WO2021241367A1 - Tissu non tissé à charge par friction et son procédé de fabrication - Google Patents

Tissu non tissé à charge par friction et son procédé de fabrication Download PDF

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Publication number
WO2021241367A1
WO2021241367A1 PCT/JP2021/019046 JP2021019046W WO2021241367A1 WO 2021241367 A1 WO2021241367 A1 WO 2021241367A1 JP 2021019046 W JP2021019046 W JP 2021019046W WO 2021241367 A1 WO2021241367 A1 WO 2021241367A1
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WIPO (PCT)
Prior art keywords
triboelectric
fibers
web
water flow
fiber
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PCT/JP2021/019046
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English (en)
Japanese (ja)
Inventor
拓磨 白武
悠一郎 高島
Original Assignee
日本バイリーン株式会社
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Application filed by 日本バイリーン株式会社 filed Critical 日本バイリーン株式会社
Priority to CN202180038066.8A priority Critical patent/CN115667610A/zh
Priority to JP2021545840A priority patent/JP6955645B1/ja
Publication of WO2021241367A1 publication Critical patent/WO2021241367A1/fr
Priority to TW111108462A priority patent/TW202245898A/zh

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D04H1/492—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres by fluid jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/28—Plant or installations without electricity supply, e.g. using electrets

Definitions

  • the present invention relates to a triboelectric nonwoven fabric and a method for producing the same.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2006-218342 provides a needle punching process on a web in which two or more types of fibers having different constituent resins (hereinafter, may be referred to as triboelectric fibers) are mixed. Disclosed is a triboelectric non-woven fabric that is charged by rubbing the triboelectric fibers against each other.
  • a triboelectric non-woven fabric can be prepared by rubbing friction-charged fibers with each other by performing a needle punching process on a web subjected to a water flow entanglement treatment.
  • the applicant of the present application tried to provide a thin triboelectric non-woven fabric so as to meet the needs of air filters and masks having various thicknesses and shapes.
  • a thin triboelectric non-woven fabric for example, a triboelectric non-woven fabric having a thickness of 1.2 mm or less
  • the triboelectric non-woven fabric prepared by performing needle punching on a web with a light weight mixed with triboelectric fibers is thin, the needle punching forms holes derived from needle processing such as through holes in the web. Probably because of this, the strength was greatly reduced.
  • Such a friction-charged non-woven fabric having a weak strength (for example, a friction-charged non-woven fabric having a maximum point strength of 43.0 N / 50 mm or less) is processed so as to have a three-dimensional shape such as pleats by punching with tension applied.
  • breaks or cracks may occur, which may cause deterioration of the filtration performance of the prepared air filter or mask.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a triboelectric nonwoven fabric in which two or more types of fibers having different constituent resins are mixed, which is thin and has excellent strength. Is to be.
  • the present inventors have succeeded in realizing a triboelectric non-woven fabric that is thin and has excellent strength. Specifically, we have succeeded in realizing a triboelectric non-woven fabric having the physical characteristics of "thickness is 1.2 mm or less and maximum point strength is higher than 43.0 N / 50 mm". Further, the present inventors have described in a method for producing a triboelectric non-woven fabric, in which a water flow entangled web prepared by subjecting a web containing triboelectric fibers to a water flow entanglement treatment is subjected to a step of rubbing and charging the triboelectric fibers.
  • the water flow entangled web was deformed in the thickness direction, and tension was applied to the water flow entangled web after being deformed in the thickness direction in a direction perpendicular to the thickness direction. It has been found that a triboelectric non-woven fabric that is thin and has excellent strength can be realized for the first time by efficiently rubbing the constituent fibers of the water flow entangled web with each other without using the needle punching process by the manufacturing method having this step. .. Specifically, by the method for producing a triboelectric nonwoven fabric according to the present invention, a triboelectric nonwoven fabric having the physical characteristics of "thickness is 1.2 mm or less and maximum point strength is higher than 43.0 N / 50 mm" is realized. succeeded in.
  • the first invention is a triboelectric nonwoven fabric in which two or more types of fibers having different constituent resins are mixed, and the thickness is 1.2 mm or less, and the maximum point strength is higher than 43.0 N / 50 mm. , Triboelectric non-woven fabric.
  • the second invention is a method for producing a triboelectric nonwoven fabric in which two or more types of fibers having different constituent resins are mixed.
  • various configurations such as the following configurations can be appropriately selected.
  • the various measurements described in the present invention were carried out under normal pressure under 25 ° C. temperature conditions. Then, unless otherwise specified or specified, the various measurement results described in the present invention were obtained by measurement up to a value one digit smaller than the desired value, and the value to be obtained was calculated by rounding off the value.
  • the value up to the first decimal place is the value to be obtained
  • the value up to the first decimal place is calculated by finding the value up to the second decimal place by measurement and rounding off the obtained value to the second decimal place. Then, this value was used as the value to be calculated.
  • each upper limit value and each lower limit value exemplified in the present invention can be arbitrarily combined.
  • the triboelectric nonwoven fabric according to the present invention is a charged nonwoven fabric composed of two or more types of charged fibers having different constituent resins.
  • the term "two or more types of fibers having different constituent resins" as used herein means that two or more types of fibers are mixed in the triboelectric non-woven fabric, and in the two or more types of fibers, the surface (both ends) of the first type of fiber is used. It means that the constituent resin of (excluding the portion) and the constituent resin of the surface of other fibers (excluding both ends) are different.
  • the fiber constituting the triboelectric nonwoven fabric according to the present invention may be referred to as a triboelectric fiber.
  • a mixture of two or more types of fibers having different constituent resins here means that the above-mentioned two or more types of triboelectric fibers are intertwined with each other.
  • a web prepared by uniformly mixing two or more types of triboelectric fibers and supplying them to a card machine two or more types of fibers having different constituent resins are mixed, and the present invention can be made by using the web.
  • Such a triboelectric non-woven fabric can be prepared.
  • the triboelectric non-woven fabric is breathable and the constituent fibers are randomly present, so that it provides an air filter and mask with high void ratio, uniform pore diameter, low pressure loss, and excellent breathability and collection efficiency. can.
  • the type of triboelectric fibers may be appropriately selected as long as it is a combination of fibers that are charged by rubbing against each other.
  • a combination of the first kind of friction charged fiber and the second kind of friction charged fiber for example, a combination of a polyolefin fiber and an acrylic fiber; a fluorine fiber and a polyamide fiber, wool, a glass fiber, silk or rayon.
  • the amount of charge can be increased by rubbing the triboelectric fibers against each other, and it is possible to provide an air filter or mask having excellent collection efficiency. It is preferable because a triboelectric non-woven fabric can be realized.
  • the constituent resin of the polyolefin-based fiber examples include polypropylene resin, polyethylene resin, polystyrene resin, vinyl acetate copolymer resin, ethylene-propylene copolymer, or a part of these resins using a nitrile group, a cyano group, or a halogen.
  • the polyolefin-based fiber can be a composite fiber composed of one kind or two or more kinds of these constituent resins.
  • it may be a core-sheath type composite fiber
  • the sheath component may be a polyolefin-based fiber made of a polyolefin-based resin.
  • the constituent resin of the polyolefin fiber contains a phosphorus-based additive or a sulfur-based additive.
  • a phosphorus-based additive or a sulfur-based additive By containing a phosphorus-based additive or a sulfur-based additive, the amount of charge can be increased and the initial collection efficiency can be improved.
  • other additives such as phenol-based and amine-based additives may be further contained. If the total amount of these additives is large, the spinnability may be deteriorated. Therefore, the total amount of the additives is preferably 5% by mass or less of the polyolefin fiber, and preferably 2% by mass or less. It is more preferably 1% by mass or less, and further preferably 1% by mass or less.
  • Examples of the phosphorus-based additive include trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, and bis (2,4-di-t-butyl).
  • This phosphorus-based additive is preferably contained in an amount of 0.01% by mass or more, more preferably 0.2% by mass or more, and more preferably 0.3% by mass or more in the polyolefin-based fiber. Is more preferable, and it is more preferable that the content is 0.6% by mass or more.
  • Sulfur-based additives include sulfur such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, disstearyl-3,3'-thiodipropionate, and pentaerythritol tetrakis. A system antioxidant or the like can be preferably used.
  • the sulfur-based additive is preferably contained in the polyolefin fiber in an amount of 0.01% by mass or more, more preferably 0.1% by mass or more.
  • acrylic fiber either a polyacrylonitrile fiber containing acrylonitrile as a main component (85% or more) or a modacrylic fiber containing acrylonitrile 35% or more and less than 85% can be used. Further, there are two types of polyacrylonitrile-based fibers, one spun using an organic solvent and one spun using an inorganic solvent, and any polyacrylonitrile-based fiber may be used.
  • the friction-charged fiber is, for example, a melt spinning method, a dry spinning method, a wet spinning method, a direct spinning method (melt blow method, spunbond method, electrostatic spinning method, etc.), and removal of one or more resin components from a composite fiber. It can be obtained by a known method such as a method of extracting a fiber having a small fiber diameter and a method of beating the fiber to obtain a divided fiber.
  • the fineness of the triboelectric fiber is not particularly limited as long as the object of the present invention can be achieved.
  • the fineness of the triboelectric fiber is preferably 0.1 to 10 dtex, preferably 0.3 to 7 dtex, so that the triboelectric non-woven fabric can provide an air filter or mask having low pressure loss and excellent air permeability and collection efficiency. It is preferably 0.6 to 5 dtex, and most preferably 0.8 to 3 dtex.
  • the "fineness" is obtained by the method A specified in JIS L1015: 2010, 8.5.1 (positive amount fineness).
  • the fineness of various triboelectric fibers can be increased because the triboelectric fibers can be efficiently rubbed against each other for two or more types of triboelectric fibers that are intertwined with each other and exist in the triboelectric non-woven fabric. Is preferably close. Specifically, the percentage of the fineness of the other type of triboelectric fiber to the fineness of one type of triboelectric fiber is preferably 250% or less, more preferably 220% or less, 130. It is more preferably% or less. Ideally, the fineness of the various triboelectric fibers is most preferably the same (ie, the percentage is 100%). When the triboelectric non-woven fabric contains three or more types of triboelectric fibers, the fineness is confirmed for the two types of triboelectric fibers having a large mass ratio as described above.
  • the fiber length of the triboelectric fiber is not particularly limited as long as the object of the present invention can be achieved, and may be a short fiber, a long fiber or a continuous fiber. However, by realizing a triboelectric non-woven fabric in which triboelectric fibers are randomly present, it is possible to provide an air filter or mask having a high void ratio, a uniform pore diameter, low pressure loss, and excellent air permeability and collection efficiency.
  • the fiber length is preferably 3 to 150 mm, more preferably 10 to 100 mm, and even more preferably 30 to 80 mm, because it is a triboelectric non-woven fabric.
  • the "fiber length" is obtained by JIS L1015: 2010, 8.4.1 [corrected staple diagram method (B method)].
  • the mixing ratio of each triboelectric fiber is appropriately adjusted.
  • the mixing ratio of the triboelectric fiber A and the triboelectric fiber B is 5% by mass: 95% by mass. It can be up to 95% by mass: 5% by mass, 15% by mass: 85% by mass to 85% by mass: 15% by mass, 25% by mass: 75% by mass to 75% by mass: 25% by mass. Can be.
  • the triboelectric non-woven fabric may contain fibers other than the triboelectric fibers.
  • the percentage of the mass of triboelectric fibers in the mass of the fibers that make up the triboelectric non-woven fabric can be adjusted as appropriate, but triboelectric charging can provide air filters and masks with low pressure loss and excellent air permeability and collection efficiency.
  • triboelectric it is preferably 50% by mass or more, more preferably 65% by mass or more, further preferably 80% by mass or more, and the fibers constituting the triboelectric non-woven fabric are triboelectric fibers. Most preferably only.
  • the fibers constituting the triboelectric non-woven fabric may contain an oil agent.
  • the type of oil agent can be appropriately selected, and a hydrophilic oil agent or a non-hydrophilic oil agent can be adopted.
  • the hydrophilic oil agent referred to here refers to a treatment agent that enhances the hydrophilicity of the fiber surface, and known components and formulations can be used.
  • a lubricant such as mineral oil or synthetic oil containing a wetting agent such as an anionic surfactant or a nonionic surfactant may be mentioned.
  • the non-hydrophilic oil agent refers to a treatment agent that reduces the hydrophilicity of the fiber surface, and known components and formulations can be used.
  • those in which the type and amount of the surfactant are adjusted, and those in which a lubricant such as mineral oil or synthetic oil contains a fluorine-based or silicone-based component can be mentioned.
  • the type of the oil agent can be confirmed by subjecting the oil agent extracted from the fibers constituting the triboelectric nonwoven fabric as described later to a known analyzer such as FT-IR (ATR method).
  • the triboelectric non-woven fabric can be used as a constituent fiber because it can prevent an increase in the water content of the triboelectric non-woven fabric and increase the amount of charge due to rubbing between the triboelectric fibers to realize a triboelectric-charged non-woven fabric having excellent collection efficiency. It is preferable to contain triboelectric fibers to which a non-hydrophilic oil agent is applied.
  • the percentage of the oil agent contained in the constituent fibers of the friction-charged non-woven fabric can be adjusted as appropriate, but the percentage of the oil agent mass in the fiber mass is preferably 0.01% by mass or more, preferably 0.05% by mass or more. It is more preferably 0.08% by mass or more, further preferably 0.10% by mass or more, and particularly preferably 0.11% by mass or more. The upper limit can be adjusted as appropriate, but it is realistic that it is 1% by mass or less.
  • the percentage (unit: mass%) of the oil agent mass contained in the fibers constituting the triboelectric nonwoven fabric was first subjected to the sampled test piece to the methanol extraction method described in the JIS L-1015 chemical staple test method.
  • the mass of the oil contained in the test piece is obtained from the measured mass. Then, determine the conversion value in terms of the mass of oil contained in the test piece of 1 m 2 around (g / m 2), further, the converted value to total fiber mass constituting the test piece (g / m 2) The percentage of oil is calculated, and the calculated value is taken as the percentage of the oil mass (unit: mass%).
  • the fibers constituting the triboelectric non-woven fabric may be in a state where the fibers are integrated with each other by a binder or fiber adhesion.
  • the triboelectric fibers can efficiently rub against each other to provide a triboelectric non-woven fabric having a large amount of charge, and the constituent fibers of the triboelectric non-woven fabric can be connected to each other while the gas passes through the triboelectric non-woven fabric. Since the triboelectric fibers are maintained in charge by efficiently rubbing against each other, it is possible to provide a triboelectric non-woven fabric that can provide an air filter or mask having excellent collection efficiency.
  • the fibers constituting the triboelectric non-woven fabric are triboelectric non-woven fabrics in which the fibers are not integrated with each other by a binder or fiber adhesion, and the fibers are simply entangled with each other. Further, it is preferable to use a triboelectric nonwoven fabric in which fibers are simply entangled with each other, because it is possible to provide a triboelectric nonwoven fabric in which contamination is less likely to occur and the texture is less likely to deteriorate.
  • the friction-charged nonwoven fabric has a fiber layer in which fibers are oriented in one direction (for example, a direction parallel to the transport direction) (fiber layer A, for example, a fiber layer derived from a one-way web) and a direction different from the above-mentioned one direction. It is preferable to have a structure in which a fiber layer in which the fibers are oriented (fiber layer B, for example, a fiber layer derived from crosslay web) is laminated.
  • fiber layer B for example, a fiber layer derived from crosslay web
  • a fiber layer made by laminating one-way webs containing triboelectric fibers so as to have different fiber orientations, and one-way webs and crosslay webs containing triboelectric fibers are laminated.
  • the fiber layer is made of the Chris Crossweb. Due to the triboelectric non-woven fabric having such a layer structure, the fiber layer B is applied to the non-woven fabric or the web in the transport direction in the step of rubbing the constituent fibers of the web according to the present invention. The fiber orientation of the fabric moves so as to be parallel to the transport direction. As a result, the triboelectric fibers in the fiber layer B are strongly rubbed against each other, and the triboelectric fibers existing between the layers are rubbed more strongly due to the rubbing between the fiber layer A and the fiber layer B. It is preferable because a triboelectric non-woven fabric can be realized.
  • a non-woven fabric having a fiber layer in which the fibers are oriented in various directions is preferable.
  • the orientation of the fibers in the fiber layer of the triboelectric non-woven fabric can be confirmed visually or by a micrograph of the surface or cross section of the fiber layer. Further, when the manufacturing process of the triboelectric nonwoven fabric is known, the orientation of the fibers in the fiber layer can be determined from the type of web used in the manufacturing process.
  • the texture of the triboelectric nonwoven fabric is not particularly limited, but it is preferably 15 to 200 g / m 2 and 25 to 150 g / m 2 so that a triboelectric nonwoven fabric having excellent rigidity such as the maximum point strength described later can be prepared. It is more preferably present, and even more preferably 30 to 100 g / m 2 .
  • the "Metsuke” is the mass per 1 m 2 , and is obtained by the method specified in JIS L1085: 1998, 6.2 "Mass per unit area".
  • the thickness of the triboelectric nonwoven fabric according to the present invention is 1.2 mm or less, which can meet the needs of air filters and masks having various thicknesses and shapes. If the thickness of the triboelectric non-woven fabric is 1.2 mm or less, the value can be adjusted as appropriate according to the needs, but it can be widely met by the needs of air filters and masks having various thicknesses and shapes (for example, thick air filters). However, if it is a thin charged nonwoven fabric, it can meet the needs by laminating a plurality of thin charged nonwoven fabrics), and it is 1.1 mm or less. It is preferably 1.0 mm or less, more preferably 0.9 mm or less, and particularly preferably 0.8 mm or less.
  • the lower limit value can be adjusted as appropriate, but it is realistic that it is 0.1 mm or more.
  • the apparent density of the frictional charging nonwoven can be 0.15 g / cm 3 or less, preferably less than 0.15 g / cm 3, more preferably 0.14 g / cm 3 or less , further preferably 0.13 g / cm 3 or less, particularly preferably 0.12 g / cm 3 or less.
  • the lower limit can be adjusted as appropriate, but since it is possible to realize an air filter or mask that is less likely to reduce pressure loss due to its high strength, it is higher than 0 g / cm 3 and 0.04 g / cm 3 or more. Is preferable.
  • the apparent density (g / cm 3 ) of the triboelectric nonwoven fabric can be calculated by dividing the triboelectric nonwoven fabric's texture (g / m 2 ) by the thickness (mm).
  • the triboelectric nonwoven fabric according to the present invention is characterized in that it is highly rigid even though its thickness is 1.2 mm or less, and its maximum point strength is higher than 43.0 N / 50 mm. Since the triboelectric nonwoven fabric according to the present invention has a maximum point strength higher than 43.0 N / 50 mm, it can be used for air filters and masks, for example, by punching it in a state where tension is applied or by processing it into a three-dimensional shape such as pleats. It is prevented from breaking or cracking during processing, and it is difficult to deteriorate the filtration performance of the prepared air filter or mask.
  • the maximum point strength of the triboelectric nonwoven fabric is higher than 43.0 N / 50 mm, the value can be appropriately adjusted according to the needs. It is preferably 50 N / 50 mm or more, more preferably 60 N / 50 mm or more, further preferably 70 N / 50 mm or more, further preferably 80 N / 50 mm or more, and 90 N / 50 mm or more. Is particularly preferable.
  • the upper limit value can be adjusted as appropriate, but it is realistic that it is 300 N / 50 mm or less.
  • the maximum point strength referred to in the present invention is a value obtained by subjecting the object to be measured to the following measuring method.
  • the initial grip interval is adjusted to be longer than the fiber length of the short fiber with the longest fiber length excluding the long fiber.
  • a test piece collected from the object to be measured is provided to a rapid extension type tensile tester, and the maximum point strength (unit: N / 50 mm) of the object to be measured is obtained by the same measurement.
  • the initial gripping interval of 10 mm or more can be secured, and the maximum point strength (unit: N / 50 mm) of the object to be measured can be obtained by the same measurement.
  • the length of the test piece (shape: rectangle, long side: length that can be measured by the above-mentioned constant speed extension type tensile tester) from various directions of the object to be measured. Collect multiple pieces (short side: 50 mm) longer than 100 mm. Then, each of the collected test pieces is subjected to the above-mentioned measurement method. Then, among the maximum values of the measured intensities in each measured test piece, the highest value is regarded as the maximum point intensity (unit: N / 50 mm) of the object to be measured.
  • a test piece (shape: rectangular, long side: length that can be measured by the above-mentioned constant speed extension type tensile tester) collected from the measurement object. (Longer than 100 mm, short side: smaller than 50 mm) is applied to a constant-speed elongation type tensile tester in the same manner as described above, and the maximum per length of the short side in the object to be measured is measured in the same manner. Find the point strength.
  • the maximum point strength of the object to be measured ( Unit: N / 50 mm) can be calculated. Specifically, a test piece having a short side length of 10 mm was subjected to a constant-speed extension type tensile tester, and the maximum point strength per 10 mm short side length in the measurement object obtained by measurement was 1N. If so, it can be calculated that the maximum point strength of the object to be measured is 5N / 50 mm by conversion.
  • Triboelectric non-woven fabric can be collected from an air filter or mask in order to obtain each of the above-mentioned values. At that time, a section is collected from a portion other than the welded portion of the air filter or mask which has a flat plate shape by opening the pleated fold. Then, by removing unnecessary components such as a cover material from the section, a test piece used for obtaining each value can be collected.
  • the points where the triboelectric fibers rub against each other are positively or negatively charged. That is, positively charged portions and negatively charged portions are randomly distributed and exist on the surface of the triboelectric fiber.
  • the charged nonwoven fabric obtained for the corona charging treatment positively charged portions are unevenly distributed on the surface of one main surface side of the charged nonwoven fabric in the constituent fibers, and the positively charged portions are unevenly distributed on the other main surface side of the charged nonwoven fabric. Negatively charged parts are unevenly distributed on the surface. Therefore, the triboelectric nonwoven fabric according to the present invention and the charged nonwoven fabric provided for the corona charging treatment have different charged states in the constituent fibers.
  • the triboelectric non-woven fabric according to the present invention has the triboelectric fibers in the charged state described above, dust, pollen and the like tend to be uniformly collected on the surface of the triboelectric fibers. As a result, it is possible to realize an air filter or mask having excellent collection efficiency.
  • This manufacturing method includes (1) a step of preparing a web in which two or more types of fibers having different constituent resins are mixed.
  • the two or more types of fibers having different constituent resins are a plurality of types of triboelectric fibers constituting the triboelectric nonwoven fabric according to the present invention, or a plurality of types of triboelectric fibers and fibers other than the triboelectric fibers.
  • the method of preparing the web in which these fibers are mixed can be appropriately selected, but the method of preparing the web by blending each fiber at the desired blending ratio and supplying it to the card device, and the method of preparing the web by supplying each fiber of the desired blending ratio to the air array device and depositing them.
  • a method of preparing a web, or a method of preparing a web in which each fiber is mixed at a required compounding ratio by using direct spinning such as a melt blow nonwoven fabric, a spunbonded nonwoven fabric, or an electrostatically spun nonwoven fabric can be adopted.
  • the web may contain a binder or an adhesive fiber
  • the web may contain a triboelectric non-woven fabric having a large amount of charge by efficiently rubbing the triboelectric fibers with each other in the charging method according to the present invention. It is preferable that it does not contain binders or adhesive fibers, and it is preferable that the web is composed of only constituent fibers (more preferably only triboelectric fibers).
  • the fiber is provided with a hydrophilic oil agent or a non-hydrophilic oil agent. Since the web contains an oil agent, it is possible to prevent the occurrence of fiber breakage in the step of rubbing the constituent fibers of the step (3) described later. As a result, it is possible to provide a triboelectric non-woven fabric that can prevent a decrease in the amount of charge and provide an air filter or mask having excellent collection efficiency. In particular, it is preferable to use triboelectric fibers to which a non-hydrophilic oil agent is applied, because it is possible to prevent an increase in water content and increase the amount of charge due to rubbing between the triboelectric fibers.
  • This manufacturing method has (2) a step of applying a water flow entanglement treatment to the web to prepare a water flow entanglement web.
  • water flow entanglement process applied to the web adjust the strength of the water flow and the spacing and arrangement of the nozzles that radiate the water flow as appropriate.
  • the type of water used for the water flow entanglement treatment can be appropriately selected, and may be, for example, industrial water, clean water, distilled water, pure water, or the like.
  • water after being used for the water flow entanglement treatment (which may contain an oil agent or the like that has fallen off from the fiber) may be repeated and used for the water flow entanglement treatment.
  • the average water pressure per nozzle is preferably 2 MPa or more, preferably 3 MPa or more, so that the fibers can be entangled with each other and have excellent rigidity and a thin triboelectric non-woven fabric can be prepared. It is more preferably 4 MPa or more, and further preferably 4 MPa or more.
  • the average water pressure is preferably 25 MPa or less, more preferably 20 MPa or less, further preferably 18 MPa or less, and most preferably 16 MPa or less.
  • only one main surface of the web may be subjected to the water flow entanglement treatment, or both main surfaces of the web may be subjected to the water flow entanglement treatment. Further, the number of times of the water flow entanglement treatment may be once or a plurality of times.
  • the water flow entanglement web thus prepared may be subjected to the next step in a wet state by the water flow entanglement treatment, but the dry water flow is so that triboelectric charging is performed more efficiently. It is preferable to use the entangled web for the next step.
  • a method of drying the water flow entangled web moistened by the water flow entanglement treatment can be appropriately selected, but a method of providing the web to a heating device, a method of drying by exposing to atmospheric pressure or reduced pressure, and the like can be adopted.
  • the type of heating device can be selected as appropriate, and for example, a method using a device that heats or pressurizes with a roller, an oven dryer, a far-infrared heater, a dry heat dryer, a hot air dryer, a device that can irradiate and heat infrared rays, etc. is adopted. can.
  • the heating temperature by the heating device is appropriately selected, but it is appropriately adjusted so that the water content can be evaporated and the constituent components such as constituent fibers are not unintentionally decomposed or denatured.
  • the binder may be bonded or the fiber may be bonded by subjecting the web to a heat treatment, or the crosslinkable resin may be crosslinked. ..
  • the water flow entangled web is deformed in the thickness direction, and tension is applied to the water flow entangled web after being deformed in the thickness direction in a direction perpendicular to the thickness direction. It has a step of rubbing the constituent fibers of the water flow entangled web.
  • the triboelectric fibers contained in the water flow entangled web can be rubbed against each other to charge the water flow entangled web. ..
  • the method of deforming the water flow entangled web in the thickness direction can be appropriately selected, but a method of applying a roller to the water flow entangled web, a method of providing the water flow entangled web with a clearance that can be deformed in the thickness direction, and the like can be adopted.
  • a mode to provide a water flow entanglement web -A mode in which the water flow entanglement web is provided to the clearance formed by a member such as a plate, a rod, a conveyor, and a roller, which is adjusted to have a clearance thinner than the thickness of the water flow entanglement web. -For plates, rods, conveyors, etc.
  • the length of the clearance may be any as long as the water flow entangled web can be deformed in the thickness direction, and the length can be adjusted as appropriate, but it is preferably less than 100% of the thickness of the water flow entangled web, and is preferably 80% or less. It is preferably 60% or less, and preferably 40% or less.
  • the clearance may be 0.
  • the material of the pressure member (hereinafter referred to as the pressure member) used to deform the water flow entangled web such as rollers and conveyors in the thickness direction, and various physical properties such as the hardness of the surface thereof are efficient. Select as appropriate so that a triboelectric non-woven fabric can be produced well.
  • -The contact is made by bringing the water entangled web into contact with the surface of the roller and changing the transport direction of the water entangled web before contacting the roller and the transport direction of the water entangled web after contacting the roller.
  • Examples thereof include a mode in which a force acts in the thickness direction of the water flow entangled web in the portion where the water flow is entangled.
  • pressure is applied to the main surface of the water flow entangled web in contact with the surface of the roller on the opposite side to the roller side by using another roller or a conveyor so that the triboelectric nonwoven fabric can be efficiently manufactured. May act.
  • a speed difference may be provided between the speed at which the roller conveys the water flow entangled web and the speed at which the other roller or the transfer conveyor conveys the water flow entangled web.
  • the presence or absence of rotation, the rotation speed, and the rotation direction of the roller can be selected as appropriate.
  • the presence / absence of rotation, the rotation speed, and the rotation direction between the two rollers may be different combinations.
  • the speed at which the conveyor conveys the water flow entangled web can be appropriately adjusted.
  • the pressure acting in the thickness direction of the water flow entangled web and the magnitude of the tension acting on the water flow entangled web during transportation are appropriately adjusted so that the desired triboelectric non-woven fabric can be produced. Adjust appropriately so that the entangled web does not crack, break, or change unintended physical properties.
  • tension is applied to the water flow entangled web after being deformed in the thickness direction in a direction perpendicular to the thickness direction of the water flow entangled web.
  • the triboelectric fibers contained in the water flow entangled web can be further rubbed against each other to further charge the water flow entangled web.
  • "tension is applied in a direction perpendicular to the thickness direction” means that the water flow entanglement web acts on the water flow entanglement web before it comes into contact with the pressurizing member.
  • a method of applying tension to the water flow entangled web after contact with the pressurizing member in a direction perpendicular to the thickness direction can be appropriately selected.
  • Method, Etc. can be adopted.
  • the transport direction of the water flow entangled web until the pressurizing member is applied and the transport direction of the water flow entangled web after the pressurizing member is acted on may be the same direction or different directions. However, when the directions are different from each other, tension can be applied more effectively in the thickness direction of the water flow entangled web and the direction perpendicular to the thickness direction, and a triboelectric non-woven fabric having a large amount of charge can be produced, which is preferable.
  • the magnitude of the tension applied to the water flow entangled web after contacting the pressure member is appropriately adjusted so that the desired triboelectric nonwoven fabric can be produced, but the water flow entangled web is cracked, broken or has unintended physical properties. Adjust appropriately so that no change occurs.
  • the frictionally charged fibers which are constituent fibers, are not only in the thickness direction (one dimension in the Z-axis direction) but also in the thickness direction and the transport direction (Z-axis direction and the X-axis direction).
  • Friction-charged fibers efficiently interact with each other in a three-dimensional direction (Z-axis direction, X-axis direction, and Y-axis direction) other than the transport direction (Z-axis direction, X-axis direction, and Y-axis direction) that are perpendicular to the thickness direction, the transfer direction, and the thickness direction. Rubbing and friction charging are performed. Therefore, it is possible to realize a triboelectric non-woven fabric having a large amount of charge and excellent filter performance even though the thickness is as thin as 1.2 mm or less.
  • the triboelectric non-woven fabric produced in this way can be used as a filter material by itself, but a cover material, a support, and / or a pre-filter, a backup filter, etc. are laminated on the triboelectric non-woven fabric to form a filter material.
  • a cover material, a support, and / or a pre-filter, a backup filter, etc. are laminated on the triboelectric non-woven fabric to form a filter material.
  • the cover material, the support, and / or the pre-filter and the backup filter known ones can be adopted, and for example, a cloth, a porous film, a breathable foam, or the like can be adopted.
  • the laminated filter material is made by simply laminating the illustrated material and the triboelectric non-woven fabric, it can be bonded by using a binder, hot melt web, or fiber bonding to perform bonding treatment such as heat sealing or ultrasonic welding. It may be a laminated filter material made of.
  • the outer shape of the filter material provided with the triboelectric nonwoven fabric and the triboelectric nonwoven fabric can be appropriately adjusted and is not particularly limited, but for example, a two-dimensional sheet shape, a three-dimensional corrugated shape, a pleated shape, or a cylinder. It can be a shape or the like.
  • the filter material provided with the triboelectric nonwoven fabric and the triboelectric nonwoven fabric may have a cutout portion, a punched portion, or a notch portion.
  • a unidirectional web and a crosslay web were prepared by uniformly mixing 70% by mass of polypropylene fibers having the configurations shown in Table 1 and 30% by mass of acrylic fibers and feeding them to a card machine. Then, a Chris Crossley web was prepared by laminating a one-way web and a crosslay web. A water flow entanglement treatment (water pressure: 3 MPa, process transfer speed: 5 m / min) was performed from one main surface side (A) to the other main surface side (B) of the Chris Rossley web.
  • the prepared water flow entangled web was a web formed by laminating a fiber layer A in which fibers are oriented in one direction and a fiber layer B in which fibers are oriented in a direction different from the above one direction. ..
  • Comparative Example 2 A water flow entangled web was prepared in the same manner as in the reference example, except that the basis weight of the Chris Crosley web used was increased. A triboelectric nonwoven fabric was prepared in the same manner as in Comparative Example 1 except that the water flow entangled web prepared in this manner was used.
  • Example 1 With the water flow entangled web prepared in the reference example placed on a transport conveyor whose surface is made of polyurethane material and is easily deformed, the fiber orientation of the fiber layer A constituting the water flow entangled web and the transport direction are parallel to each other. Then, it was conveyed at a transfer speed of 25.0 m / min. Then, the water flow is brought into contact with the metal roller (roller rotation direction: rotation direction in which the water flow entanglement web can be conveyed downstream in the transfer direction) whose clearance with the transfer conveyor is adjusted to 0 mm. The entangled web was deformed in the thickness direction and triboelectrically charged.
  • a speed difference (conveying speed of the water flow entangled web by the transport conveyor: 25.0 m / min, moving speed on the surface of the metal roller: 24.5 m / min) is generated between the conveyor in contact with the water flow entangled web and the metal roller. By providing it, the friction between the triboelectric fibers is further promoted.
  • the water flow entangled web after contacting the metal roller was conveyed toward the downstream side in the transport direction of the water flow entangled web at a transport speed of 25.5 m / min.
  • Example 2 A water flow entangled web was prepared in the same manner as in the reference example, except that the basis weight of the web used was increased.
  • a triboelectric nonwoven fabric was prepared in the same manner as in Example 1 except that the water flow entangled web prepared in this manner was used.
  • Table 1 shows various physical properties of the water flow entangled web of the reference example and each triboelectric nonwoven fabric manufactured as described above.
  • the fibers to which the alkylphosphate ester, which is a non-hydrophilic oil agent, is given are marked with the NH mark, and the fibers to which the hydrophilic oil agent is given are marked with the H mark.
  • the percentage of the oil agent mass contained in the fibers constituting the water flow entangled web or the triboelectric non-woven fabric is described in the "percentage of the oil agent (mass%)" column.
  • the ventilation resistance (unit: Pa) and the collection efficiency (unit:%) were determined by using the water flow entangled web of the reference example and each triboelectric non-woven fabric for the following measurement methods. Further, a QF value capable of evaluating the filter performance was calculated from the obtained values of the aeration resistance (unit: Pa) and the collection efficiency (unit:%).
  • Specimens were collected from each of the water flow entangled webs and each triboelectric non-woven fabric of the reference example. Then, the collected test piece was attached to a measuring device "AP-9000" manufactured by Sibata Scientific Technology Co., Ltd., and the collection efficiency and the ventilation resistance were measured. At the time of measurement, the test piece was attached so that the main surface side derived from one main surface side (A) of the web in the test piece faces the upstream side of the measuring device.
  • the test flow rate is adjusted so that the effective filtration area of the test piece is 40 liters per minute per 124 cm 2 (for example, the test flow rate supplied to the test piece having an effective filtration area of 12.4 cm 2 is 4 liters per minute).
  • the differential pressure between the upstream and the downstream in the piece was measured, and the ventilation resistance (unit: Pa) of the test piece was obtained from the measured differential pressure.
  • test flow rate is adjusted so that the effective filtration area of the test piece is 30 liters per minute at 124 cm 2 (for example, the test flow rate supplied to the test piece having an effective filtration area of 12.4 cm 2 is 3 liters per minute).
  • Test containing sodium chloride particles (median particle size distribution: 0.06 to 0.10 ⁇ m, geometric standard deviation: 1.8 or less) at a concentration of 50 mg / m 3 or less (concentration variation: ⁇ 15% or less)
  • concentration variation ⁇ 15% or less
  • the concentrations of the sodium chloride particles present on the upstream side and the downstream side of the test piece were measured using a light scattering type dust densitometer, and the test was performed from both of the measured concentrations.
  • the concentration of sodium chloride particles collected in the pieces was calculated.
  • the percentage of the concentration of the sodium chloride particles collected in the test piece to the concentration of the sodium chloride particles supplied to the upstream side of the test piece is calculated, and the value is used as the collection efficiency of the test piece (unit::). %).
  • the aeration resistance is preferably 50 Pa or less, preferably 40 Pa or less, preferably 30 Pa or less, preferably 20 Pa or less, preferably 10 Pa or less, and most preferably 5 Pa or less.
  • the lower limit can be adjusted as appropriate, but 0.5 Pa or more is realistic.
  • the collection efficiency is preferably 50% or more, preferably 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more, and most preferably 95 or more.
  • such a friction-charged nonwoven fabric having a weak strength (for example, a friction-charged nonwoven fabric having a maximum point strength of 43.0 N / 50 mm or less) has a three-dimensional shape such as pleats, which is punched in a state where tension is applied.
  • a friction-charged nonwoven fabric having a maximum point strength 43.0 N / 50 mm or less
  • has a three-dimensional shape such as pleats, which is punched in a state where tension is applied.
  • the triboelectric nonwoven fabrics prepared in Examples 1 and 2 are triboelectric nonwoven fabrics having physical properties such that the thickness is 1.2 mm or less and the maximum point strength is higher than 43.0 N / 50 mm. rice field.
  • the reason for this is that in the method for producing a triboelectric nonwoven fabric according to the present invention, the constituent fibers of the water flow entangled web can be rubbed against each other to be triboelectricly charged without performing needle punching on the web, so that the web is thin and has excellent strength. It was possible to realize a triboelectric non-woven fabric.
  • Example 3 A water flow entangled web was prepared in the same manner as in the reference example except that the acrylic fiber having the composition shown in Table 2 was adopted. A triboelectric nonwoven fabric was prepared in the same manner as in Example 1 except that the water flow entangled web thus prepared was used.
  • Example 4 A water flow entangled web was prepared in the same manner as in the reference example except that polypropylene fibers having the configurations shown in Table 2 were adopted.
  • a triboelectric nonwoven fabric was prepared in the same manner as in Example 1 except that the water flow entangled web thus prepared was used.
  • Table 2 shows various physical properties of each triboelectric nonwoven fabric manufactured as described above. In Table 2, the results of Example 1 are also shown for easy understanding.
  • the triboelectric nonwoven fabrics prepared in Examples 3 to 4 were all triboelectric nonwoven fabrics having a thickness of 1.2 mm or less and a maximum point strength of more than 43.0 N / 50 mm. From this, according to the present invention, even when various triboelectric fibers having different fineness and fiber length are adopted, "the thickness is 1.2 mm or less and the maximum point strength is more than 43.0 N / 50 mm". It was possible to realize a triboelectric non-woven fabric having the physical characteristics of "high".
  • Example 5 A water flow entangled web was prepared in the same manner as in the reference example, except that polypropylene fibers and acrylic fibers having the configurations shown in Table 3 were adopted. Then, the water flow entangled web is placed in a calendar roll whose surface is made of a metal material so that the fiber orientation of the fiber layer A constituting the water flow entangled web is parallel to the transport direction (rotation direction: transport direction of the water flow entangled web). The water flow entangled web was pressurized under the conditions of a rotation direction capable of transporting to the downstream side and a linear pressure of 100 kg / cm), deformed in the thickness direction, and frictionally charged.
  • Example 6 A triboelectric nonwoven fabric was prepared in the same manner as in Example 5 except that the water flow entangled web was pressurized under the condition of a linear pressure of 60 kg / cm.
  • Example 7 A unidirectional web was prepared by uniformly mixing 70% by mass of polypropylene fibers having the configurations shown in Table 3 and 30% by mass of acrylic fibers and feeding them to a card machine.
  • a water flow entanglement treatment (water pressure: 3 MPa, process transfer speed: 5 m / min) was performed from one main surface side (A) of the one-way web to the other main surface side (B). Then, under the same conditions, water flow entanglement treatment (water pressure: 3 MPa, process transfer speed: 5 m / min) is performed again from the other main surface side (B) of the one-way web to the one main surface side (A). bottom.
  • the prepared water flow entangled web was a web composed of only the fiber layer A in which the fibers were oriented in one direction.
  • a triboelectric nonwoven fabric was prepared in the same manner as in Example 5, except that the water flow entangled web thus prepared was used.
  • Example 8 A water flow entangled web was prepared in the same manner as in the reference example except that polypropylene fibers and acrylic fibers having the configurations shown in Table 3 were adopted. A triboelectric nonwoven fabric was prepared in the same manner as in Example 5, except that the water flow entangled web thus prepared was used. Table 3 shows various physical properties of each triboelectric nonwoven fabric manufactured as described above.
  • the triboelectric nonwoven fabrics prepared in Examples 5 to 8 were all triboelectric nonwoven fabrics having a thickness of 1.2 mm or less and a maximum point strength of more than 43.0 N / 50 mm.
  • a triboelectric non-woven fabric having a low ventilation resistance is provided because the apparent density is less than 0.15 g / cm 3 (more preferably 0.12 g / cm 3 or less). It turned out that it could be done. From the result of comparing Example 5 and Example 7, the fiber layer A in which the fibers are oriented in one direction and the fiber layer B in which the fibers are oriented in a direction different from the one direction are laminated. It has been found that by having the structure, it is possible to provide a triboelectric non-woven fabric having high collection efficiency.
  • the triboelectric fibers constituting the triboelectric nonwoven fabric contain a non-hydrophilic oil agent, so that the triboelectric nonwoven fabric with high collection efficiency can be provided. bottom.
  • the fiber layer A in which the fibers are oriented in one direction and the fiber layer B in which the fibers are oriented in a direction different from the above one direction are used. It had a structure in which and were laminated. Further, since it is manufactured without performing needle punching, the triboelectric nonwoven fabric prepared in each example does not have holes derived from needle processing such as through holes by needle punching.
  • the frictionally charged non-woven fabric according to the present invention for example, it is used in a production factory for foods and medical products, a manufacturing factory for precision equipment, an indoor cultivation facility for agricultural products, a general household use or an industrial facility such as an office building, and air. It is possible to prepare air filters for electric appliances such as purifiers and OA equipment, and for various vehicles such as automobiles and aircraft. Further, a mask can be prepared by using the triboelectric nonwoven fabric according to the present invention. Further, the above-mentioned triboelectric nonwoven fabric can be produced by the method for producing a triboelectric nonwoven fabric according to the present invention.

Abstract

Le problème à résoudre par la présente invention est de fournir un tissu non tissé à charge par friction dans lequel deux types de fibres ou plus ayant différentes résines constitutives sont mélangés, le tissu non tissé étant mince et présentant une résistance supérieure.　La présente invention concerne un tissu non tissé à charge par friction dans lequel deux types ou plus de fibres ayant différentes résines constitutives sont mélangés, l'épaisseur du tissu non tissé étant de 1,2 mm ou moins, et la résistance de point maximale étant supérieure à 43,0 N/50 mm. De plus, la présente invention concerne un procédé de fabrication d'un tissu non tissé à charge par friction dans lequel deux types ou plus de fibres ayant différentes résines constitutives sont mélangés, ledit procédé comprenant : (1) une étape consistant à préparer une bande dans laquelle au moins deux types de fibres ayant différentes résines constitutives sont mélangés ; (2) une étape consistant à effectuer un processus d'hydro-enchevêtrement sur la bande et à formuler une bande hydro-enchevêtrée ; et (3) une étape consistant à déformer la bande hydro-enchevêtrée dans la direction de l'épaisseur et à appliquer, à la bande hydro-enchevêtrée qui a été déformée dans la direction de l'épaisseur, une force de traction dans une direction perpendiculaire à la direction de l'épaisseur, moyennant quoi les fibres constitutives de la bande hydro-enchevêtrée sont torsadées ensemble.
PCT/JP2021/019046 2020-05-27 2021-05-19 Tissu non tissé à charge par friction et son procédé de fabrication WO2021241367A1 (fr)

Priority Applications (3)

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CN202180038066.8A CN115667610A (zh) 2020-05-27 2021-05-19 摩擦带电无纺布以及其制造方法
JP2021545840A JP6955645B1 (ja) 2020-05-27 2021-05-19 摩擦帯電不織布、および、その製造方法
TW111108462A TW202245898A (zh) 2021-05-19 2022-03-09 摩擦帶電不織布及其製造方法

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220773A (ja) * 2000-11-28 2002-08-09 Carl Freudenberg:Fa 摩擦電気を帯電した不織布の製造方法
JP2008093501A (ja) * 2006-10-06 2008-04-24 Toyobo Co Ltd 再生使用可能な摩擦帯電濾材

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220773A (ja) * 2000-11-28 2002-08-09 Carl Freudenberg:Fa 摩擦電気を帯電した不織布の製造方法
JP2008093501A (ja) * 2006-10-06 2008-04-24 Toyobo Co Ltd 再生使用可能な摩擦帯電濾材

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