EP0667413B1 - Floc pour implantation electrostatique de fibres - Google Patents

Floc pour implantation electrostatique de fibres Download PDF

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Publication number
EP0667413B1
EP0667413B1 EP93922635A EP93922635A EP0667413B1 EP 0667413 B1 EP0667413 B1 EP 0667413B1 EP 93922635 A EP93922635 A EP 93922635A EP 93922635 A EP93922635 A EP 93922635A EP 0667413 B1 EP0667413 B1 EP 0667413B1
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EP
European Patent Office
Prior art keywords
flock
fibers
polymer layer
electrically conductive
conductive polymer
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EP93922635A
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German (de)
English (en)
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EP0667413A4 (fr
EP0667413A1 (fr
Inventor
Ikuo Mizoguchi
Mamoru Ito
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Achilles Corp
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Achilles Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/12—Applying particulate materials
    • B05D1/14—Flocking
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • D06Q1/04—Decorating textiles by metallising
    • 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Definitions

  • the present invention relates to flock to be used for electrostatic pile planting, and more specifically, it relates to flock for electrostatic pile planting which may be used repeatedly in the process of electrostatic pile planting in a constantly dry environment, since it requires no moisture regulation during the process of electrostatic pile planting.
  • the present invention further relates to a method for the production of such flock, and to electrostatically pile-planted goods on the surfaces of which the (originally electrically conductive) flock is planted.
  • electrostatic pile planting refers to the technique of causing shortly cut flock to move by an electrostatic attracting force in an electric field formed by the application of a high voltage and planting it onto a substrate which has been pre-coated with an adhesive, and the flock used in this technique is usually any of a variety of natural, regenerated or synthetic short fibers cut to a length of about 0.5-5 mm.
  • the methods for the pre-coating in flocking conventionally and commonly been carried out include a method wherein the cut fibers are treated with tannin, tartar emetic and the like to maintain the electrical conductivity of their surfaces by means of the water retention characteristics of the tannin compounds formed on their surfaces, and a method wherein a surfactant, sodium silicate, colloidal silica or the like is adhered to the cut fibers to maintain the electrical conductivity of their surfaces by means of the water of crystallization contained in said materials.
  • the former method is adopted mainly in Europe, and the latter in Japan.
  • fibers with an electric leakage resistance value on their surfaces within the range of 10 5 to 10 8 ⁇ /cm are considered to be suitable flock for electrostatic pile planting on which sufficient moving forth is conferred.
  • the conventional flocking-property improvers are not only a factor or instigation of such inconveniences and disadvantages, but they also have drawbacks in that, in the case of tannin and the like, color fastness is low and, in the case of sodium silicate and the like, the planted fibers exhibit a stiff appearance, the adhesion strength of the adhesive used is weakened, and the aging of the fibers is accelerated. In addition, in the latter case, there has been the problem of the production of so-called white dust consisting of silicate dust and so on during the electrostatic pile planting process.
  • White dust is sometimes harmful to human health when absorbed upon inhalation, and it can only be removed under severe conditions of high-temperature, highly concentrated alkali treatment, for example, treatment with a 5 % aqueous solution of sodium hydroxide at 60°C for 30 minutes.
  • the present invention provides flock for electrostatic pile planting which, by eliminating the need for mositure regulation, renders unnecessary the humidity-regulating devices in electrostatic pile planting apparatuses and the step, as pre-treatment, of regulating the moisture of flock as raw material.
  • the present invention relates to flock for electrostatic pile planting which is characterized in that the entire surfaces including the ends of short fibers are substantially or completely coated with an electrically conductive polymer layer.
  • the ratio of the portion of the flock surface which is not coated with said layer to the entire surface is 3 % or less.
  • the electric leakage resistance value of the surface of the flock according to the present invention is preferably adjusted within a range of 10 5 to 10 8 ⁇ /cm.
  • the short fibers consist of natural, semi-synthetic or synthetic fibers, and the aspect ratio thereof is preferably within the range of 1:30 to 1:100.
  • the short fibers may also be colored ones.
  • the electrically conductive polymer layer is a polymer layer or copolymer layer formed by polymerizing one or more monomers selected from the group consisting of pyrrole, N-methylpyrrole, aniline, thiophene and thiophene-3-sulfonic acid, and the particularly preferred is a polymer layer obtained by polymerizing pyrrole as a monomer.
  • the thickness of the electrically conductive polymer layer is preferably or necessarily within a range of 0.01 ⁇ m to 0.1 ⁇ m, as an average.
  • a more desirable thickness is 0.01 ⁇ m to 0.03 ⁇ m as an average when the short fibers are permeable fibers, and 0.02 ⁇ m to 0.05 ⁇ m as an average when they are non-permeable fibers.
  • the present invention further relates to a method for the production of flock for electrostatic pile planting, which comprises allowing the polymerization reaction of monomer(s) in a treating liquid containing short fibers, using a chemical oxidative polymerization agent as catalyst, together with a dopant and/or a surface tension reducing agent which are optionally added, and coating the surfaces of the fibers in said liquid with the resultant electrically conductive polymer layer.
  • the present invention also relates to electrostatically pile-planted goods produced using the above-mentioned flock as raw material, in accordance with the up-type electrostatic pile planting method, the down-type electrostatic pile planting method, the up/down-type electrostatic pile planting method, or the side-type electrostatic pile planting method, or by means of a electrostatic pile planting apparatus of fluidizing tank type.
  • Fig. 1 is a microphotograph showing the tip of a piece, enlarged by an electron microscope, of the conventional flock for electrostatic pile planting consisting of polyester fibers which have undergone the pre-coating in flocking with sodium silicate.
  • the length of the white line in the lower right-hand section of the photograph is 50 ⁇ m.
  • Fig. 2 is a microphotograph showing the tip of a piece, enlarged by an electron microscope, of the flock for electrostatic pile planting according to the present invention consisting of polyester fibers (fineness: 1.5 deniers) the entire surface of which, including the ends, have been completely coated with a pyrrole polymer layer.
  • the length of the white line in the lower right-hand section of the photograph is 20 um.
  • Fig. 3 is a microphotorgaph showing the tip of a pre-colored filament, enlarged by an electron microscope, of the same polyester fiber as shown in Fig. 2 (but on the surfaces of which no pyrrole polymer layer is formed).
  • the length of the white line in the lower right-hand section of the photograph is 20 ⁇ m.
  • the flock according to the present invention is substantially or completely coated with an electrically conductive polymer layer on the circumferential faces along the entire length of the fibers and at both front and back ends thereof, thereby enabling the electric leakage resistance value of its surface to be adjusted within a range of 10 5 to 10 8 ⁇ /cm.
  • the ratio of the portion of the flock surface not coated with the electrically conductive polymer layer to the entire surface is 3 % or less.
  • the fibers may be of natural, regenerated (semi-synthetic) or synthetic type, and convenient fibers include aromatic polyamide fibers (trade names: Kevlar, Nomex, Konex, etc.), other polyamide fibers (6-nylon, 6,6-nylon, 4,6-nylon, etc.), regular polyester fibers, cation dyeable polyester fibers, acrylic fibers, vinylon fibers, regenerated cellulose fibers (rayon), wool fibers, cotton fibers, flax fibers, and polyethylene, polypropylene as well as other composite spun fibers, and so on. Further, the fibers may be colored, and there may be used so-called pre-colored fibers which have been colored during the spinning stage with pigments incorporated.
  • the above-mentioned fibers having the properties of a denier value of about 1 to 65 d, a fiber length of about 0.3 to 6.0 mm, and an aspect ratio of 1:30 to 1:100 are preferable.
  • the fibers having an aspect ratio greater than 1:100 uniform electrostatic pile planting may not be achieved at times.
  • fibers with a fiber length (mm) of 0.3 times the denier value are said to be most suitable as raw material fibers for flock for electrostatic pile planting.
  • the electrically conductive polymer layer may be a layer of a polymer or copolymer prepared by the polymerization of, for instance, pyrrole, N-methylpyrrole, aniline, thiophene, thiophene-3-sulfonic acid or a derivative thereof as a monomer, but any polymer layer may be used so long as it confers the above-mentioned electrical conductivity.
  • the monomers to be used to form said electrically conductive polymer layer may include, for instance, aniline and aniline derivatives such as o-chloroaniline, m-chloroaniline, p-chloroaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-ethoxyaniline, m-ethoxyaniline, p-ethoxyaniline, o-methylaniline, m-methylaniline and p-methylaniline; thiophene and thiophene derivatives such as 3-methylthiophene and 3-methoxythiophene; and pyrroles including various substituted pyrroles such as, 3,5-substituted pyrroles like 3,5-dimethylpyrrole, 3,4-substituted pyrroles like methyl 4-methylpyrrole-3-carboxylate, N-substituted pyrrole like N-methylpyrrole, as well as
  • a preferred electrically conductive polymer layer is a polymer layer or copolymer layer prepared by the polymerization of pyrrole, N-methylpyrrole, aniline, thiophene or thiophene-3-sulfonic acid as a monomer.
  • Particularly preferred one from the viewpoint of adhesion strength to fibers, degree of electrical conductivity, processing properties and so on, is a polymer layer obtainable by the polymerization of pyrrole as a monomer.
  • the thickness of the electrically conductive layer may basically be optional, so long as the layer exhibits the above-mentioned electrical conductivity and appropriate separability, etc. Nonetheless, where the thickness of the electrically conductive polymer layer is less than 0.01 ⁇ m as an average, it is difficult to form an electrically conductive polymer layer with uniform thickness owing to the influence of the coarseness of the surfaces of the fibers themselves, often resulting in conferring insufficient electrical conductivity to flock for obtaining satisfactory moving force.
  • the thickness of the polymer layer is over 0.1 ⁇ m as an average, the fastness to crocking of said layer is reduced and, as the thickness becomes greater, the resistance value becomes smaller than required and the electrical conductivity becomes larger, even if the required electrical conductivity is secured, and in consequence, sparks are generated during electrostatic pile planting by the proximity or contact of the flock pieces, that sometimes causes clearly recognizable irregularity in the pile density on the surfaces of the pile-planted goods.
  • the thickness as an average of the electrically conductive polymer layer is preferably or necessarily within the range of 0.01 ⁇ m to 0.1 ⁇ m. Since the layer is such a ultra-thin film, there is no major impairment in the original appearance, flexibility, etc. of the fibers, by the presence of the layer. For instance, when such flock is used in a weatherstrip on an automobile window glass, the weatherstrip with a stable rubbing resistance value is obtainable, since the original elasticity of the fibers is retained because of the extremely rare hardening of the fibers.
  • the monomer to be used for the preparation of the polymer should be added in a proportion of about 0.3 % to about 1.0 % relative to the weight of the fibers, though the amount may vary slightly depending on the type of the fibers.
  • pyrrole a type of monomer
  • a pyrrole polymer layer with an average thickness of 0.044 ⁇ m (calculated value) is formed on the surfaces around and both ends of the fibers.
  • the thickness of the electrically conductive polymer layer formed on the surfaces of the fibers will vary depending on the condition (coarseness) of the fiber surface, and the porosity, the composition, etc. of the fibers.
  • an electrically conductive polymer layer is formed with an average thickness almost equal to the thickness as calculated on the basis of the amount of the added monomer
  • permeable fibers such as 6-nylon fiber, 6,6-nylon fiber and vinylon fiber
  • the layer is formed with an average thickness somewhat smaller than the thickness as calculated on the basis of the amount of the added monomer.
  • the thickness of the layer also varies depending on the dispersing condition and so on of the fibers in a treating liquid as described below.
  • Preferable thickness of the electrically conductive polymer layer is generally about 0.01 to 0.03 ⁇ m in the case of permeable fibers such as nylon fiber, vinylon fiber, cellulose fiber, and about 0.02 to 0.05 ⁇ m in the case of non-permeable fibers such as polyester fiber, aramid fiber and acrylic fiber.
  • Such electrically conductive polymer layer as described above is formed by carrying out polymerization reaction of a monomer in a treating liquid containing short fibers, using an oxidative polymerization agent as catalyst, thereby the resulting electrically conductive polymer binds with the fibers in the liquid to coat their surfaces.
  • the present invention relates to a process for the production of flock for electrostatic pile planting, which comprises allowing polymerization reaction of monomer(s) to proceed in a treating liquid containing short fibers (which may be colored), using a chemical oxidative polymerization agent as catalyst, together with a dopant and/or a surface tension reducing agent which are optionally added, thereby coating the surfaces of the fibers in the liquid with the resulting electrically conductive polymer.
  • the monomer and the chemical oxidative polymerization agent may be added to the liquid together or in the order of the monomer first and then the agent. Further, the agent as catalyst may be added all at once or in portions, or may be added continuously in a small amount.
  • the polymerization reaction of the monomer is preferably effected as slowly as possible. It is preferably effected under the condition of low temperature, at 2-35°C, more preferably at 2-25°C.
  • the polymerization reaction is carried out while stirring or circulating the treating liquid.
  • solubility of the monomer decreases as the polymerization proceeds, the resulting polymer is selectively deposited or adhered to the surfaces of the fibers. As a result, the reaction is extremely quantitative.
  • all the surfaces, including the ends thereof, of the short fibers are required to be substantially coated with the electrically conductive polymer layer, preferably in a uniform thickness.
  • the flock according to the present invention is most preferably prepared by the polymerization reaction of the monomer for the pre-coating in flocking in a slurry-state treating liquid, while stirring or circulating it, to form an electrically conductive polymer layer on the surfaces of the fibers.
  • the fibers are present in the slurry-state treating liquid in a weight ratio to said slurry of 1:8-15.
  • the stirring speed is not specifically restricted, but, owing to the necessity of preventing sedimentation of the flock, it should be higher in the case of using, for example, polyester fibers than in the case of using polyamide fibers.
  • Monomers selected from pyrrole, N-methylpyrrole, aniline, thiophene and thiophene-3-sulfonic acid are preferably used alone or in combination of two or more. Pyrrole is the most preferred.
  • any substance which accelerates the polymerization of the above-mentioned monomers may be used in general.
  • Such substances may be, for instance, persulfuric acid as well as persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; ferric salts such as ferric chloride, ferric perchloride, ferric sulfate, ferric nitrate, ferric periodate, ferric citrate and ferric p-toluenesulfonate; permanganic acid as well as permanganates such as potassium permanganate; chromates such as chrome trioxide; halogens such as chlorine, bromine and iodine; peroxides such as hydrogen peroxide and benzoyl peroxide; and metal chlorides such as copper chloride. Water-soluble ferric salts are particularly preferred.
  • the chemical oxidative polymerization agent to be used may be any of the above-mentioned compounds, alone or in an appropriate combination, and is used normally in a ratio of about 1 to 3 moles per mole of the monomer.
  • a dopant may also be used optionally for the purpose of enhancing the electrical conductivity of the fibers.
  • the dopant is preferably used under the condition of pH 1-5, more preferably pH 1-3.
  • Suitable dopants may include, for example, p-toluenesulfonic acid, benzenesulfonic acid, monochlorobenzenesulfonic acid, dichlorobenzenesulfonic acid, trichlorobenzenesulfonic acid, naphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, sulfosalicylic acid and other aromatic sulfonic acids; perchloric acid, hydrochloric acid, sulfuric acid, nitric acid and trifluorosulfonic acid. An aromatic sulfonic acid or an alkali metal salt thereof is particularly preferred.
  • a surface tension reducing agent may further be added for the formation of a uniform film of the electrically conductive polymer on the fiber surface.
  • the surface tension reducing agent may be a surfactant, and in addition, it may be an organic solvent or anti-forming agent of silicon-type, acetylene glycol-type or of fluorine-type.
  • Surfactants are used to improve the wettability of the fiber surface, and alcohols are additionally added so as to improve the wettability of fiber surface upon mixture with water.
  • the above-mentioned surfactants may include, for example, anionic surfactants such as sodium alkyl sulfates, sodium alkylbenzenesulfonates, sodium alkylsulfosuccinates, sodium polyoxyalkylenesulfonates and sodium alkylnaphthalenesulfonates; and nonionic surfactants such as polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers and polyethylene glycol alkylphenyl ethers.
  • anionic surfactants such as sodium alkyl sulfates, sodium alkylbenzenesulfonates, sodium alkylsulfosuccinates, sodium polyoxyalkylenesulfonates and sodium alkylnaphthalenesulfonates
  • nonionic surfactants such as polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers and polyethylene glycol alky
  • the above-mentioned organic solvents may include, for example, alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol and isoamyl alcohol; as well as dimethylformamide, tetrahydrofuran, dioxane, acetonitrile, cyclohexanone, methyl ethyl ketone and acetone.
  • alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol and isoamyl alcohol
  • dimethylformamide tetrahydrofuran, dioxane, acetonitrile, cyclohexanone, methyl ethyl ketone and acetone.
  • the amount of the surface tension reducing agent to be added may be a minute amount to a small amount, and for example, an amount of about 0.01 % to about 2 % to the total weight of the treating liquid is sufficient in the case of a surfactant, and about 0.1 % to about 5.0 % in the case of an alcohol.
  • the polymerization of the above-mentioned monomer conveniently proceeds under the pH condition ranging 1-4, in said range the desired electrically conductive polymer being obtained efficiently.
  • the fibers are washed with water after the completion of the polymerization, and, on that occasion, a small amount of a softening agent, smoothing agent or the like, such as stearic acid amide, may be added if necessary to prevent the entanglement of flock pieces and to improve their conveyability by a screw or the like in the feeding path from the storage tank in the electrostatic pile planting apparatus.
  • a softening agent, smoothing agent or the like such as stearic acid amide
  • non-colored polyester fibers are used as raw material fibers
  • the pre-coating in flocking may be carried out after the coloring or before the coloring.
  • said coloring since alkali coloring of polyester fibers causes dedoping and, thus, reduces the electrical conductivity, said coloring, if carried out, should be carried out before the above-mentioned pre-coating, and it is preferable to wash the colored fibers with an acid by way of precaution.
  • alkali coloring after said pre-coating should be carried out under acidic condition.
  • flock with a variety of color tones is obtainable due to blending of the color phase of the dye used and the color phase of the electrically conductive polymer.
  • the dyes to be used may vary depending on the fiber, but may include, for example, acidic dyes, metal complex dyes such as chrome complex dye, dispersion dyes, cationic dyes and reactive dyes.
  • coloring with a dispersion dye requires reductive washing, which accelerates dedoping of the electrically conductive polymer, and thus, the pre-coating in flocking should be carried out after the coloring.
  • other fibers such as polyamide fibers and acrylic fibers, no reductive washing is required.
  • the fibers are dried after said pre-coating, and for the drying of flock, it is most preferable to use the fluidiz- ing tank-type drying method in which slurry-state flock or flock after dehydrated from the slurry-state by centrifugal separation is dried by contact with a hot air flow in a fluidizing tank, so as to minimize the entanglement of flock pieces.
  • the drying according to this method may be carried out under the conditions of a temperature about 120-180°C and a residence time in the tank of 0.1-5 seconds, for more favorable operation. When the drying is effected under such conditions, the flock according to the present invention having the moisture of about 1-5 % is easily obtainable.
  • the flock according the present invention is produced through the steps as described above.
  • the moisture regain of said flock is usually about 1 to 5 %, close to the official regain, which is distinctively lower than the moisture regain of 20 to 25 % (value for flock after-conditioned and planted) of the conventional flock.
  • the flock is lighter, and the transportation and handling thereof is facilitated.
  • the electrically conductive polymer layer is substantially not affected by moisture, the moisture regain remains almost unchanged at about 1 to 5 % even if the surrounding air is of a high humidity, and thus, the flock of the present invention is constantly maintained in almost absolute dry state. As a result, the color fastness of the flock is improved and the transportation costs are reduced.
  • the area of both ends of the raw material fibers may essentially be ignored, since it is as small as 1-3 % relative to the entire surface area due to the large aspect ratio of said fibers.
  • D/M 2.5x wherein x is ranging from 1 to 100.
  • the preferable range of the D/M ratio is about 2-4 for the raw material fibers of 3 deniers, about 10-20 for the raw material fibers of 15 deniers, and about 150-250 for the raw material fibers of 65 deniers.
  • the above equation particularly applies in the case of polyester fibers, nylon fibers, acrylic fibers and so on.
  • the flock according to the present invention may be used in the electrostatic pile planting in the conventional manner, enabling the production of a wide variety of electrostatically pile-planted goods.
  • the method of electrostatic pile planting is not particularly restricted, and there may be employed any of the up-type electrostatic pile planting method (a method in which the flock is placed on a lower electrode and the material to be planted is arranged at an upper electrode, and a voltage is applied between the upper and lower electrodes to cause the flock to move upward), the down-type electrostatic pile planting method (a method in which the material to be planted is arranged at a lower electrode and a linear or lattice-shaped upper electrode is used, and while a voltage is applied between the upper and lower electrodes, the flock is allowed to fall down through the lattice holes of the upper electrode, thereby it move downward) and the side-type electrostatic pile planting method (a method in which the material to be planted is arranged in connection with electrode on a side of the electric field, and the flock is discharged from a hopper into the electric field while
  • pile planted goods such as automobile interior parts
  • a fluidizing tank-type electrostatic pile planting apparatus an apparatus wherein there is employed as supply tank a fluidizing tank so constructed that a porous sheet is placed therein and vibrations are applied thereto, and it may be of up/down-type, side-type, etc.
  • the present invention further relates to the electrically pile-planted goods which are prepared by electrically planting the above-mentioned flock as raw material on the surface to be planted of substrates according to the up-type, down-type or side-type electrostatic pile planting method or by means of the fluidizing tank-type electrostatic pile planting apparatus.
  • the surface electric leakage resistance value of the flock may easily be adjusted within the range accepted to be suitable for electrostatic pile planting because the flock surface is substantially coated with the electrically conductive polymer layer, and the exhibition of such antistatic function enables to use this flock, which is obtained in almost absolute dry state, in electrostatic pile planting.
  • the present invention particularly in the case of the flock of which entire surface, including not only the circumferential face but also both front and rear ends, is covered with the electrically conductive polymer layer, it is possible to make it more reliable to plant the flock at a right angle to the surface of the substrate to be pile-planted, and that enables to reduce the ratio of producing defective goods and to produce pile-planted goods with higher quality. It is thought that, in the electrostatic pile planting, the application of a high voltage creates the positive charge at one end of the flock and the negative charge at the other end to produce clearer polarization and, therefore, the flock is planted at a right angle to the substrate surface to be pile-planted.
  • the separability (manageability) of the flock does not receive any such adverse affect as to cause problems by the raising and falling of the moisture and humidity of the surroundings. Therefore, it does not cause any such inconveniences as the tacky flock surface, the formation of doughy masses resulting from twisting and entanglement of the flock pieces, and the generation of sparks resulting from the contact between the flock pieces.
  • a satisfactory moving force is always obtainable during the electrostatic pile planting process because the electrical conductivity and the separability of the flock may stably be maintained within the aimed range and conditions with no substantial influence by the surrounding moisture, and thus, stable electrostatic pile planting may be carried out by any pile planting method.
  • the flock is in almost absolute dry state and, accordingly, it may be used repeatedly in the electrostatic pile planting in a dry environment, thus enabling the continuous electrostatic pile planting to be carried out smoothly and stably.
  • the present invention does not require at all the regulation of moisture in the flock (the after-conditioning) which has been carried out in the conventional electrostatic pile planting, and besides, it renders such measures as the humidity-regulating device in the electrostatic pile planting device and the step, as pre-treatment, for regulating moisture in the flock as raw material, unnecessary.
  • Cut 6,6-nylon fibers (fineness: 3 deniers, fiber length: 0.5 mm) were colored with a metal complex dye: Kayakalan Black (a product of Nihon Kayaku K.K.) under the conditions of 95°C for 60 minutes, and then well washed with water.
  • a metal complex dye Kayakalan Black (a product of Nihon Kayaku K.K.)
  • Pyrrole monomer was used in an amount of 0.63 % in weight ratio relative to the fibers, and the polymerization thereof was carried out continuously in water at 5°C for 240 minutes, using ammonium persulfate as catalyst, while stirring together with the colored 6,6-nylon fibers in the water. Then, the 6,6-nylon fibers were well washed with water and subsequently dried to the moisture of 2.5 %.
  • the surface electric leakage resistance value of the resulting flock was measured to be 3 x 10 6 ⁇ /cm.
  • Cut acrylic fibers (fineness: 1.3 deniers, fiber length: 0.4 mm) were well pre-washed with water to remove the surfactant, oils and the like, and put into water, to which 0.35 % (weight ratio relative to the fibers) of N-methylpyrrole and 0.3 % (weight ratio relative to the fibers) of pyrrole were then added as monomers, and the polymerization was carried out continuously at 5°C for 200 minutes, using ferric chloride as catalyst. Then, the acrylic fibers were well washed and dried to the moisture of 2.5 %.
  • the surface electric leakage resistance value of the resulting flock was measured to be 7 x 10 7 ⁇ /cm.
  • Example 1 the electrostatic pile planting was carried out under the conditions analogous to Example 1, and good moving force and satisfactory results were obtained in any of the planting methods, as in Example 1.
  • Cut 6-nylon fibers (fineness: 1.5 deniers, fiber length: 0.5 mm) were colored with a milling-type dye: Kayanol Milling Black (a product of Nihon Kayaku K.K.) under the conditions of 90°C for 60 minutes, and then well washed with water.
  • Aniline p-toluenesulfonate was used as a monomer in an amount of 1.0 % in weight ratio relative to the fibers, the polymerization thereof was carried out continuously in water at 5°C for an adequate period of time,using potassium persulfate as catalyst, while stirring together with the colored 6-nylong fibers in the water. Then, the 6-nylon fibers were well washed with water and dried to the moisture of 3.5 %.
  • the surface electric leakage resistance value of the resulting flock was measured to be 1 x 10 8 ⁇ /cm.
  • Example 1 the electrostatic pile planting was carried out under the conditions analogous to Example 1, and good moving force and satisfactory results were obtained in any of the planting methods, as in Example 1.
  • Cut para-aromatic polyamide fibers (fineness: 2.0 deniers, fiber length: 0.5 mm) and 0.5 %, in weight ratio relative to the fibers, of pyrrole monomer were put into water, and the polymerization was carried out continuously at 3°C for 240 minutes, while stirring, using ammonium persulfate as catalyst. Then, the fibers were well washed and dried to the moisture of 1.0 %.
  • the resulting flock was dark green, and its surface electric leakage resistance value was measured to be 3 x 10 7 ⁇ /cm.
  • Example 1 the electrostatic pile planting was carried out under the conditions analogous to Example 1, and good moving force and satisfactory results were obtained in any of the planting methods, as in Example 1.
  • Polyethylene terephthalate fibers (fineness: 15 deniers, fiber length: 2.1 mm) were colored with a dispersion dye: Kayalon Polyester Black (a product of Nihon Kayaku K.K.) under the conditions of 130°C for 60 minutes, and were then washed reductively with a mixed hydrosulfite/sodium hydroxide solution at 60°C for 20 minutes. Then, the pre-coating in flocking was carried out in the conventional manner using sodium silicate to prepare flock for pile planting.
  • a dispersion dye a product of Nihon Kayaku K.K.
  • the moisture regain of the flock was adjusted to 0.5 %, 3.0 % and 18 %, and the planting (applied voltage: 60 kV) was carried out onto the same substrate as the one in Example 1.
  • the planting applied voltage: 60 kV
  • moisture regains of 0.5 % and 3.0 % only insufficient moving force was obtained and uniform planting could not be achieved.
  • moisture regain of 18 % though planting is effected to some extent, it was not possible to carry out the continuous planting by repeating the collection and re-using of the flock.
  • Example 4 1.0 % Up 60 kV o ⁇ No. 11
  • Example 4 1.0 % Down 60 kV o ⁇ No. 12
  • Example 4 1.0 % 60 kV o ⁇ No. 13 0.5 % 60 kV x No. 14 3.0 % 60 kV x No. 15 18 % 60 kV o
  • "o ⁇ " indicates that the flock obtained sufficient moving force and the planting was uniform and very good.
  • o indicates that the flock obtained necessary moving force and the planting was good while the continuous planting was not possible.
  • " x indicates that the flock did not obtain necessary moving force and the planting was not good.
  • the electric leakage resistance value of the resulting flock was 4.0 x 10 5 ⁇ /cm, and the moisture regain was 1.5 %.
  • electrostatic pile planting was carried out (applied voltage: 50-80 kV) by means of an up-type, a down-type, a fluidizing tank- side-type, and a fluidizing tank-up/down-type planting apparatuses, and the flock showed a sufficiently high moving force and high quality electrostatically pile-planted goods were obtained in any of the planting methods, without any particular after conditioning.
  • Figs. 1-3 are microphotographs showing the tips of the flock pieces or the like in the above examples, enlarged by an electron microscope.
  • the length of the white line in the lower right-hand section of the photograph is 50 ⁇ m (Fig. 1) or 20 ⁇ m (Figs. 2 and 3).
  • Fig. 1 shows the conventional flock for electrostatic pile planting, comprising polyester fiber which has been subjected to the pre-coating in flocking with sodium silicate
  • Fig. 2 shows the flock according to the present invention corresponding to Example 5, comprising polyester fiber (fineness: 1.5 deniers) the entire surface of which is coated with a pyrrole polymer layer
  • Fig. 3 shows a pre-colored filament (no pyrrole polymer layer is formed on its surface) of the polyester fiber which is the raw material for the flock in Fig. 2.
  • 6,6-nylon continuous fibers (fineness: 3 deniers) were rolled up onto a bobbin, which was then placed in a tank together with a treating liquid consisting of 20 liters of water, 13.4 g of pyrrole and 64.9 g of ferric chloride, and said liquid was repeatedly passed through the bobbin and through the gaps between fibers to give them electrical conductivity, thereby obtaining long fibers having the surface electric leakage resistance value of 1.0 x 10 6 ⁇ /cm.
  • the long 6,6-nylon fibers thus treated were cut to 0. 5 mm, and planted electrostatically in the same manner and conditions as those in Example 1.
  • the flock obtained sufficient moving force and the continuous planting was possible, although there were recognized on the planted goods a few fibers not planted at a right angle to the substrate surface.
  • the flock according to the present invention may be used in electrostatic pile planting in general, and are suitable for the production of various kinds of electrostatically pile-planted goods for a wide range of uses, including interior materials for construction (wallpapers, curtains, carpets, mats, etc.), footwear (Japanese sandals, clog thongs, etc.), daily goods (decorative covers, decorative cords, jewel cases, stationery, etc.), goods for automobiles (dashboards, sun visors, weather-strips, flocky yarn for car sheets, etc.), air conditioner/heaters, warmers with quilts on them, foot warmers, etc.), clothing (hats, jackets, gloves, etc.) and electronic devices (brush rolls, etc.).

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Artificial Filaments (AREA)

Claims (16)

  1. Agent de flocage destiné à une implantation de poils électrostatique, caractérisé en ce que les surfaces entières comprenant les extrémités de courtes fibres sont en majeure partie ou complètement revêtues d'une couche de polymère électriquement conducteur.
  2. Agent de flocage selon la revendication 1, caractérisé en ce que le rapport de la partie de la surface de l'agent de flocage qui n'est pas revêtue de la couche de polymère électriquement conducteur sur la surface entière est de 3 % ou moins.
  3. Agent de flocage selon la revendication 1 ou 2, caractérisé en ce que la couche de polymère électriquement conducteur est une couche de polymère ou de copolymère formé par la polymérisation d'un ou plusieurs monomères sélectionnés à partir du pyrrol, du N-méthylpyrrol, de l'aniline, du thiophène et de l'acide thiophène-3-sulfonique.
  4. Agent de flocage selon la revendication 3, caractérisé en ce que la couche de polymère électriquement conducteur est une couche d'un polymère formé par la polymérisation du pyrrol en tant que monomère.
  5. Agent de flocage selon l'une quelconque des revendications précédentes, caractérisé en ce que l'épaisseur de la couche de polymère électriquement conducteur est dans la plage entre 0,01 µm et 0,1 µm en moyenne.
  6. Agent de flocage selon l'une quelconque des revendications précédentes, caractérisé en ce que l'épaisseur de la couche de polymère électriquement conducteur est dans la plage entre 0,01 µm et 0,03 µm en moyenne, lorsque les courtes fibres sont des fibres perméables, et d'environ 0,02 µm à 0,05 µm en moyenne lorsqu'il s'agit de fibres non perméables.
  7. Agent de flocage selon l'une quelconque des revendications précédentes, caractérisé en ce que les courtes fibres comprennent des fibres naturelles, semi-synthétiques ou synthétiques, et que le rapport de forme des fibres est entre 1:30 et 1:100.
  8. Agent de flocage selon l'une quelconque des revendications précédentes, caractérisé en ce que la résistance de fuite électrique en surface de l'agent de flocage est dans la plage de 105 Ω/cm à 108 Ω/cm.
  9. Agent de flocage selon l'une quelconque des revendications précédentes, caractérisé en ce que les courtes fibres sont colorées.
  10. Procédé de production de l'agent de flocage pour une implantation de poils électrostatique selon la revendication 1 ou 2, comprenant le fait de laisser la réaction de polymérisation d'un monomère ou de monomères se dérouler dans un liquide de traitement contenant de courtes fibres, en utilisant un agent de polymérisation oxydant chimique en tant que catalyseur, de même qu'un dopant et/ou un agent de réduction de tension superficielle qui sont ajoutés optionnellement, en revêtant ainsi les surfaces des fibres dans le liquide de traitement par la couche de polymère électriquement conducteur qui en résulte.
  11. Procédé selon la revendication 10, dans lequel un ou plusieurs monomères sélectionnés à partir du pyrrol, du N-méthylpyrrol, de l'aniline, du thiophène et de l'acide thiophène-3-sulfonique sont utilisés en tant que monomère ou monomères.
  12. Procédé selon la revendication 11, dans lequel le pyrrol est utilisé en tant que monomère.
  13. Procédé selon l'une quelconque des revendications 10 à 12, dans lequel les courtes fibres sont colorées.
  14. Procédé selon l'une quelconque des revendications 10 à 12, dans lequel l'agent de polymérisation oxydant chimique utilisé en tant que catalyseur est un sel ferrique soluble dans l'eau.
  15. Procédé selon l'une quelconque des revendications 10 à 12, dans lequel, après la réaction de polymérisation, les fibres revêtues sont rincées avec de l'eau de même qu'avec un agent d'adoucissement ou un agent de lissage.
  16. Articles à implantation de poils électrostatique produits par une implantation de poils électrostatique à la surface d'un substrat devant recevoir l'implantation de poils, en utilisant l'agent de flocage pour implantation de poils électrostatique selon l'une quelconque des revendications 1 à 9.
EP93922635A 1992-10-23 1993-10-15 Floc pour implantation electrostatique de fibres Expired - Lifetime EP0667413B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP30952192 1992-10-23
JP309521/92 1992-10-23
PCT/JP1993/001481 WO1994010371A1 (fr) 1992-10-23 1993-10-15 Floc pour implantation electrostatique de fibres

Publications (3)

Publication Number Publication Date
EP0667413A1 EP0667413A1 (fr) 1995-08-16
EP0667413A4 EP0667413A4 (fr) 1995-12-27
EP0667413B1 true EP0667413B1 (fr) 1998-07-15

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EP93922635A Expired - Lifetime EP0667413B1 (fr) 1992-10-23 1993-10-15 Floc pour implantation electrostatique de fibres

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EP (1) EP0667413B1 (fr)
KR (1) KR950704564A (fr)
CN (1) CN1111170A (fr)
DE (1) DE69319738T2 (fr)
TW (1) TW253920B (fr)
WO (1) WO1994010371A1 (fr)

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EP1518471B1 (fr) 2002-06-28 2015-06-03 S.T. Corporation Gants retenant l'humidite et procede de fabrication
CN1295731C (zh) * 2002-11-25 2007-01-17 财团法人工业技术研究院 场发射源组件的金属性纳米丝或纳米管的植入方法
JP5256454B2 (ja) * 2006-02-28 2013-08-07 国立大学法人山梨大学 導電性高分子の処理方法
EP3389057A1 (fr) 2007-11-27 2018-10-17 Uppsala Universitets Projekt AB Matériaux composites comportant un polymère intrinsèquement conducteur et procédés et dispositifs
GB2475714A (en) * 2009-11-27 2011-06-01 Pangaea Lab Ltd Hair building solids
CN101844872B (zh) * 2010-05-07 2012-05-02 上海长悦涂料有限公司 一种植绒液的制备方法
CN109023989A (zh) * 2018-09-06 2018-12-18 山东领潮新材料有限公司 一种天然抗菌防霉的麻纤维静电植绒面料及其制备方法
CN109763317A (zh) * 2019-01-16 2019-05-17 广东顺德贰发毛绒有限公司 一种防尘绒毛的电着处理工艺
CN109734905B (zh) * 2019-02-13 2022-02-08 东北大学 一种增强电催化剂性能的部分结晶共聚物制备方法和应用

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JPS5497647A (en) * 1978-01-19 1979-08-01 Unitika Ltd Electrostatic flocking
US4975317A (en) * 1987-08-03 1990-12-04 Milliken Research Corporation Electrically conductive textile materials and method for making same
US4803096A (en) * 1987-08-03 1989-02-07 Milliken Research Corporation Electrically conductive textile materials and method for making same
JP2986857B2 (ja) * 1989-08-29 1999-12-06 アキレス株式会社 導電性繊維基材の製造方法
JPH0726333B2 (ja) * 1990-04-11 1995-03-22 アキレス株式会社 導電性繊維の製造方法

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Publication number Publication date
EP0667413A4 (fr) 1995-12-27
EP0667413A1 (fr) 1995-08-16
TW253920B (fr) 1995-08-11
DE69319738D1 (de) 1998-08-20
KR950704564A (ko) 1995-11-20
CN1111170A (zh) 1995-11-08
WO1994010371A1 (fr) 1994-05-11
DE69319738T2 (de) 1999-01-07

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