EP2242064B1 - Fibre électriquement conductrice et brosse - Google Patents

Fibre électriquement conductrice et brosse Download PDF

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Publication number
EP2242064B1
EP2242064B1 EP09251108.8A EP09251108A EP2242064B1 EP 2242064 B1 EP2242064 B1 EP 2242064B1 EP 09251108 A EP09251108 A EP 09251108A EP 2242064 B1 EP2242064 B1 EP 2242064B1
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EP
European Patent Office
Prior art keywords
conductive
carbon black
fiber
component
particle size
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.)
Not-in-force
Application number
EP09251108.8A
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German (de)
English (en)
Other versions
EP2242064A1 (fr
Inventor
Yoshiki Shirakawa
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.)
Teijin Ltd
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Teijin Ltd
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Publication date
Application filed by Teijin Ltd filed Critical Teijin Ltd
Priority to EP09251108.8A priority Critical patent/EP2242064B1/fr
Priority to PL09251108T priority patent/PL2242064T3/pl
Publication of EP2242064A1 publication Critical patent/EP2242064A1/fr
Application granted granted Critical
Publication of EP2242064B1 publication Critical patent/EP2242064B1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent

Definitions

  • conductive carbon black As fibers having static elimination performance, for example, conductive carbon black has hitherto been caused to be contained to impart conductive performance (patent document 1 and patent document 2). Like this, the carbon black has been widely used because of its low price and excellent conductivity. However, there has been the problem of large resistance fluctuations in the conductive resistance range of 10 8 to 10 12 ⁇ /cm, namely in a so-called middle to high resistance region. This is caused by a conductivity expression mechanism of the carbon black. When the carbon black is low in concentration, it has no conductivity. However, when it exceeds a certain degree of concentration, conductivity is rapidly expressed.
  • the above-mentioned conductive resistance range of 10 8 to 10 12 ⁇ /cm just corresponds to between the expression of conductivity and the saturation thereof, and there has been the problem of the easy occurrence of fluctuations in conductivity of the carbon black even when the carbon black has the same concentration.
  • Patent document 3 discloses a "composition of fluoropolymer and dispersed conductive particulate [that] provides an electrically conductive polymeric material resistant to static charge buildup".
  • Patent document 4 discloses a "[m]olding composition [that] has electroconductive cellulose fibers in a polymer matrix”.
  • Patent document 5 discloses a "conductive thermoplastic composition [that] includes a polycarbonate, a polyester, a conductive filler, an impact modifier, a transesterification quench, and glass fibers".
  • An object of the present invention is to provide a conductive polyester fiber containing conductive carbon black as a conductive substance, which fiber has small fluctuations in conductive performance and stable conductive performance.
  • the present invention relates to a conductive polyester fiber containing carbon black as a main conductive component in the polyester, wherein the carbon black is composed of a mixture of at least two kinds of the following carbon blacks (A) and (B) at an A/B ratio (by weight) of 90/10 to 10/90:
  • the conductive polyester fiber of the present invention contains the carbon black having at least two kinds of characteristics at the time of imparting conductivity, thereby being able to provide the conductive fiber having a more stable resistance value.
  • matrix polymers with which conductive carbon black is mixed include a polyester such as polyethylene terephthalate. These matrix polymers maybe copolymerized with a third component, and may contain a delustering agent such as titanium dioxide. For example, copolymerization of isophthalic acid or adipic acid in an amount of about 10 to 20 mol% based on the whole acid components is preferred in terms of fiber-making properties. Further, ethylene glycol may be changed to a glycol component such as trimethylene glycol, tetramethylene glycol, 1,5-pentanediol or 1, 6-hexanediol, or such a glycol component may be copolymerized.
  • a glycol component such as trimethylene glycol, tetramethylene glycol, 1,5-pentanediol or 1, 6-hexanediol, or such a glycol component may be copolymerized.
  • the conductive polyester fiber of the present invention is a sheath-core type composite fiber.
  • the conductive component may be arranged in either a core or a sheath.
  • the ratio of the conductive component is usually in the range of 10 to 20% by weight of the whole fiber in terms of fiber-making properties and cost.
  • fiber-making properties and fiber strength are particularly excellent.
  • the delustering agent is caused to be contained in the sheath polymer, excellent aesthetic properties are preferably obtained.
  • the conductive component is arranged in the sheath, it is preferred in that the value of surface resistance of the conductive fiber is equalized.
  • a polymer other than the conductive component is herein composed of a polyester, especially polyethylene terephthalate, has good texture, excellent handling properties in a processing process and good chemical resistance. Further, although the polyester is characterized in that the stiffness of the fiber is high compared to nylon and the like, the good results of improving toner scraping properties are obtained particularly by adjusting the Young's modulus to 70 cN/dtex or more when the fiber is used as a brush used in a copying machine.
  • the conductive fiber of the present invention is caused to contain carbon black in order to impart conductivity.
  • carbon black there can be used known one, for example, acetylene black, oil furnace black thermal black channel black, Ketchen black or carbon nanotubes. These can be usually dispersed in matrix polymers to use.
  • matrix polymers the above-mentioned various polyesters are used.
  • the carbon black used as the conductive component is a mixture of at least two or more kinds of carbon blacks each having different characteristics.
  • the average particle size of one carbon black (A) is from 20 to 70 nm, and preferably from 30 to 60 nm.
  • the average particle size is less than 20 nm, it is difficult to homogeneously disperse the carbon black in the matrix polymer, resulting in a decrease in process yield such as an increase in yarn breakage due to coagulation at the time of fiber making.
  • the average particle size exceeds 70 nm, a larger amount of carbon black becomes necessary for obtaining desired conductive performance, as well as the problem of yarn breakage at the time of fiber making. This is also unfavorable in cost.
  • the oil absorption of carbon black (A) which is defined in JIS K 5101, is from 100 to 600 ml/100 g, and preferably from 150 to 300 ml/100 g.
  • the oil absorption is less than 100 ml/100 g, the structure of the carbon black excessively develops, resulting in a decrease in process yield such as an increase in yarn breakage due to a decrease in fluidity.
  • the degree of development of the structure is low, so that a large amount of carbon black becomes necessary for expressing conductivity. This unfavorably causes a cost rise.
  • conductive carbon black (A) can be used either alone or as a combination of two or more thereof.
  • Commercial products of conductive carbon black (A) include "Ketchen Black” manufactured by Mitsubishi Chemical Corporation such as “EC300J” (average particle size:39.5 nm) and “EC600JD” (average particle size:34.0 nm), “TOKABLACK(TM)” manufactured by Tokai Carbon Co., LTD.
  • conductive carbon black (B) in which the average particle size ratio thereof to the above-mentioned conductive carbon black (A) is from 1.1 to 3, and the oil absorption ratio thereof to the above-mentioned conductive carbon black (A) is from 0.9 to 0.2 is blended, thereby stabilizing the conductive resistance.
  • the average particle size ratio is less than 1.1, there is no effect of stabilizing the conductive resistance. Accordingly, it is necessary to blend the carbon black having an average particle size ratio of 1.1 or more. On the other hand, when the ratio exceeds 3, fiber-making performance extremely decreases.
  • conductive carbon black (B) can be used either alone or as a combination of two or more thereof.
  • Commercial products of conductive carbon black (B) include "Ketchen Black” manufactured by Mitsubishi Chemical Corporation such as “EC300J” (average particle size: 39.5 nm) and “EC600JD” (average particle size: 34.0nm), “TOKABLACK(TM)” manufactured by Tokai Carbon Co., Ltd.
  • the (A)/(B) ratio (by weight) is usually from 90/10 to 10/90, and preferably from 30/70 to 70/30 although it depends on a desired resistance region.
  • the conductive resistance is stabilized. The reason for this is not clear at the present time. However, it is believed that the behavior of changes in electric conductivity to the amount of carbon blacks added becomes slow, compared to the case where the carbon black is singly used, by blending the carbon blacks different in particle size and structure development.
  • the carbon black comprising the above-mentioned components (A) and (B) to be blended with the conductive component is added preferably in an amount of 10 to 35% by weight, and more preferably in an amount of 10 to 25% by weight. Less than 10% by weight results in no increase in electric conductivity, whereas exceeding 35% by weight results in poor fluidity, which is unfavorable in terms of a fiber-making process.
  • the amount of the conductive carbon black added is appropriately adjustable depending on the kind of carbon black used.
  • FIG. 1 shows the conductive polyester fiber in which the conductive carbon black mixture comprising at least two kinds of components (A) and (B) is homogeneously blended with the polyester acting as a matrix component to form the whole cross section of the fiber as a conductive component.
  • Figs. 2 to 4 show examples of the sheath-core type conductive composite fibers, wherein the reference numeral 1 denotes a sheath component, and the reference numeral 2 denotes a core component.
  • Figs. 2 and 4 show examples in which a conductive component is disposed as the core component, and Fig.
  • the core component may be in modified cross section as shown in Fig. 4 .
  • the ratio of a portion in which the core component is not covered with the sheath component is 5% or less of the whole periphery of the sheath component. If the ratio of the portion in which the core component is not covered with the sheath component exceeds 5%, the core and the sheath are separated from each other, or the conductive carbon black component drops off, resulting in a high possibility of causing contamination.
  • the mixture of at least two kinds of the above-mentioned carbon blacks (A) and (B) is homogeneously blended with the polyester acting as a matrix component in an amount of 10 to 35% by weight to form the whole cross section of the fiber as a conductive component.
  • the mixture of at least two kinds of the above-mentioned carbon blacks (A) and (B) is caused to be contained in the core component in an amount of 10 to 35% by weight.
  • the mixture of at least two kinds of the above-mentioned carbon blacks (A) and (B) may be caused to be contained in the sheath component in an amount of 10 to 35% by weight.
  • the conductive polyester fiber of the present invention has static elimination performance excellent in fiber physical properties and durability in actual use, and can be suitably used as charging brushes, static eliminating brushes and cleaning brushes incorporated in OA equipment such as copying machines and printers.
  • a brush having static elimination performance is obtained, for example, by weaving the conductive fiber of the present invention as a pile fabric, backing it with a backing agent having conductivity, and then, wrapping a pile tape cut to a width of 10 to 30 mm around a cylindrical metal rod, or simply adhering the pile fabric to a plate to make it in brush form.
  • the oil absorption was measured based on JIS K 5101.
  • the average particle size of carbon black was measured using a laser diffraction type size distribution measuring apparatus, SALD-200V ER, manufactured by Shimadzu Corporation.
  • the strength and elongation of a fiber was measured based on JIS L 1013.
  • conductive carbon black (A) ("Denka Black FX-35” manufactured by Denki Kagaku Kogyo Kabushiki Kaisha) having an average particle size of 26 nm and an oil absorption of 220 ml/100g and 9 parts by weight of conductive carbon black (B) ("Denka Black HS-100” manufactured by Denki Kagaku Kogyo Kabushiki Kaisha) having an average particle size of 48 nm and an oil absorption of 140 ml/100g were blended with 81 parts by weight of polyethylene terephthalate copolymerized with isophthalic acid in an amount of 15 mol%.
  • conductive carbon black (A) (“Denka Black FX-35" manufactured by Denki Kagaku Kogyo Kabushiki Kaisha) having an average particle size of 26 nm and an oil absorption of 220 ml/100g was blended with 85 parts by weight of polyethylene terephthalate used in Example 1. Melt extrusion was performed using this composition as a core component and polyethylene terephthalate as a sheath component at a weight ratio of 10/90 to obtain a sheath-core type composite filament yarn of 50 dtex/24 filaments having a cross section as shown in Fig. 2 . This operation was repeated three times to obtain 3 composite filament yarns, for each of which the cross-sectional resistance value was measured. As a result, the resistance value was in the range of 5 ⁇ 10 9 to 7 ⁇ 10 10 ⁇ /cm to show a variation.
  • the conductive fiber of the present invention contains conductive carbon black as a conductive substance, and has stable conductive performance with a small variation in its conductive performance, so that it has static elimination performance excellent in fiber physical properties and durability in actual use, and can be suitably used as charging brushes, static eliminating brushes and cleaning brushes incorporated in OA equipment such as copying machines and printers.

Claims (3)

  1. Fibre de polyester conductrice contenant du noir de carbone comme composant conducteur principal dans le polyester, le noir de carbone étant composé d'un mélange d'au moins deux types des noirs de carbone (A) et (B) suivants dans un rapport (en poids) A/B de 90/10 à 10/90 :
    (A) un noir de carbone conducteur ayant une taille moyenne de particule de 20 à 70 nm et une absorption d'huile définie en GIS K 5101 de 100 à 600 ml/100 g ; et
    (B) un noir de carbone conducteur ayant un rapport entre la taille moyenne de particules de celui-ci et ledit noir de carbone conducteur (A) de 1,1 à 3, et un rapport entre l'absorption d'huile de celui-ci et ledit noir de carbone conducteur (A) de 0,9 à 0,2,
    la fibre de polyester conductrice étant une fibre composite de type gaine-âme,
    et le composant âme de la fibre composite de type gaine-âme contenant le mélange d'au moins deux types de noirs de carbone (A) et (B) dans une quantité de 10 à 35 % en poids.
  2. Fibre de polyester conductrice selon la revendication 1, caractérisée en ce que la valeur de résistance transversale est de 108 à 1012 Ω/cm.
  3. Brosse utilisant la fibre de polyester conductrice selon la revendication 1 ou la revendication 2.
EP09251108.8A 2009-04-16 2009-04-16 Fibre électriquement conductrice et brosse Not-in-force EP2242064B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP09251108.8A EP2242064B1 (fr) 2009-04-16 2009-04-16 Fibre électriquement conductrice et brosse
PL09251108T PL2242064T3 (pl) 2009-04-16 2009-04-16 Elektrycznie przewodzące włókna i szczotki

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09251108.8A EP2242064B1 (fr) 2009-04-16 2009-04-16 Fibre électriquement conductrice et brosse

Publications (2)

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EP2242064A1 EP2242064A1 (fr) 2010-10-20
EP2242064B1 true EP2242064B1 (fr) 2013-08-28

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PL (1) PL2242064T3 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2020263599A1 (en) * 2019-04-26 2021-11-25 Ecofibre USA Inc. Hemp-based char or oils and polymers formed as fibers or films having enhanced properties

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6673864B2 (en) * 2000-11-30 2004-01-06 General Electric Company Conductive polyester/polycarbonate blends, methods for preparation thereof, and articles derived therefrom
DE10336473A1 (de) * 2003-08-08 2005-03-03 Degussa Ag Elektrisch leitfähige Kunststoffe
JP2005194650A (ja) 2004-01-05 2005-07-21 Nippon Ester Co Ltd 導電性複合繊維
JP2006009177A (ja) 2004-06-24 2006-01-12 Toray Ind Inc 導電性複合断面繊維およびブラシ
US7381765B2 (en) * 2004-11-08 2008-06-03 Freudenberg-Nok General Partnership Electrostatically dissipative fluoropolymers

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EP2242064A1 (fr) 2010-10-20
PL2242064T3 (pl) 2014-01-31

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