes advantage of the spinnability of a concentrated sol obtained by hydrolyzing an aqueous solution consisting of a mixture of a metal alkoxide and a substituted metal alkoxide.
The purpose is to obtain conductive fibers by impregnating the resulting porous fibrous gel with a conductive substance and heat-treating it.
この発明に用いる金属アルコキシドとしては、加熱処理
して脱水することによりゲルを与えうるちのであればよ
く例えば、シリコンアルコキシド、アルミニウムアルコ
キシド、チタンアルコキシド、ボロンアルコキシド、ナ
トリウムアルコキシド、カルシウムアルコキシド等が挙
げられ、シリコンアルコキシド、アルミニウムアルコキ
シド、チタンアルコキシドが好ましい。The metal alkoxide used in this invention may be any metal alkoxide as long as it can form a gel by heat treatment and dehydration, such as silicon alkoxide, aluminum alkoxide, titanium alkoxide, boron alkoxide, sodium alkoxide, calcium alkoxide, etc. Silicon alkoxide, aluminum alkoxide, and titanium alkoxide are preferred.
またアルコキシ基には低級アルコキシ基が適しており、
例えばメトキシ基、エトキシ基、プロピオキシ基等が挙
げられる。In addition, a lower alkoxy group is suitable for the alkoxy group,
Examples include methoxy group, ethoxy group, propioxy group, and the like.
上記金属アルコキシドには例えば、
シリコンテトラエトキシドＳ ｉ（ＯＣｔＨＳ）４、ト
リエトキシアルミニウムＡ Ｉ（ＯＣｔＨａ）ｓ、テト
ライソプロピオキシチタンＴ １（０−ｉＣ３Ｈｆｆ）
４、テトラエトキノジルコニウムＺ ｒ（ＯＣｔＨｓ）
ａ等が挙げられ、シリコンテトラエトキシドが好ましい
。Examples of the metal alkoxides include silicon tetraethoxide Si (OCtHS)4, triethoxyaluminum AI (OCtHa)s, and tetraisopropioxytitanium T1 (0-iC3Hff).
4. Tetraethoquinozirconium Zr (OCtHs)
a and the like, with silicon tetraethoxide being preferred.
また、上記金属アルコキシドのアルコキン基が置換され
る脂肪族炭化水素基としては、低級アルキル基、ビニル
基等が挙げられるか、低級アルキル基で置換された置換
金属アルコキシドとしては、例えばＳ ＋（ＯＣｔＨ５
）ｓ（ＣＨ３）、５ｉ（ＯＣｚＨ・５）ｚ（ＣＨｓ）ｚ
、。Furthermore, examples of the aliphatic hydrocarbon group substituted with the alkokene group of the metal alkoxide include a lower alkyl group and a vinyl group, and examples of the substituted metal alkoxide substituted with a lower alkyl group include, for example, S + (OCtH5
)s(CH3), 5i(OCzH・5)z(CHs)z
,.
Ｓ ＋（ＯＣｔＨ５）３（ＣｐＨｓ）、Ｓ ｉ（ＯＣｔ
Ｈ５）２（ＣｚＨｓ）ｔ、Ｓ ｉ（ＯＣｔＨ５）３（ｉ
ＣｓＨ？）、Ｓ ｉ（ＯＣｘＨ５）ｚ（ｉ ＣｓＨ７
）ｔ、Ｔ １（０−ｉｃ ３Ｈ７）３（ＣｐＨｓ）、Ｔ
ｉ（０−ｉ ＣｓＨｔ）ｔ（０２Ｈ５）ｔｓＡ Ｉ（
０−ｉ Ｃ３Ｈ７）ｔ（ＣＨ３）、Ａ Ｉ（０−ｉ Ｃ
３Ｈｔ）ｔ（ＣｘＨｓ）、Ａ Ｉ（０−ｉＣ３Ｈ？）（
ＣＨｓ）ｔ、Ｂ （ＯＣ２Ｈ５）ｔ（ＣｔＨｓ）、
Ｃａ（ＯＣｔＨ５）（ＣｘＨｓ）等が挙げられる。S + (OCtH5)3 (CpHs), S i (OCt
H5)2(CzHs)t, Si(OCtH5)3(i
CsH? ), S i(OCxH5)z(i CsH7
)t, T 1(0-ic 3H7)3(CpHs), T
i(0-i CsHt)t(02H5)tsA I(
0-i C3H7)t(CH3), A I(0-i C
3Ht)t(CxHs), A I(0-iC3H?)(
CHs)t, B(OC2H5)t(CtHs), Ca(OCtH5)(CxHs), and the like.
金属アルコキシドのアルコキシ基が置換される芳香族炭
化水素基としては、フェニル基またはメチル、エチルも
しくはプロピル基等の低級アルキル基で置換されたフェ
ニル基が挙げられる。Examples of the aromatic hydrocarbon group substituted with the alkoxy group of the metal alkoxide include a phenyl group or a phenyl group substituted with a lower alkyl group such as methyl, ethyl or propyl group.
金属アルコキシドのアルコキシ基が置換されるアルキル
置換アミノ基としては、メチル、エチルもしくはプロピ
ル基等の低級アルキル基で置換されたアミノ基が挙げら
れる。Examples of the alkyl-substituted amino group on which the alkoxy group of the metal alkoxide is substituted include amino groups substituted with lower alkyl groups such as methyl, ethyl, or propyl groups.
前記金属アルコキシドと置換金属アルコキシドとの混合
重量比は、得られる濃縮ゾルの曳糸性の点から、ｌ：ｌ
〜５二ｌが好ましい。The mixing weight ratio of the metal alkoxide and the substituted metal alkoxide is 1:1 from the viewpoint of the spinnability of the obtained concentrated sol.
~52 l is preferred.
上記金属アルコキシドまたは金属アルコキシドと置換金
属アルコキシドとの混合物を含有する水性溶媒としては
、従来法と同様に、水とメタノール、エタノール、プロ
パツール等の低級アルコールとの混合溶液が用いられる
。As the aqueous solvent containing the metal alkoxide or the mixture of metal alkoxide and substituted metal alkoxide, a mixed solution of water and a lower alcohol such as methanol, ethanol, propatool, etc. is used as in the conventional method.
また加水分解触媒は従来法と同様に、塩酸、硫酸、アン
モニア水溶液等が用いられる。Further, as the hydrolysis catalyst, hydrochloric acid, sulfuric acid, ammonia aqueous solution, etc. are used as in the conventional method.
金属アルコキシドと置換金属アルコキシドとの混合物の
水性溶液を加水分解してゾルとする場合、これら水性溶
液に前記加水分解触媒を添加して常温で撹拌して行うこ
とができるが、若干昇温しで加水分解反応を速めてもよ
い。また上記加水分解反応は、金属アルコキシド、置換
金属アルコキシド、水性溶媒および加水分解触媒を同時
に添加混合して行ってもよい。When an aqueous solution of a mixture of a metal alkoxide and a substituted metal alkoxide is hydrolyzed to form a sol, it can be carried out by adding the hydrolysis catalyst to the aqueous solution and stirring at room temperature; The hydrolysis reaction may be accelerated. Further, the above hydrolysis reaction may be carried out by simultaneously adding and mixing a metal alkoxide, a substituted metal alkoxide, an aqueous solvent, and a hydrolysis catalyst.
このようにして得られたゾルは、さらに加熱されて濃縮
されるが、この場合の加熱処理条件は比較的穏やかに例
えば大気中、８０℃程度のオイルバス中で加熱処理する
等の条件下で行われる。The sol obtained in this way is further heated and concentrated, but the heat treatment conditions in this case are relatively mild, such as in the air or in an oil bath at about 80°C. It will be done.
上記加熱はゾルの体積が１１５程度に濃縮されるまで行
われることが好ましい。It is preferable that the heating is performed until the volume of the sol is concentrated to about 115 sol.
上記加熱処理間にゾルの脱水反応が徐々に進行する。During the heat treatment, the dehydration reaction of the sol gradually progresses.
この発明において、上記の処理により得られた濃縮ゾル
は所定の粘度例えばｌＯポアズ程度になったところでガ
ラス棒等の先端を接触させて常温で引き出すことにより
糸状に成形され繊維状ゲル（ゲルファイバ）が得られる
。In this invention, when the concentrated sol obtained by the above treatment reaches a predetermined viscosity, for example, about 10 poise, the tip of a glass rod or the like is brought into contact with the sol and drawn out at room temperature to form a filamentous gel (gel fiber). is obtained.
この繊維状ゲルは太さが２０〜１００μ程度に調整され
るものが強度等の点で好ましく、これは引き出し強度お
よびゾルの濃縮度により調節される。The thickness of this fibrous gel is preferably adjusted to about 20 to 100 μm from the viewpoint of strength, and this is adjusted depending on the drawing strength and the concentration of the sol.
また上記繊維状ゲルの成形は巻取り機等で連続して紡糸
し、用途に応じて適宜適当な長さに切断することもでき
る。Further, the above-mentioned fibrous gel can be formed by continuously spinning it using a winder or the like, and then cutting it into appropriate lengths depending on the application.
上記の方法により成形された繊維状ゲルは、多孔質のも
のとして得られ、上記方法によれば通常気孔率が３０〜
８０％のものが得られる。またこの気孔率は乾燥条件を
調節することにより調整可能である。The fibrous gel molded by the above method is obtained as a porous gel, and according to the above method, the porosity is usually 30 to 30.
80% is obtained. Moreover, this porosity can be adjusted by adjusting the drying conditions.
以上の方法により得られた多孔質繊維状ゲルは、所定の
金属イオンまたは金属錯イオンを含有する水溶液に浸漬
される。The porous fibrous gel obtained by the above method is immersed in an aqueous solution containing a predetermined metal ion or metal complex ion.
上記金属イオンまたは金属錯イオンには、後述する熱処
理後の金属酸化物においても導電性を有するものが選択
され、例えばルテニウム錯イオン、インジウム錯イオン
、スズ錯イオン等が挙げられる。As the metal ion or metal complex ion, one is selected that has conductivity even in the metal oxide after heat treatment described below, and examples thereof include ruthenium complex ion, indium complex ion, tin complex ion, and the like.
ルテニウム錯イオンを含有する水溶液としてはルテニウ
ムレッドを用いることが好ましい。It is preferable to use ruthenium red as the aqueous solution containing ruthenium complex ions.
インジウム錯イオン、スズ錯イオン等はそれぞれアセチ
ルアセトナート錯体として含有するアルコール性溶液を
用いることが好ましい。It is preferable to use an alcoholic solution containing indium complex ions, tin complex ions, and the like as acetylacetonate complexes.
上記水溶液は通常０．Ｏ１〜０．１（ｎ＋ｏｌ＃り程度
の濃度のものが用いられる。The above aqueous solution is usually 0. A concentration of about 01 to 0.1 (n+ol#) is used.
前記繊維状ゲルの上記水溶液中への浸漬時間は１０秒〜
１０分程度が適している。The fibrous gel is immersed in the aqueous solution for 10 seconds or more.
Approximately 10 minutes is suitable.
上記水溶液に所定時間浸漬した繊維状ゲルは、空気中で
所定の加熱乾燥（例えば１２０℃で３０ｍ１ｎ程度）さ
れた後、加熱処理がなされる。The fibrous gel immersed in the aqueous solution for a predetermined period of time is heated and dried in air for a predetermined amount (for example, about 30 ml at 120° C.), and then subjected to a heat treatment.
上記加熱処理は、空気中、高温でなされこれにより繊維
状のガラスまたはセラミックが得られる。The above heat treatment is performed in air at a high temperature, thereby obtaining a fibrous glass or ceramic.
上記処理は意図する温度（３００〜１０００℃程度）ま
では比較的速く昇温した後該温度で所定時間（１０分〜
１５時間程度）保持されることが適している。The above treatment involves raising the temperature relatively quickly to the intended temperature (approximately 300 to 1000 degrees Celsius) and then maintaining it at that temperature for a predetermined period of time (10 minutes to 1000 degrees Celsius).
15 hours) is suitable.
例えば２００℃／ｈｒ程度で１０００℃まで昇温しその
後該温度で１０時間程度保持する等が挙げられる。、上
記加熱処理により多孔質内および表面に均一に金属酸化
物が保持された導電性のガラスまたはセラミック繊維が
得られる。For example, the temperature may be raised to 1000° C. at a rate of about 200° C./hr and then maintained at that temperature for about 10 hours. By the heat treatment described above, conductive glass or ceramic fibers with metal oxides uniformly retained within the pores and on the surface can be obtained.
以上のごとくして得られた導電性繊維はそれ自身新規な
ものである。The conductive fiber obtained as described above is itself new.
（ホ）作用
この発明によれ、ば、金属アルコキシドと置換金属アル
コキンドとの混合物からなる水性溶液を加水分解して得
られる濃縮ゾルを紡糸すると多孔質繊維状にゲル化しこ
の繊維状ゲルを特定の金属錯イオンまたは金属イオンを
含有する水溶液に浸漬した後、加熱処理することにより
ゲルの多孔質網目内に金属酸化物が均質に含浸されると
同時にゲルはガラス化する。(E) Effect According to the present invention, when a concentrated sol obtained by hydrolyzing an aqueous solution consisting of a mixture of a metal alkoxide and a substituted metal alkoxide is spun, it is gelled into a porous fiber, and this fibrous gel is formed into a specific fibrous gel. After being immersed in a metal complex ion or an aqueous solution containing metal ions, the gel is heat-treated to homogeneously impregnate the metal oxide into the porous network of the gel and at the same time vitrify the gel.
以下実施例によりこの発明の詳細な説明するが、これに
よりこの発明は限定されるものではない。The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereby.
（へ）実施例
アルコキシドファイバの作製
Ｓ ｉ（ＯＣ２Ｈ３）４４０ｍＱ、 Ｓ ｉ（ＯＣｔＨ
ｓ）ｓ（ＣＨｚ）ＬＯ＠Ｌエタノール５０ｍ（、水 ８
ｍＱおよび１．ＯＮ −ＨＣ１１ｍＱを混合してｌ）Ｈ
約３の水溶液を調整しこの溶液を１時間撹拌して加水分
解し均一なゾルを得る。次にこのゾルを６０℃に保って
約６時間撹拌して濃縮する。このときこの濃縮ゾルの粘
度が１０ポアズ程度になったところでガラス棒の先端を
該ゾルに挿入し、ついで引き上げて直径約１００μ、長
さ約３０ｃｍの多孔質ゲルファイバを得た。(f) Example Preparation of alkoxide fiber S i (OC2H3) 440 mQ, S i (OCtH
s)s(CHz)LO@L ethanol 50m(, water 8
mQ and 1. Mix ON-HC11mQ l)H
Prepare an aqueous solution of about 3 and stir this solution for 1 hour to hydrolyze and obtain a homogeneous sol. Next, this sol is kept at 60° C. and stirred for about 6 hours to concentrate. At this time, when the viscosity of this concentrated sol reached about 10 poise, the tip of a glass rod was inserted into the sol and then pulled up to obtain a porous gel fiber with a diameter of about 100 μm and a length of about 30 cm.
導電性繊維の製造
上記ゲルファイバをルテニウムレッド水溶液（０，１ｇ
／ １ｍ６Ｈ７Ｏ）中に２時間浸漬した後、１２０℃空
気中で３０分乾燥し、次いでこれを２００℃／ｈｒの昇
温速度で１０００℃まで昇温し、この温度で１０時間熱
処理してアルコキシドガラス繊維を得た。この繊維の電
気抵抗率は６ Ｘ １０−’Ωｃｎ＋であった。Production of conductive fibers The above gel fibers were mixed with a ruthenium red aqueous solution (0.1g
/ 1m6H7O) for 2 hours, dried in air at 120℃ for 30 minutes, then heated to 1000℃ at a heating rate of 200℃/hr, and heat-treated at this temperature for 10 hours to form alkoxide glass. Obtained fiber. The electrical resistivity of this fiber was 6 x 10-'Ωcn+.
また上記ゲルファイバをルテニウムレッドの水溶液（０
，Ｏ１ｇ／１ｍＮＨ＊Ｏ）中に５分浸漬した後、上記と
同様の処理をして得られた繊維の電気抵抗率を測定した
ところ、２ Ｘ １０−’Ωｅｌｆであった。In addition, the above gel fiber was mixed with an aqueous solution of ruthenium red (0
, O1g/1mNH*O) for 5 minutes and then treated in the same manner as above.The electrical resistivity of the obtained fiber was measured and found to be 2 x 10-' Ωelf.
以上の結果から、この実施例に従って作製されたアルコ
キシドガラスからなる繊維には導電性が付与されており
、耐熱性（９００℃程度）も優れたものである。From the above results, the fibers made of alkoxide glass produced according to this example are endowed with electrical conductivity and have excellent heat resistance (approximately 900° C.).
（ト）発明の効果
この発明によれば、金属アルコキシドと置換金属アルコ
キシドとの混合物の加水分解物からなる濃縮ゾルを紡糸
することにより形成される多孔質ゲルに所定の導電物質
を含浸担持して加熱処理して成形しているので、均一に
設けられた多孔質内および表面に均一に導電物質が担持
され耐熱性および耐久性に優れた導電性繊維が得られる
。(G) Effects of the Invention According to this invention, a predetermined conductive substance is impregnated and supported on a porous gel formed by spinning a concentrated sol consisting of a hydrolyzate of a mixture of a metal alkoxide and a substituted metal alkoxide. Since it is heat-treated and molded, the conductive substance is uniformly supported in the uniformly provided pores and on the surface, resulting in a conductive fiber with excellent heat resistance and durability.
Claims (1)
も１つのアルコキシ基が脂肪族もしくは芳香族の炭化水
素基、アミノ基またはアルキルアミノ基で置換された置
換金属アルコキシドとの混合物からなる水性溶液に、加
水分解触媒を添加して加水分解してゾルとし、これを濃
縮し、この濃縮ゾルを紡糸して繊維状ゲルとし、これを
導電性金属酸化物を形成しうる金属イオンまたは金属錯
イオンを含有する水溶液に浸漬して該金属イオンまたは
金属錯イオンを上記ゲル体中に含浸させ、次いでこの含
浸処理繊維状ゲルを空気中で高温で熱処理して導電性繊
維を得ることを特徴とする導電性繊維の製造方法。 ２、金属アルコキシドおよび置換金属アルコキシドの金
属原子がケイ素、アルミニウム、チタン、ホウ素、ナト
リウムまたはカルシウムである特許請求の範囲第１項記
載の製造方法。 ３、金属錯イオンまたは金属イオンを含有する水溶液が
ルテニウムレッド水溶液である特許請求の範囲第１項記
載の製造方法。[Claims] 1. An aqueous product consisting of a mixture of a metal alkoxide and a substituted metal alkoxide in which at least one alkoxy group of the metal alkoxide is substituted with an aliphatic or aromatic hydrocarbon group, an amino group, or an alkylamino group. A hydrolysis catalyst is added to the solution to hydrolyze it to form a sol, this is concentrated, this concentrated sol is spun to form a fibrous gel, and this is mixed with metal ions or metal complexes that can form conductive metal oxides. The gel body is immersed in an aqueous solution containing ions to impregnate the metal ions or metal complex ions into the gel body, and then the impregnated fibrous gel is heat-treated in air at a high temperature to obtain conductive fibers. A method for producing conductive fibers. 2. The manufacturing method according to claim 1, wherein the metal atom of the metal alkoxide and substituted metal alkoxide is silicon, aluminum, titanium, boron, sodium or calcium. 3. The manufacturing method according to claim 1, wherein the metal complex ion or metal ion-containing aqueous solution is a ruthenium red aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7182786A JPS62230644A (en) | 1986-03-29 | 1986-03-29 | Production of electrically conductive fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7182786A JPS62230644A (en) | 1986-03-29 | 1986-03-29 | Production of electrically conductive fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62230644A true JPS62230644A (en) | 1987-10-09 |
Family
ID=13471770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7182786A Pending JPS62230644A (en) | 1986-03-29 | 1986-03-29 | Production of electrically conductive fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230644A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003106362A1 (en) * | 2002-06-18 | 2003-12-24 | Siemens Aktiengesellschaft | Corona shield |
| JP2005132708A (en) * | 2003-10-31 | 2005-05-26 | Kwangju Inst Of Science & Technol | Method for manufacturing optical fiber or optical element in which reduced metal ion and/or rare earth ion are doped, and method for manufacturing optical fiber or optical element in which reduced metal fine particle and/or rare earth element are doped |
| CN106830693A (en) * | 2016-12-30 | 2017-06-13 | 雷笑天 | A kind of preparation method of high-strength conductive glass fibre |
-
1986
- 1986-03-29 JP JP7182786A patent/JPS62230644A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003106362A1 (en) * | 2002-06-18 | 2003-12-24 | Siemens Aktiengesellschaft | Corona shield |
| CN100374387C (en) * | 2002-06-18 | 2008-03-12 | 西门子公司 | Corona shield |
| JP2005132708A (en) * | 2003-10-31 | 2005-05-26 | Kwangju Inst Of Science & Technol | Method for manufacturing optical fiber or optical element in which reduced metal ion and/or rare earth ion are doped, and method for manufacturing optical fiber or optical element in which reduced metal fine particle and/or rare earth element are doped |
| CN106830693A (en) * | 2016-12-30 | 2017-06-13 | 雷笑天 | A kind of preparation method of high-strength conductive glass fibre |
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