EP3187653B1 - Method for manufacturing surface-modified fiber material - Google Patents

Method for manufacturing surface-modified fiber material Download PDF

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Publication number
EP3187653B1
EP3187653B1 EP15825331.0A EP15825331A EP3187653B1 EP 3187653 B1 EP3187653 B1 EP 3187653B1 EP 15825331 A EP15825331 A EP 15825331A EP 3187653 B1 EP3187653 B1 EP 3187653B1
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EP
European Patent Office
Prior art keywords
fibrous material
titania
treatment
plasma
attached
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EP15825331.0A
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German (de)
English (en)
French (fr)
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EP3187653A1 (en
EP3187653A4 (en
Inventor
Yasuo Ozawa
Shinichi Kuroda
Katsuhiko Hosoi
Tsunenori OZAWA
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Silk Wave Sangyo Co Ltd
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Silk Wave Sangyo Co Ltd
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    • 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
    • D06M19/00—Treatment of feathers
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
    • D06B23/14—Containers, e.g. vats
    • D06B23/16—Containers, e.g. vats with means for introducing or removing textile materials without modifying container pressure
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/84—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising combined with mechanical treatment
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B2700/00—Treating of textile materials, e.g. bleaching, dyeing, mercerising, impregnating, washing; Fulling of fabrics
    • D06B2700/27—Sizing, starching or impregnating fabrics
    • 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
    • D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/02—Treating compositions in the form of solgel or aerogel

Definitions

  • the present invention relates to a method of manufacturing a surface-modified fibrous material (hereinafter, also simply referred to as "manufacturing method") and a surface-modified fibrous material. More particularly, the present invention relates to a method of manufacturing a surface-modified fibrous material for obtaining a highly functional fibrous material, by enhancing the functionality of a natural fibrous material derived from an animal or a plant, or a synthetic fiber, by surface modification; and a surface-modified fibrous material thereby obtained.
  • Patent Document 1 discloses a titanium oxide-containing natural fiber in which the surface of the fiber is plated with titanium oxide, and a method of manufacturing the same.
  • Patent Document 1 WO 98/053132 .
  • US3620802A discloses a method of producing fabric duplicating ribbons formed from synthetic thermoplastic filaments.
  • JPH0116293B discloses a product comprising feathers with alumina sol deposited on the suface.
  • JPS5216977A discloses a method adsorping particles to a fabric treated with low-temperature plasma.
  • US2008/190841A1 discloses a ceramic membrane which is adhered to a polymeric non-woven material.
  • US2011/180387A1 discloses a method of treating plasma by using air flow to prevent localised plasma discharges and burning of material.
  • Patent Document 1 has not been sufficient, and realization of a surface-modified fibrous material with higher functionality has been demanded.
  • an object of the present invention is to provide a method of manufacturing a highly functional surface-modified fibrous material with high added value, to which a novel functionality is imparted while making use of the characteristics inherent in the fibrous material, by modifying the surface of a natural fibrous material derived from an animal or a plant, or of a synthetic fiber; and a surface-modified fibrous material thereby obtained.
  • the method of manufacturing a surface-modified fibrous material according to the present invention comprises attaching an inorganic material on the surface of a natural fibrous material by a sol-gel reaction, while allowing the fibrous material to move via an air stream, wherein an atmospheric-pressure low-temperature plasma is applied to the surface of the fibrous material on the surface of which an inorganic material has been attached, while allowing the fibrous material to move via an air stream.
  • preferred examples of the inorganic material include titania, alumina, and ceramic.
  • feathers, a powder or a microfiber made from cocoons, silk, wool, cotton, hemp, pulp, orespecially feathers, can be suitably used.
  • the surface-modified fibrous material according to the present invention is characterized by being manufactured by the above described manufacturing method according to the present invention.
  • titania is used as an inorganic material to be attached on the surface of a fibrous material by sol-gel reaction.
  • a specific description will be given below regarding the case in which titania is attached on the surface of a fibrous material by a sol-gel reaction of a titanium compound, while allowing the fibrous material to move via an air stream, in order to carry out a surface modification of the fibrous material.
  • titania is attached on the surface of a fibrous material while allowing the fibrous material to move via an air stream, a uniform treatment can be applied to the entire fibrous material.
  • the surface modification can be carried out while maintaining the shape and the characteristics inherent in the fibrous material, particularly in a natural fiber, it is possible to obtain a surface-modified fibrous material having a high quality. Therefore, by using the surface-modified fibrous material obtained according to this embodiment as a raw material, it is possible to realize a surface-modified fibrous product with high added value, in which the functionality of the fibrous material is utilized.
  • a treatment for attaching titania (TiO 2 , molecular weight: 79.87) to the surface of a fibrous material in this embodiment can be carried out, for example, by using titanium tetraisopropoxide (TTIP, molecular weight: 284.22) as the titanium compound, according to the following sol-gel reaction.
  • FIG. 1 shows a schematic diagram of a treatment apparatus used for applying the titania-attaching treatment to the surface of a fibrous material, in the method of manufacturing a surface-modified fibrous material according to this embodiment.
  • the treatment apparatus shown in FIG. 1 includes: an apparatus body 11 for carrying out the treatment; a feed inlet 12 for introducing the fibrous material into the apparatus body 11, a discharge outlet 13 for discharging the treated fibrous material from the apparatus body 11; and an introduction port 14 for introducing the titanium compound into the apparatus body 11.
  • the introduction of the fibrous material into the apparatus body 11 and the discharging of the fibrous material from the apparatus body 11 are carried out via an air stream.
  • air is allowed to flow, for example at a speed of from 500 to 5,000 cm/s, particularly at about 2,000 cm/s, so that the fibrous material is allowed to move with the flowing air.
  • an opening may be provided at the upper portion or the like of the apparatus body 11, and the fibrous material may be directly fed into and retrieved from the apparatus body through the opening, and the method thereof is not particularly limited.
  • the titanium compound After introducing the fibrous material into the treatment apparatus 11, the titanium compound is introduced into the treatment apparatus 11 through the introduction port 14.
  • the compound can be introduced into the apparatus body 11 in the form of a mist, by spraying a solution of the titanium compound in an alcohol or the like via the introduction port 14.
  • the solution of the titanium compound By injecting the solution of the titanium compound at a high pressure, at this time, it is possible to generate a transporting air stream rotating within the apparatus body 11 in the direction of height, and titania generated by the above described sol-gel reaction can be attached on the surface of the fibrous material filled in the apparatus body 11, while allowing the fibrous material to move via the transporting air stream.
  • an atmospheric-pressure low-temperature plasma be further applied to the surface of the fibrous material on the surface of which titania has been attached. This allows titania attached on the surface of the fibrous material to be strongly fixed to the surface of the fibrous material, and thus it is possible to reliably prevent the peeling off of titania during the handling of the fibrous material after the surface modification, and to maintain the functionality imparted to a synthetic fiber or a natural fiber for a long period of time.
  • the atmospheric-pressure low-temperature plasma as used herein refers to a plasma which is generated under atmospheric pressure and at normal temperature of about 40°C or lower.
  • a pressure reduction is not required in the present invention, and thus the cost of facility and the treatment can be reduced.
  • Such an atmospheric-pressure low-temperature plasma irradiation treatment can be carried out, for example using an atmospheric-pressure normal-temperature plasma jet generator, CAPPLAT, manufactured by Cresur Corporation.
  • a gas for generating a plasma jet is not particularly limited, and any of various types of commonly used gases can be used. However, argon gas is preferred in terms of cost.
  • FIG. 2 shows a schematic diagram of a treatment apparatus used for applying a plasma irradiation treatment to the titania-attached fibrous material, in the method of manufacturing a surface-modified fibrous material according to the embodiment.
  • the treatment apparatus shown in FIG. 2 includes: an apparatus body 21 for carrying out the treatment; a feed inlet 22 for introducing the titania-attached fibrous material into the apparatus body 21; a discharge outlet 23 for discharging the treated titania-attached fibrous material from the apparatus body 21; an irradiation device 24 for applying plasma to the fibrous material in the apparatus body 21; and a gas inflow port 25 for allowing air to flow into the apparatus body 21.
  • the introduction of the titania-attached fibrous material into the apparatus body 21 and the discharging of the titania-attached fibrous material from the apparatus body 21 are carried out via an air stream.
  • air is allowed to flow, for example at a speed of from 500 to 5,000 cm/s, particularly at about 2,000 cm/s, so that the fibrous material is allowed to move with the flowing air.
  • the introduction of air from the gas inflow port 25 allows for generation of a transporting air stream rotating within the apparatus body 21 in the direction of height. Therefore, in this embodiment, the plasma irradiation treatment can also be performed while allowing the titania-attached fibrous material to move via the transporting air stream, thereby allowing for a uniform application of the treatment to the entire titania-attached fibrous material.
  • the treatment can be carried out while alternately switching between the introduction and discharge of the fibrous material into and out of the apparatus body, and between the introduction of the titanium compound and the introduction of air, in each of the apparatuses.
  • the fibrous material is first introduced into the apparatus body 11 or 21 through the feed inlet 12 or 22 via an air flow, with the introduction port 14 or the gas inflow port 25, and the discharge outlet 13 or 23 closed. Then the feed inlet 12 or 22 is closed, a titanium compound or air is introduced through the introduction port 14 or the gas inflow port 25, and the titania-attaching treatment or the plasma irradiation treatment is carried out.
  • the introduction port 14 or the gas inflow port 25 is closed, and the treated fibrous material is retrieved from the discharge outlet 13 or 23.
  • the treatment of the fibrous material can be carried out in batches.
  • the positions of the feed inlet 12, the discharge outlet 13 and the introduction port 14 to be provided on the apparatus body 11, as well as the positions of the feed inlet 22, the discharge outlet 23, the irradiation device 24, and the gas inflow port 25 to be provided on the apparatus body 21, are not limited to those in the examples shown in FIG. 1 and FIG. 2 , and the positions may be changed as desired and as appropriate.
  • the interior of the apparatus such as a nozzle and the like, be cleaned with an alcohol or the like after the titania-attaching treatment, to maintain the apparatus clean.
  • any natural fibrous material can be used.
  • the invention enables the manufacture of a surface-modified fibrous material, using as a base material, a natural fiber, namely, a natural fibrous material derived from an animal or a plant.
  • a natural fiber namely, a natural fibrous material derived from an animal or a plant.
  • the fibrous material derived from an animal or a plant include feathers, a powder or a microfiber made from cocoons, silk, wool, cotton, hemp, and pulp.
  • the powder made from cocoons refers to a powder of silk, so to speak, obtained by crushing the cocoons themselves, not by drawing a thread of raw silk from the cocoons; and the microfiber made from cocoons refers to minute fuzz attached on the surface of the cocoons.
  • the silk as used herein includes both a single silk thread drawn from cocoons and a spun silk yarn, and also includes a silk thread obtained by a specialized method, such as SILKWAVE (trade name (registered trademark, manufactured by Mapepe Co. Ltd.), and the like. Further, fibrous materials obtained from fibrous raw materials which are used for paper products in general are also included in the present invention.
  • the attachment of titania provides an effect of increasing the bulkiness of the fibrous material itself.
  • the quality of feathers is represented by their bulkiness (filling power). Therefore, the application of the present invention to feathers provides an advantage of serving to provide high quality and low cost feathers, by enabling to significantly increase the bulkiness of the feathers, and thus to obtain a high quality feathers from low quality and low cost feathers.
  • the treatment when the titania-attaching treatment of 2 t of down using TTIP is carried out for 20 days per month (160 hs), the treatment can performed at a cost of 70,000 to 700,000 yen/month, to achieve the amount of titania supported on the down of from 0.1 to 1% by mass. Further, an additional cost in the case of using the atmospheric-pressure low-temperature plasma in combination is about 60,000 yen/month. Thus, an advantage of low manufacturing cost can be provided.
  • Another embodiment of the present invention may be, for example, one in which alumina is used as the inorganic material to be attached on the surface of the fibrous material by the sol-gel reaction.
  • the same operation as in the above described embodiment can be carried out except for using an aluminum compound, preferably aluminum isopropoxide, instead of the titanium compound in the above embodiment.
  • the effect of increasing the bulkiness of the fibrous material itself can be obtained by the attachment of alumina, in the surface-modified fibrous material obtained according to the another embodiment as well.
  • the attachment of alumina to feathers provides an advantage of serving to provide high quality and low cost feathers, by enabling to significantly increase the bulkiness of the feathers, and thus to obtain a high quality feathers from low quality and low cost feathers.
  • Still another embodiment of the present invention may be, for example, one in which a ceramic is used as the inorganic material to be attached on the surface of the fibrous material by the sol-gel reaction.
  • the same operation as in the above described embodiment can be carried out, except for using a ceramic compound instead of the titanium compound in the above described embodiment.
  • the effect of increasing the bulkiness of the fibrous material itself can be obtained by the attachment of a ceramic, in the resulting surface-modified fibrous material as well. Accordingly, as with the case of attaching titania or alumina, the attachment of a ceramic to feathers enables to significantly increase the bulkiness of the feathers, and thus to obtain a high quality feathers from low quality and low cost feathers.
  • TTIP titanium tetraisopropoxide
  • the weights of methanol and the Ti sol before and after spraying for 1 minute were measured 3 times at an N 2 pressure of about 0.07 MPa, and the measured values were averaged to obtain a mean value, thereby confirming the liquid spray velocity of the nozzle.
  • the liquid spray velocity was 11.4 g/min in the case of methanol.
  • the liquid spray velocity of the Ti sol was 8.5 g/min, which was slightly decreased probably due to high viscosity, but not significantly different, as compared to that of methanol.
  • the titania-attaching treatment was applied to down as a fibrous material, using a treatment apparatus having the configuration shown in FIG. 3 .
  • the treatment apparatus shown in FIG. 3 includes an apparatus body 31 for carrying out the attachment of titania to down; an injection inlet 32 for injecting air; a discharge outlet 33 for discharging the treated down from the apparatus body 31; and an introduction port 34 for introducing TTIP into the apparatus body 31.
  • a blower 36 is connected through a valve 35.
  • a nozzle 37 for spraying a titanium compound is disposed to the introduction port 34, and a flow passage 39a connected to the nozzle 37 is configured to be able to communicate with a flow passage 39b on the side of the atmosphere, or with a flow passage 39c on the side of the titanium compound, by switching a three-way cock 38.
  • the flow passage 39c is further configured to be able to communicate with a flow passage 39d on the side of the Ti sol or a flow passage 39e on the side of methanol, by switching a three-way cock 40, and an N 2 balloon 43 is connected to a Ti sol container 41 and a methanol container 42.
  • the discharge outlet 33 is connected to a storage container 44 for storing the treated down. Still further, an opening 45 for feeding down is provided on the upper portion of the apparatus body 31, and mesh portions M for discharging gas are each provided on the upper portion of the apparatus body 31, and on the upper portion of the storage container 44.
  • the three-way cock 40 was switched so as to allow communication between the flow passage 39c on the side of three-way cock 38 and the flow passage 39d on the side of the Ti sol.
  • the three-way cock 38 was switched so as to allow communication between the flow passage 39a connected to the nozzle 37 and the flow passage 39c, and a mist of the Ti sol was sprayed into the apparatus body 31 for 15 seconds.
  • the titania-attaching treatment was applied to the surface of the down, while allowing the down to move rotationally within the apparatus body 31 in the direction of height.
  • the three-way cock 40 was switched so as to allow communication between the flow passage 39c on the side of the three-way cock 38, and the flow passage 39e on the side of methanol, to wash the nozzle 37 with methanol.
  • the three-way cock 38 was switched so as to allow communication between the flow passage 39a connected to the nozzle 37 and the flow passage 39b on the side of the atmosphere, to discharge methanol remaining in the nozzle 37.
  • the flow of N 2 gas was terminated, the opening 45 and the mesh portion M provided on the upper portion of the apparatus body 31 were closed, and the blower 36 was activated with the valve 35 open, to transfer the treated down to the storage container 44.
  • FIG. 4(a) and FIG. 4(b) show the photographs of the Ti gel
  • FIG. 5(a) and FIG. 5(b) show the photographs of untreated down
  • FIG. 5(c) and FIG. 5(d) show the photographs of titania-attached down, all obtained by a digital microscope (VHX-600; manufactured by KEYENCE CORPORATION).
  • VHX-600 manufactured by KEYENCE CORPORATION
  • FIG. 7 (a) and FIG. 7 (b) show the spectral graphs showing the analysis results of EDX (energy dispersive X-ray spectroscopy) measurements of (a) the untreated down, and (b) the titania-treated down. It can be seen from the results that, no titanium is detected in the untreated down in the EDX measurement as well, while on the other hand, titanium is detected in the deposited portion of the titania-attached down. These results confirmed that there is hardly any difference in the shape between the titania-treated down and the untreated down, and that titania is covering the down as a uniform film.
  • EDX energy dispersive X-ray spectroscopy
  • the plasma irradiation treatment to the titania-attached down was carried out using a treatment apparatus having the configuration shown in FIG. 8 .
  • the treatment apparatus shown in FIG. 8 includes an apparatus body 51 for carrying out the plasma irradiation treatment to down; an injection inlet 52 for injecting air; a discharge outlet 53 for discharging the treated down from the apparatus body 51; an irradiation device 54 for applying plasma to the down in the apparatus body 51; and a gas inflow port 55 for allowing air to flow into the apparatus body 51.
  • a blower 56 is connected to the injection inlet 52 for injecting air.
  • the discharge outlet 53 is connected to a storage container 58 for storing the treated down, through a valve 57.
  • a bag made of fabric is used as the storage container 58.
  • an opening 59 for feeding down and a mesh portion M for discharging gas are provided on the upper portion of the apparatus body 51.
  • the irradiation device 54 is connected to a high voltage power supply HV.
  • an atmospheric-pressure normal-temperature plasma jet generator, CAPPLAT, (manufactured by Cresur Corporation) equipped with a quadruple plasma torch system as shown in FIG. 9 was used as the irradiation device 54.
  • the quadruple plasma torch system shown in FIG. 9 includes four plasma torches 61 which are disposed in parallel at intervals of 40 mm.
  • reference numeral 62 denotes an acrylic plate
  • reference numeral 63 denotes a connector
  • reference numeral 64 denotes a vinyl chloride tube.
  • FIG. 10 shows a partial sectional view of the configuration of the plasma torch 61. As shown in FIG.
  • the plasma torch 61 includes a glass capillary 65; a Cu pipe (outer diameter: 8 mm, inner diameter: 7 mm, high voltage electrode) 66 covering the outer periphery of the glass capillary 65; a double-layered silicone tube (outer diameter: 12 mm, inner diameter: 8 mm; and outer diameter: 16 mm, inner diameter: 12 mm) 67 covering one end of the Cu pipe 66; and a silicone tube 68 covering the glass capillary 65 at the other end side of the Cu pipe 66.
  • a pinch cock 69 is attached to the silicone tube 68, and a Cu tape (width: 20 mm, earth electrode) 70 and a metal mesh (150 mesh) 71 are disposed on the side of the double-layered silicone tube 67 of the plasma torch 61.
  • the plasma irradiation was carried out by applying a voltage of ⁇ 8kV in the form of pulses, at 20 kHz, and using Ar gas as the plasma gas at 20 LPM (l/min).
  • Ar gas was supplied to the plasma torches of the irradiation device 54 and a high voltage was applied thereto, and then plasma was applied to the down for 30 seconds, while allowing the down to move rotationally within the apparatus body 51 by air in the direction of height. Subsequently, the supply of Ar gas and air was terminated, the mesh portion M was closed, and the blower 56 was activated with the valve 57 open, to transfer the treated down to the storage container 58.
  • a quantity of 20 g of down subjected to the titania-attaching treatment and the plasma irradiation treatment, and 20 g of untreated down were used to prepare the comforter samples of Example 1 and Comparative Example, respectively, each having a size of 500 mm ⁇ 380 mm.
  • the evaluation of these comforter samples was carried out as follows.
  • a ribbon heater (diameter: 80 mm, height: 40 mm) was adjusted to about 40°C by a variable transformer. After measuring the temperature of each of the comforters before heating, a ribbon heater 82 adjusted to 40°C was placed under a comforter 81 so that the ribbon heater 82 was positioned at the central portion of the comforter 81, as shown in FIG. 11(a) , and the ribbon heater 82 was left to stand on a mat 83. Then a paper guide 84 as shown in FIG.
  • FIG. 12(a) and FIG. 12(b) are graphs showing the measurement results of the temperature of the top surface of the comforters at location 1 of the paper guide, with respect to: (a) the temperature; and (b) the temperature change.
  • FIG. 13(a) and FIG. 13(b) are explanatory diagrams showing the state of temperature change at respective portions of the comforters of: (a) Example 1; and (b) Comparative Example; 55 minutes after the start of the heating.
  • FIG. 14(a) and FIG. 14(b) are graphs showing the changes in the internal temperature of the comforters, with respect to: (a) the temperature; and (b) the temperature change.
  • the temperature of the ribbon heater 82 which had been set at about 40°C, started to increase after placing the heater inside the comforter 81.
  • the increase in the temperature was higher as compared to that in the untreated down, perhaps because heat is less likely to escape to the exterior of the comforter.
  • a cotton fabric having a size of 450 mm ⁇ 100 mm was folded in half. After sewing two sides of the fabric, 3 g of down was placed therein, and then the remaining side was sewn to prepare a washing sample.
  • a quantity of 5 ml of neutral detergent was dissolved in 2 L of water (about 25°C). The washing sample was placed into the resultant, and washed 40 times with pressing, followed by draining.
  • ii) Next, the washing sample was washed 40 times with pressing in water to carry out rinsing and draining. This step was repeated twice. The above described i) and ii) were repeated 10 times, and the sample was then dried in a dryer controlled at 60°C overnight.
  • the apparatus shown in FIG. 15 includes an apparatus body 91 for carrying out the blowing treatment of down; a blower 92 for blowing air into the apparatus body 91; and a valve 93.
  • An opening 94 for feeding down into the apparatus body 91 and a mesh portion M for discharging the air inside the apparatus body 91 are provided at the upper portion of the apparatus body 91.
  • the down was retrieved from the washed cotton fabric, the retrieved down was fed into the apparatus body 91 through the opening 94 with a funnel, and the opening 94 was closed. Then the valve 93 was closed, the blower 92 was activated, and the down inside the treatment apparatus 91 was subjected to the blowing treatment (air flow velocity: 1600 cm/s) for 10 minutes. Thereafter, the down was retrieved from the treatment apparatus 91.
  • the surface composition of the untreated down, the titania-attached down, and the down subjected to the plasma treatment after attaching titania thereto, were analyzed by XPS (X-ray photoelectron spectroscopy).
  • XPS X-ray photoelectron spectroscopy
  • ESCA 5600 manufactured by PerkinElmer Inc. was used, and the measurement was carried out under the conditions of X-ray source: Mg K ⁇ , 14 kV, 400 W, and TOA: 45°.
  • FIG. 16 shows the analysis results of the surface composition of each down, obtained by XPS.
  • FIG. 17 and FIG. 18 show the C1s and Ti2p narrow spectra, respectively, of the titania-treated down before and after the plasma treatment.
  • FIG. 19 shows a graph illustrating the analysis results of the surface composition, obtained by XPS, of the titania-attached and plasma-treated down, after 1 to 10 times of washings; and FIG. 20 shows a graph illustrating the changes in the concentration of Ti, with respect to the number of times of washing.
  • FIG. 21 to FIG. 23 show the analysis results of the surface compositions obtained by XPS of the synthetic fiber, silk and wool, respectively. It can be seen from the results shown in FIG. 21 to FIG. 23 that each of the surfaces of the synthetic fiber, silk and wool is coated with titanium, by carrying out the titania treatment.
  • the titania-attached and plasma-treated down has a higher rigidity as compared to the untreated down, even after the washing.
  • the titania-attached and plasma-treated down also has a higher elastic modulus as compared to the untreated down, revealing that the effect of the treatment is retained even after the washing.
  • the difference between the untreated down and the titania-attached and plasma-treated down was reduced after the washing, the difference between the untreated down and the titania-attached and plasma-treated down was increased again, by subjecting the washed down to the blowing treatment.
  • Example 1 The same procedure as in Example 1 was repeated except that aluminum isopropoxide was used instead of titanium tetraisopropoxide, to prepare an Al sol. Then an alumina-attaching treatment was carried out in the same manner as in Example 1.
  • FIG. 28(a) and FIG. 28(b) show the photographs of the alumina-attached down, obtained by a digital microscope (VHX-600; manufactured by KEYENCE CORPORATION). As shown in FIG. 28(a) and FIG. 28(b) , no change in the feather structure is observed when the untreated down and the alumina-attached down are compared, and it can be seen that the feather structure is maintained.
  • FIG. 29 The analysis results of the surface compositions of the untreated down and the alumina-attached down obtained by XPS in the same manner as in Example 1 are shown in FIG. 29 . Further, FIG. 30 shows the XPS spectra of the down before and after the alumina treatment.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP15825331.0A 2014-07-22 2015-07-16 Method for manufacturing surface-modified fiber material Active EP3187653B1 (en)

Applications Claiming Priority (2)

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JP2014149283 2014-07-22
PCT/JP2015/070404 WO2016013484A1 (ja) 2014-07-22 2015-07-16 表面改質繊維材料の製造方法および表面改質繊維材料

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CN111511979B (zh) * 2017-10-31 2023-07-11 日本制纸株式会社 氧化钛复合纤维及其制造方法
CN113829545B (zh) * 2021-09-27 2023-04-07 江西宏柏新材料股份有限公司 一种气凝胶复合材料卷式生产装置及方法

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US3620802A (en) * 1969-12-08 1971-11-16 Columbia Ribbon Carbon Mfg Duplicating ribbons and process
JPS59216977A (ja) * 1983-05-19 1984-12-07 株式会社クラレ 耐久性良好な微粒子付着方法
JPS60108075A (ja) * 1983-11-17 1985-06-13 安眠工業株式会社 中入綿
TW473575B (en) * 1997-05-23 2002-01-21 Kyorasha Co Ltd Natural fibers containing titanium oxide and process for producing the same
TW595618U (en) * 2002-03-01 2004-06-21 Greatforce Biochem Tech Co Ltd Photo catalytic cover structure of fiber, organic material or metal
JP3938704B2 (ja) * 2002-04-04 2007-06-27 康男 小澤 表面改質繊維材料、表面改質繊維製品並びに低温プラズマを用いた表面改質繊維材料の製造方法および製造装置
GB0208261D0 (en) * 2002-04-10 2002-05-22 Dow Corning An atmospheric pressure plasma assembly
NZ543027A (en) * 2003-05-05 2007-06-29 Commw Scient Ind Res Org Plasma treatment apparatus and method
JP2005256213A (ja) * 2004-03-11 2005-09-22 Mitsubishi Paper Mills Ltd インクジェット用記録材料
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JP2010095812A (ja) * 2008-10-15 2010-04-30 Tadashi Kokubo 金属酸化物で被覆された繊維性材料を製造する方法、及びその方法によって得られた繊維性材料、並びに結合組織修復材料
EP2569474A2 (en) * 2010-05-12 2013-03-20 Christopher M. Pavlos Method for producing improved feathers and improved feathers thereto
CN102505447B (zh) * 2011-09-27 2013-10-09 东华大学 大气压低温射频等离子体连续处理纤维表面的装置及方法

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CN106536816B (zh) 2020-05-12
TWI719943B (zh) 2021-03-01
KR20170033366A (ko) 2017-03-24
CN106536816A (zh) 2017-03-22
US20170211226A1 (en) 2017-07-27
WO2016013484A1 (ja) 2016-01-28
JP6655013B2 (ja) 2020-02-26
EP3187653A1 (en) 2017-07-05
JPWO2016013484A1 (ja) 2017-04-27
EP3187653A4 (en) 2018-03-28

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