JPH01266280A - Production of electrically conductive yarn - Google Patents
Production of electrically conductive yarnInfo
- Publication number
- JPH01266280A JPH01266280A JP63092215A JP9221588A JPH01266280A JP H01266280 A JPH01266280 A JP H01266280A JP 63092215 A JP63092215 A JP 63092215A JP 9221588 A JP9221588 A JP 9221588A JP H01266280 A JPH01266280 A JP H01266280A
- Authority
- JP
- Japan
- Prior art keywords
- pyrrole
- polymer
- fibers
- yarn
- fiber
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims description 94
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 11
- 238000004043 dyeing Methods 0.000 abstract description 7
- 238000009987 spinning Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 20
- 238000005406 washing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004313 glare Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ピロール重合物が付着した導電性繊維の製造
方法に関するものである。ざらに詳しくは、染色条件下
において安定で、かつ耐摩擦性、耐洗濯性、耐久性に優
れた導電性繊維の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing conductive fibers to which a pyrrole polymer is attached. More specifically, the present invention relates to a method for producing conductive fibers that are stable under dyeing conditions and have excellent abrasion resistance, washing resistance, and durability.
（従来の技術）
導電性高分子を用いて繊維に導電性を付与することは、
通常の導電性無機微粒子を繊維に混合または付着させた
導電性繊維に比べて、導電率が高い、製法が容易などの
特徴がある。特に、ピロールの重合物を用いた場合はド
ーピングなしでも高い導電性が得られるのみならず、安
定性も高いため、注目を集めている。(Conventional technology) Adding conductivity to fibers using conductive polymers is
Compared to conductive fibers in which ordinary conductive inorganic particles are mixed or attached to fibers, they have characteristics such as higher conductivity and easier production. In particular, the use of pyrrole polymers is attracting attention because it not only provides high conductivity without doping but also has high stability.
特開昭６３−２０３６１号公報には、塩化第二鉄を含有
する高分子化合物で形成した基体とピロールを接触し、
ピロールを重合して基体の表面および内部に導電性重合
体を生成させる方法が示されている。JP-A No. 63-20361 discloses that pyrrole is brought into contact with a substrate formed of a polymer compound containing ferric chloride,
A method for polymerizing pyrrole to form a conductive polymer on and within a substrate is shown.
しかし、本方法は、導電性と透明性の両者を求めるため
、高分子中に塩化第二鉄を分散させなければならず、工
程が複雑である上、水溶性の高分子以外には適用が困難
という欠点があり、ざらには基材となる高分子の特性を
損ねるという欠点があった。However, in order to achieve both conductivity and transparency, this method requires dispersing ferric chloride into the polymer, making the process complicated and not applicable to anything other than water-soluble polymers. It has the disadvantage of being difficult, and moreover, it has the disadvantage of impairing the properties of the polymer that is the base material.
特開昭６３−４２９７２＠公報には、合成繊維からなる
布帛を塩化第二鉄水溶液に含浸し、この塩化第二鉄水溶
液を含浸せる布帛にピロール蒸気を接触させて布帛にポ
リピロール層を形成させる方法、また特開昭６１−２８
２４７９号公報には、合成重合体からなる繊維表層部に
ピロールを含浸後沃素溶液を作用させどロールの酸化重
合物と沃素置換とを同時に行い導電性を付与する方法が
示されている。しかし、いずれにおいても、導電性を有
するピロール重合体もしくはポリピロールはほとんどが
繊維の表面に付着１ノでいるのみであるので、耐摩擦性
に劣り、使用時においてピロール重合物が脱離し、導電
性が低下するという欠点を有していた。ざらに、俊者の
方法においては、処理時間が長く、また過剰に付着した
沃素が繊維や繊維が接触する他の物質の特性を劣化させ
るという問題点も生じていた。JP-A-63-42972@ discloses that a fabric made of synthetic fibers is impregnated with an aqueous ferric chloride solution, and the fabric impregnated with the aqueous ferric chloride solution is brought into contact with pyrrole vapor to form a polypyrrole layer on the fabric. method, also published in JP-A-61-28
No. 2479 discloses a method of impregnating the surface layer of a fiber made of a synthetic polymer with pyrrole and then acting on an iodine solution to simultaneously replace the oxidized polymer of the roll with iodine to impart conductivity. However, in either case, most of the electrically conductive pyrrole polymer or polypyrrole remains attached to the surface of the fiber, resulting in poor abrasion resistance, and the pyrrole polymer detaches during use, resulting in electrical conductivity. It had the disadvantage of decreasing. Furthermore, Toshiya's method requires a long processing time, and there are also problems in that excessive iodine deteriorates the properties of the fibers and other substances with which the fibers come into contact.
（発明が解決しようとする課題）
本発明はかかる課題を解決し、高い導電性を有し、かつ
染色条件下でも安定で、さらには使用時の耐摩擦性、耐
洗濯性、耐久性に著しく優れた導電性繊維を容易に提供
することを目的とするものである。(Problems to be Solved by the Invention) The present invention solves the above problems, has high conductivity, is stable under dyeing conditions, and has outstanding abrasion resistance, washing resistance, and durability during use. The purpose is to easily provide excellent conductive fibers.
（課題を解決するための手段）
上記目的を達成するために本発明は、次の構成を有する
。(Means for Solving the Problems) In order to achieve the above object, the present invention has the following configuration.
（１）繊維表面にくぼみを有する繊維の該くぼみ部へ、
ピロールの重合物を付着させることを特徴とする導電性
繊維の製造方法。(1) To the hollow part of the fiber having a hollow on the fiber surface,
A method for producing conductive fibers, which comprises attaching a polymer of pyrrole.
（２）くぼみの大きさが、幅１ミクロン以上、深さ１ミ
クロン以上である請求項１記載の導電性繊維の製造方法
。(2) The method for producing conductive fibers according to claim 1, wherein the size of the depression is 1 micron or more in width and 1 micron or more in depth.
（３）くぼみ部へのピロール重合物の付着が、該くぼみ
部へ酸化剤を付着させた後、ピロールを接触させること
によりなされる請求項１記載の導電性繊維の製造方法。(3) The method for producing a conductive fiber according to claim 1, wherein the pyrrole polymer is attached to the recessed portions by adhering an oxidizing agent to the recessed portions and then bringing the pyrrole into contact with the recessed portions.
（４）くぼみ部への酸化剤の付着が、該酸化剤のアルコ
ール溶液を用いてなされる請求項３記載の導電性繊維の
製造方法。(4) The method for producing a conductive fiber according to claim 3, wherein the oxidizing agent is attached to the recessed portion using an alcohol solution of the oxidizing agent.
（５）くぼみ部へ酸化剤を付着させるにあたり、酸化剤
を含む溶液にくぼみを有する繊維を含浸後、超音波をか
ける請求項３または４記載の導電性繊維の製造方法。(5) The method for producing conductive fibers according to claim 3 or 4, wherein in order to attach the oxidizing agent to the recessed portion, ultrasonic waves are applied after the fiber having the recessed portion is impregnated with a solution containing the oxidizing agent.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明でいう繊維とは、特に制限はないが、本発明に必
須であるくぼみを付与するには、合成繊維や再生繊維が
より好ましい。具体的には、ボリアリレート、ポリメタ
クリレート、ポリメチルメタクリレート、ポリエチレン
、ポリプロピレン、ポリスチレン、ポリアクリロニトリ
ル、ポリ塩化ビニル、ポリフッ化ビニリデン、ポリエー
テル、ポリエステル、ポリアミド、ポリイミド、シリコ
ン、ポリビニルアルコール、ポリビニルピロリドン、ポ
リアクリルアミド、ポリスルホン、ポリフ工二しンサル
フフイド、ポリウレタン、ポリアクリル酸などの合成繊
維や、セルロース、セルロース誘導体などの再生繊維が
挙げられる。The fibers referred to in the present invention are not particularly limited, but synthetic fibers and regenerated fibers are more preferable in order to provide the recesses that are essential to the present invention. Specifically, polyarylate, polymethacrylate, polymethylmethacrylate, polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polyether, polyester, polyamide, polyimide, silicone, polyvinyl alcohol, polyvinylpyrrolidone, poly Examples include synthetic fibers such as acrylamide, polysulfone, polyphenyl sulfide, polyurethane, and polyacrylic acid, and regenerated fibers such as cellulose and cellulose derivatives.
本発明でいう繊維表面のくぼみとは、該くぼみ部にピロ
ールの重合物を付着させ、ピロール重合体が外的要因の
摩擦などにより、繊維から脱離することを防ぐと同時に
、場合により断面異形化による表面のギラツキを緩和し
、よりマイルドな光沢に変える効果を有するために存在
する形状のものをものをいう。高い導電性を有するピロ
ールの重合物が繊維軸方向につながって存在するために
は、くぼみは繊維軸と平行にかつ筋状で存在することが
好ましい。In the present invention, the dents on the fiber surface mean that a pyrrole polymer is adhered to the dents to prevent the pyrrole polymer from detaching from the fibers due to external factors such as friction, and at the same time, to prevent irregularities in cross-section in some cases. This term refers to a shape that exists to have the effect of reducing the glare on the surface caused by oxidation and giving it a milder luster. In order for the pyrrole polymer having high conductivity to exist continuously in the direction of the fiber axis, it is preferable that the depressions exist parallel to the fiber axis and in the form of streaks.
該くぼみを有する繊維の断面形状は取扱いの面から線ま
たは点対称であることが好ましいが、特にそうでなくて
もよい。The cross-sectional shape of the fibers having the depressions is preferably line- or point-symmetrical from the viewpoint of handling, but this need not be the case.
くぼみは、最低一つめれば、そのくぼみに存在するピロ
ール重合物でかなりの導電性が得られるが、目的の導電
性に応じてピロール重合物が存在する筋状のくぼみを複
数本存在させて導電性を高めても差しつかえない。筋は
導電性を損なわない程度に連続していれば特に長くつな
がっている必要はない。実質的には数ｃｍ以上あれば充
分である。If you look at at least one depression, the pyrrole polymer present in that depression will provide considerable electrical conductivity, but depending on the desired conductivity, multiple streak-shaped depressions containing pyrrole polymers may be created. There is no harm in increasing the conductivity. The streaks do not need to be particularly long as long as they are continuous to the extent that they do not impair conductivity. Substantially, several cm or more is sufficient.
くぼみが多いと、繊維の強度を損なうばかりでなく、使
用している繊維の色が、ピロールの重合物の色である黒
色に支配され、外観上好ましくない。If there are many depressions, not only will the strength of the fiber be impaired, but the color of the fiber used will be dominated by black, which is the color of the polymer of pyrrole, which is unfavorable in terms of appearance.
しかし一方では筋を分散させた方が、前述の表面のギラ
ツキを抑える効果が高くなる。さらに、最終的にピロー
ル重合物が薄く付着するため、黒色が押えられより好ま
しい。However, on the other hand, dispersing the streaks is more effective in suppressing the aforementioned glare on the surface. Furthermore, since the pyrrole polymer is thinly attached in the end, the black color is suppressed, which is more preferable.
かかるくぼみの大きさは、小さすぎるとピロールの重合
物が存在しにくい。そのくぼみの最大幅と最大深さはそ
れぞれ、１ミクロン以上であることが好ましい。くぼみ
の形状はとくに制限はない。If the size of the depression is too small, it is difficult for the pyrrole polymer to exist. Preferably, the maximum width and maximum depth of the depression are each 1 micron or more. There are no particular restrictions on the shape of the depression.
従って用いる繊維形状も特に制限なく、例えばまゆ形、
星形、凹形、Ｔ形、Ｃ形、十形などが挙げられる。ピロ
ー′ルの重合を進めるためには、該くぼみのすくなくと
も一部は繊維表面に出ていることが必要であるが、生成
したピロール重合物が摩擦などにより脱離しないことが
必要であるので、繊維断面におけるくぼみの外周はでき
るだけ繊維の内部にとり込まれておくことが好ましい。Therefore, the shape of the fibers used is not particularly limited, such as eyebrow shape,
Examples include star shape, concave shape, T shape, C shape, and ten shape. In order to proceed with the polymerization of pyrrole, it is necessary that at least a portion of the depressions be exposed on the fiber surface, but it is necessary that the formed pyrrole polymer does not come off due to friction etc. It is preferable that the outer periphery of the depression in the cross section of the fiber be incorporated into the fiber as much as possible.
具体例として第１図（ａ）〜第１図（ｉ）に示す形状が
挙げられるが、これは代表例を示したにすぎずこの゛限
りではない。Specific examples include the shapes shown in FIGS. 1(a) to 1(i), but these are merely representative examples and are not limited thereto.
かかるくぼみの作成方法には、種々の方法が考えられる
。一つは、繊維を紡糸する際に異形断面の口金を用いて
ポリマーを吐出させることで達成される。また、２種類
以上のポリマーを用いて、いわゆるブレンド紡糸や、複
合紡糸を行うことでも容易に達成される。これは、筋状
に分散したポリマーを溶出などの手段で除くことで目的
のくぼみを有する繊維を得るものである。さらには、紡
糸で得られた繊維表面を溶剤で表面処理するなどによっ
ても目的のくぼみを有する繊維は得られる。Various methods can be considered for creating such depressions. One method is achieved by using a spinneret with an irregular cross section to expel the polymer when spinning the fibers. It can also be easily achieved by performing so-called blend spinning or composite spinning using two or more types of polymers. In this method, fibers having the desired dimples are obtained by removing the polymer dispersed in streaks by means such as elution. Furthermore, fibers having the desired dimples can be obtained by surface-treating the fiber surface obtained by spinning with a solvent.
本発明において、上記くぼみにピロール重合物を付着さ
せる方法は、通常のピロール重合法がそのまま適用でき
る。In the present invention, as a method for attaching the pyrrole polymer to the above-mentioned depressions, a normal pyrrole polymerization method can be applied as is.
その一方法として、あらかじめ公知の電解重合法や化学
重合法などによりピロール重合物を製造し、次いで該重
合物をバインダーを用いて繊維表面のくぼみに接着させ
る方法が挙げられる。One method is to produce a pyrrole polymer in advance by a known electrolytic polymerization method or chemical polymerization method, and then adhere the polymer to the recesses on the fiber surface using a binder.
ざらには、くぼみに直接ピロール重合物を作成する方法
も挙げられる。すなわち、酸化剤の存在下で該くぼみを
有する繊維をピロールに接触させることでピロール重合
物が得られる。具体的には、酸化剤を含む溶液に上記繊
維を含浸させることで酸化剤を繊維に付着させた後、ピ
ロールに接触させるなどで行いうる。本方法は、作業の
容易さの点などからより好ましくなる。また、くぼみを
有する繊維を束状で処理する時には、酸化剤を付着させ
るときに、超音波をかけるなどして、束内部のｌ！ｉ維
のくぼみに速やかに酸化剤溶液を浸透させることはより
好ましい。Another example is a method of creating a pyrrole polymer directly in the hollow. That is, a pyrrole polymer can be obtained by bringing the fiber having the depressions into contact with pyrrole in the presence of an oxidizing agent. Specifically, the oxidizing agent can be applied to the fibers by impregnating the fibers in a solution containing the oxidizing agent, and then the fibers can be brought into contact with pyrrole. This method is more preferable from the viewpoint of ease of operation. In addition, when treating fibers with depressions in the form of bundles, when attaching the oxidizing agent, ultrasonic waves are applied to reduce the inside of the bundle. It is more preferable to allow the oxidizing agent solution to quickly penetrate into the recesses of the i-fibers.
本発明でいう酸化剤とは、ピロールを重合させるにあた
って触媒として作用するばかりでなく、時としてドーピ
ング剤として作用するものでありとくに制限はないが、
ピロールの重合速度の点などから好ましい物質として、
各種金属塩、特に金属塩化物が挙げられる。具体例とし
ては、塩化鉄、塩化錫、塩化亜鉛、塩化モリブデン、塩
化アンチモン、塩化アルミニウ゛ムなと種々のものが使
用可能であり、塩化第二鉄がより好ましい。場合によっ
ては、酸化剤や助触媒を共存させてもさしつかえない。The oxidizing agent used in the present invention not only acts as a catalyst in polymerizing pyrrole, but also sometimes acts as a doping agent, and is not particularly limited.
Preferred substances from the viewpoint of polymerization rate of pyrrole include:
Mention may be made of various metal salts, especially metal chlorides. Specific examples include iron chloride, tin chloride, zinc chloride, molybdenum chloride, antimony chloride, and aluminum chloride, with ferric chloride being more preferred. Depending on the case, an oxidizing agent and a co-catalyst may be present together.
この例として、酸化マンガン、酸化鉛、塩化銅などが挙
げられる。さらに、数種の金属塩化物を組み合わせて使
用したり、必要に応じて添加物を加えてもよい。Examples include manganese oxide, lead oxide, copper chloride, and the like. Furthermore, several types of metal chlorides may be used in combination, and additives may be added as necessary.
また、金属化合物を溶解させる溶剤は、特に制限なく、
水、アルコールなど種々のものが使用可能であるが、例
えば塩化第二鉄を用いる場合には、繊維との濡れ性の点
からは、モノあるいは多価アルコールが好ましく、乾燥
が容易で扱い易いといった点からはメタノール、エタノ
ールなどがより好ましい。In addition, there are no particular restrictions on the solvent for dissolving the metal compound.
Various substances such as water and alcohol can be used, but when using ferric chloride, for example, mono- or polyhydric alcohols are preferable from the viewpoint of wettability with fibers, and are easy to dry and handle. From this point of view, methanol, ethanol, etc. are more preferable.
本発明でいうピロール重合物は、導電性を有する高分子
であり、重合を促進する酸化剤の存在下でピロールを重
合することで得られるものである。The pyrrole polymer referred to in the present invention is a polymer having conductivity, and is obtained by polymerizing pyrrole in the presence of an oxidizing agent that promotes polymerization.
通常はポリピロールを指すが、その副生成物を含んでも
よい。ざらには、導電性を有すればポリピロールの誘導
体でもよい。Usually refers to polypyrrole, but may also include its by-products. In general, polypyrrole derivatives may be used as long as they have electrical conductivity.
接触は液体ピロール中への該繊維の含浸、ピロール蒸気
中への該繊維の設置等により達成される。Contacting is accomplished by impregnating the fibers in liquid pyrrole, placing the fibers in pyrrole vapor, and the like.
不純物の廃除、合成速度の制御、合成量の制御、コスト
の点からピロール蒸気中へさらす方法がより好ましい。From the viewpoints of eliminating impurities, controlling the synthesis rate, controlling the amount of synthesis, and cost, the method of exposing to pyrrole vapor is more preferable.
ピロール蒸気中へ金属化合物含有繊維を設＠する温度は
、ピロールの蒸気圧がおる程度おればよい。このときの
ピロールの温度としては、０〜１３０℃が好ましい。繊
維全体に均一にピロール蒸気を充てるためには、５０〜
１３０℃が好ましく、９０〜１２０℃がより好ましい。The temperature at which the metal compound-containing fibers are placed in the pyrrole vapor may be as low as the vapor pressure of the pyrrole. The temperature of pyrrole at this time is preferably 0 to 130°C. In order to uniformly apply pyrrole vapor to the entire fiber, it is necessary to
130°C is preferable, and 90 to 120°C is more preferable.
蒸気温度が低いとピロールの蒸発量が少なく、鉛直方向
に蒸気分布のむらが生じるばかりか、蒸発速度が遅く、
時間がかかつてしまう。また、必要以上の高温は何ら得
策ではない。When the steam temperature is low, the amount of pyrrole evaporates is small, which not only causes uneven vapor distribution in the vertical direction, but also slows the evaporation rate.
It takes time. Also, higher temperatures than necessary are not a good idea.
反応時間は、付着した塩化物の間および目的とする導電
程度に左右されるが、数秒から数分で十分である。The reaction time depends on the amount of conductivity between the attached chlorides and the desired degree of conductivity, but a few seconds to several minutes is sufficient.
本発明では、特に透明性を求める必要がない場合は、特
開昭６３−２０３６１号公報のごとく処理条件は制限さ
れることはない。In the present invention, when there is no particular need for transparency, processing conditions are not limited as in JP-A-63-20361.
かかる処理により、繊維くぼみ内にピロール重合物が生
成し、優れた導電性繊維が得られる。また、該導電性繊
維においては、導電性を生じさせるピロール重合物が繊
維表面のくぼみに存在するため、染色条件下や使用時、
洗）８時においては域的摩擦で該重合物が脱離すること
なく、耐久性に優れた導電性繊維を得ることができる。Through such treatment, a pyrrole polymer is produced within the fiber cavity, resulting in an excellent electrically conductive fiber. In addition, in the conductive fiber, the pyrrole polymer that causes conductivity exists in the hollows on the fiber surface, so under dyeing conditions and during use,
At 8 o'clock (washing), the polymer does not come off due to regional friction, and a conductive fiber with excellent durability can be obtained.
また、本発明により得られた導電性繊維を他の繊維と組
み合わせて全体として導電性、訓電性を持たせることは
もちろん可能でこの場合には、全体としての風合、外観
を損なうことがなくより好ましい。Furthermore, it is of course possible to combine the conductive fibers obtained by the present invention with other fibers to impart conductivity and conductive properties as a whole, and in this case, the overall texture and appearance will not be impaired. It is more preferable than nothing.
本発明の導電性繊維は、静電気が問題となり、制電性が
必要となる衣料分野やカーペットなどの産業用途、導電
性を必要とする産業分野、コンピューター分野など電磁
気遮蔽が必要となる用途に適する。The conductive fiber of the present invention is suitable for applications where static electricity is a problem and requires electromagnetic shielding, such as in the clothing field and carpets, which require antistatic properties, industrial fields that require conductivity, and computer fields. .
以下、本発明による導電性繊維を実施例を用いて説明す
る。Hereinafter, the conductive fiber according to the present invention will be explained using Examples.
なお、実施例中に記載の抵抗値は全て体積比抵抗で示し
ている。In addition, all the resistance values described in the examples are shown in volume specific resistance.
（実施例）
実施例１
ポリエチレンテレフタレートをＡ成分、ポリスチレンを
Ｂ成分とし、米国特許３１８８６８９号に記載する口金
を用いて複合紡糸を行い複合繊維を得た。(Examples) Example 1 Polyethylene terephthalate was used as component A and polystyrene was used as component B, and composite fibers were obtained by performing composite spinning using a spinneret described in US Pat. No. 3,188,689.
次いで、該繊維をトリクレン浴に含浸することでポリス
チレンを除去し、第１図（ａ）に示す異形断面を有する
繊維を得た。Next, the polystyrene was removed by impregnating the fiber in a trichlene bath to obtain a fiber having the irregular cross section shown in FIG. 1(a).
次いで、メチルアルコールを溶剤とした２０％の塩化第
二鉄溶液中に該繊維を超音波をかけつつ１０分間含浸し
た後、７０℃で５分乾燥し、メタノールを除去し、繊維
表面のくぼみに塩化第二鉄を付着させた。Next, the fibers were immersed in a 20% ferric chloride solution using methyl alcohol as a solvent for 10 minutes while applying ultrasonic waves, and then dried at 70°C for 5 minutes to remove methanol. Ferric chloride was deposited.
該塩化第二鉄゛付着繊維を液温１１０℃のピロール液面
上１０ＣＩＩｌにざらしピロールの蒸気をあてたところ
、数秒で該繊維は黒色に変色し、ピロールの重合物生成
が認められた。When the ferric chloride-adhered fibers were exposed to 10 CIIl of pyrrole liquid above the surface of the pyrrole liquid at a temperature of 110° C., the fibers turned black in a few seconds, and the formation of a pyrrole polymer was observed.
該繊維の表面をＳＥＭにより観察したところ、くぼみ内
部にまでピロール重合物が付着していることが確認され
た。When the surface of the fiber was observed by SEM, it was confirmed that the pyrrole polymer was attached even to the inside of the depression.
４端子法により、該繊維の電気抵抗を測定したところ、
処理前には絶縁体でめった繊維は２．７×１０３Ω・ｃ
ｍと良好な導電性を示した。When the electrical resistance of the fiber was measured by the four-terminal method,
Before treatment, the fibers covered with an insulator have a resistance of 2.7 x 103Ω・c.
It showed good conductivity of m.
該繊維は、キャリアを用いた１００℃での通常の染色後
も、同等の優れた導電性を維持し、ざらには摩擦や洗濯
に対しても以下のように優れた導電性保持力を示した。The fiber maintains the same excellent conductivity even after normal dyeing with a carrier at 100°C, and also exhibits excellent conductivity retention against friction and washing as shown below. Ta.
市販品粉末洗剤を用い、家庭用電気洗濯機で本繊維を５
分間洗濯し、次いで５分間脱水した。このサイクルを３
回繰り返した後、電気抵抗を測定したところ、８．５Ｘ
１０３Ω・ｃｍと処理前とほぼ同等の導電性を示した。Using a commercially available powdered detergent, wash the fibers in a household electric washing machine for 5 minutes.
Washed for 5 minutes, then dehydrated for 5 minutes. This cycle is 3
After repeating the test several times, the electrical resistance was measured and found to be 8.5X.
The conductivity was 103Ω·cm, which was almost the same as that before treatment.
洗濯後の繊維表面を再度ＳＥＭで観察したところ、くぼ
み内部に付着していたピロール重合物は、洗濯前と同様
付着したままでおるのが確認された。When the fiber surface after washing was observed again using SEM, it was confirmed that the pyrrole polymer that had adhered to the inside of the hollow remained attached as before washing.
実施例２
Ｃ型の異形口金を用いて、ポリエチレンテレフタレート
を溶融紡糸し、第１図（ｂ）に示す断面を有する繊維を
得た。Example 2 Polyethylene terephthalate was melt-spun using a C-shaped irregular die to obtain a fiber having the cross section shown in FIG. 1(b).
該繊維を実施例１と同様に、２０％塩化第二鉄溶液に１
０分間浸した１９５０℃で５分乾燥し、塩化第二鉄を付
着させた。The fiber was added to a 20% ferric chloride solution in the same manner as in Example 1.
It was soaked for 0 minutes and dried at 1950°C for 5 minutes to adhere ferric chloride.
次いで液温１１０℃のピロール液面上１０Ｃｍにざらし
ピロールの蒸気をあてたところ、数秒で該繊維は黒色に
変色し、ピロールの重合物生成が認められた。Next, when the steam of agarashi pyrrole was applied 10 cm above the surface of the pyrrole liquid at a liquid temperature of 110° C., the fibers turned black in a few seconds, and the formation of a polymer of pyrrole was observed.
４端子法により、該繊維の電気抵抗を測定したところ、
処理前には絶縁体でめった繊維は６．７×１０３０・ｃ
ｍと良好な導電性を示した。When the electrical resistance of the fiber was measured by the four-terminal method,
Before treatment, the fibers covered with an insulator are 6.7×1030・c
It showed good conductivity of m.
さらに、該繊維は、キャリアを用いた１００℃での通常
の染色後、実施例１と同様の耐洗濯テスト後において、
３．９Ｘ１０’Ω・ｃｍの優れた導電性を示し、摩擦や
洗濯に対して耐久性のあることが示された。Furthermore, after normal dyeing at 100°C using a carrier and after a washing resistance test similar to Example 1, the fibers showed
It showed excellent conductivity of 3.9 x 10' Ω·cm and was shown to be durable against friction and washing.
比較例
通常の断面形状が円であるポリエチレンテレフタレート
繊維を２０％塩化鉄水溶液に含浸させた後、水分を蒸発
させ、繊維表面に、塩化鉄を付着させたポリエチレンテ
レフタレート繊維を得た。Comparative Example A polyethylene terephthalate fiber having a normal circular cross-sectional shape was impregnated with a 20% iron chloride aqueous solution, and then water was evaporated to obtain a polyethylene terephthalate fiber with iron chloride adhered to the fiber surface.
該繊維を液温１１０度のピロール液面上１０ＣＩＩＩに
ざらし、ピロール蒸気をあてたところ５秒で繊維表面に
黒色のピロールの重合物が生成した。The fibers were exposed to 10CIII above the surface of the pyrrole liquid at a liquid temperature of 110 degrees Celsius, and pyrrole vapor was applied to the fibers, and a black pyrrole polymer was formed on the fiber surface in 5 seconds.
この状態で４端子方法により電気抵抗を測定したところ
、２．５Ｘ１０３Ω・ｃｍと良好な導電性を示した。When the electrical resistance was measured in this state by a four-terminal method, it showed good electrical conductivity of 2.5×10 3 Ω·cm.
ついで、該繊維を実施例１と同様、キャリヤを用いて染
色したところ表面に生成付着していたピロールの重合物
は繊維から脱離し、電気抵抗測定では、ｙ、ｏｘｉｏ
８Ω・Ｃｍと著しい導電性の劣化が認られた。Then, the fibers were dyed with a carrier in the same manner as in Example 1, and the pyrrole polymer that had formed and adhered to the surface was detached from the fibers, and electrical resistance measurements showed that y, oxio
Significant deterioration in conductivity was observed at 8Ω·Cm.
ｌｌｌＰｌ表面をＳＥＭで観察したところ、洗濯前には
ｌ！ｉＰＬ表面に付着していたピロール重合物が、洗濯
後には、はとんど脱落していることが確認された。When IllPl surface was observed with SEM, lllPl surface was observed before washing. It was confirmed that the pyrrole polymer adhering to the iPL surface was mostly removed after washing.
（発明の効果）
本発明により、高い導電性を有する繊維が、容易に得ら
れる。特に、染色条件下での安定性、耐摩擦性、耐洗濯
性、耐久性に優れた導電性繊維が容易に得られる。(Effects of the Invention) According to the present invention, fibers having high conductivity can be easily obtained. In particular, conductive fibers with excellent stability under dyeing conditions, abrasion resistance, washing resistance, and durability can be easily obtained.
第１図（ａ）〜第１図（１）は、本発明において用いら
れうる異形断面繊維の代表例である。FIG. 1(a) to FIG. 1(1) are representative examples of irregular cross-section fibers that can be used in the present invention.
Claims (5)
ピロールの重合物を付着させることを特徴とする導電性
繊維の製造方法。(1) To the hollow part of the fiber having a hollow on the fiber surface,
A method for producing conductive fibers, which comprises attaching a polymer of pyrrole.
クロン以上である請求項１記載の導電性繊維の製造方法
。(2) The method for producing conductive fibers according to claim 1, wherein the size of the depression is 1 micron or more in width and 1 micron or more in depth.
部へ酸化剤を付着させた後、ピロールを接触させること
によりなされる請求項１記載の導電性繊維の製造方法。(3) The method for producing a conductive fiber according to claim 1, wherein the pyrrole polymer is attached to the recessed portions by adhering an oxidizing agent to the recessed portions and then bringing the pyrrole into contact with the recessed portions.
ール溶液を用いてなされる請求項３記載の導電性繊維の
製造方法。(4) The method for producing a conductive fiber according to claim 3, wherein the oxidizing agent is attached to the recessed portion using an alcohol solution of the oxidizing agent.
を含む溶液にくぼみを有する繊維を含浸後、超音波をか
ける請求項３または４記載の導電性繊維の製造方法。(5) The method for producing conductive fibers according to claim 3 or 4, wherein in order to attach the oxidizing agent to the recessed portion, ultrasonic waves are applied after the fiber having the recessed portion is impregnated with a solution containing the oxidizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63092215A JPH01266280A (en) | 1988-04-14 | 1988-04-14 | Production of electrically conductive yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63092215A JPH01266280A (en) | 1988-04-14 | 1988-04-14 | Production of electrically conductive yarn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01266280A true JPH01266280A (en) | 1989-10-24 |
Family
ID=14048218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63092215A Pending JPH01266280A (en) | 1988-04-14 | 1988-04-14 | Production of electrically conductive yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01266280A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136667A (en) * | 1992-10-26 | 1994-05-17 | Achilles Corp | Electrically conductive clothing article and its production |
| WO2005003446A1 (en) * | 2003-07-03 | 2005-01-13 | Commonwealth Scientific And Industrial Research Organisation | Electroconductive textiles |
| JP2007521405A (en) * | 2003-11-03 | 2007-08-02 | アルバニー インターナショナル コーポレイション | Durable highly conductive synthetic fabric structure |
| JP2009155765A (en) * | 2007-12-27 | 2009-07-16 | Tayca Corp | Low-dusting conductive yarn and process for producing the same |
| JP2017160562A (en) * | 2016-03-10 | 2017-09-14 | ナノサミット株式会社 | Conductive fiber and manufacturing method therefor |
-
1988
- 1988-04-14 JP JP63092215A patent/JPH01266280A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136667A (en) * | 1992-10-26 | 1994-05-17 | Achilles Corp | Electrically conductive clothing article and its production |
| WO2005003446A1 (en) * | 2003-07-03 | 2005-01-13 | Commonwealth Scientific And Industrial Research Organisation | Electroconductive textiles |
| JP2007521405A (en) * | 2003-11-03 | 2007-08-02 | アルバニー インターナショナル コーポレイション | Durable highly conductive synthetic fabric structure |
| JP2009155765A (en) * | 2007-12-27 | 2009-07-16 | Tayca Corp | Low-dusting conductive yarn and process for producing the same |
| JP2017160562A (en) * | 2016-03-10 | 2017-09-14 | ナノサミット株式会社 | Conductive fiber and manufacturing method therefor |
| WO2017155043A1 (en) * | 2016-03-10 | 2017-09-14 | ナノサミット株式会社 | Conductive fiber and method for manufacturing same |
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