WO2016104784A1 - Fibre pour filtre, filtre, et procédé de traitement de l'eau - Google Patents

Fibre pour filtre, filtre, et procédé de traitement de l'eau Download PDF

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Publication number
WO2016104784A1
WO2016104784A1 PCT/JP2015/086405 JP2015086405W WO2016104784A1 WO 2016104784 A1 WO2016104784 A1 WO 2016104784A1 JP 2015086405 W JP2015086405 W JP 2015086405W WO 2016104784 A1 WO2016104784 A1 WO 2016104784A1
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Prior art keywords
fiber
filter
width
filter fiber
groove
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PCT/JP2015/086405
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English (en)
Japanese (ja)
Inventor
友浩 早川
敏道 楠木
川井　弘之
中塚　均
智貴 酒井
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株式会社クラレ
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Priority to JP2016566565A priority Critical patent/JP6553646B2/ja
Publication of WO2016104784A1 publication Critical patent/WO2016104784A1/fr

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    • 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
    • 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
    • D04H1/4391—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 characterised by the shape of the fibres
    • D04H1/43918—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 characterised by the shape of the fibres nonlinear fibres, e.g. crimped or coiled fibres
    • 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
    • D04H1/4391—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 characterised by the shape of the fibres
    • D04H1/43912—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 characterised by the shape of the fibres fibres with noncircular cross-sections
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/018—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the shape
    • 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

Definitions

  • the present invention relates to a filter fiber having water wettability despite being formed from a hydrophobic polymer, a filter having the filter fiber, and a water treatment method for treating water using the filter.
  • Patent Document 1 Japanese Patent Publication No. 2010-509099 discloses a high surface area fiber and an improved filter composite produced therefrom.
  • thermoplastic polymers polypropylene, polyester, nylon, polyethylene, TPU, copolyester, liquid crystal polymer, etc.
  • soluble outer sheath components polylactide, copolyester, polyvinyl alcohol or ethylene-vinyl alcohol copolymer, etc.
  • a high-surface-area fiber having a plurality of protrusions is obtained by producing a composite fiber to be constructed and washing and removing the outer sheath component from the composite fiber.
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-129327 discloses a fiber having 20 or more grooves on the fiber surface.
  • a method for producing a fiber for example, a composite fiber in which a polyethylene terephthalate component (X component) and a copolyester (Y component) are radially combined is spun, and the Y component is dissolved and removed from the composite fiber. Is described. It is described that the obtained fiber has a brown chestnut-like cross section (see FIG. 2 of Patent Document 2), has a high surface area, high contact resistance, and good squeaking feeling.
  • X component polyethylene terephthalate component
  • Y component copolyester
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-52161 also discloses a fiber having 20 or more grooves on the fiber surface.
  • polyethylene terephthalate is used as component X
  • heat-meltable component Y is used as component Y.
  • Composite spinning is performed using modified polyvinyl alcohol (ethylene content: 8 mol%), and after spinning, the component Y is dissolved and removed to obtain a fiber with good squeakiness.
  • Patent Document 4 Japanese Patent Laid-Open No. 2006-89851
  • polyethylene terephthalate component X
  • component Y ethylene-modified polyvinyl alcohol resin in which 8.7 mol% of ethylene is copolymerized are each divided (mandarin orange type).
  • a composite spinning pack forming an ultra-thin fiber nonwoven fabric while performing composite spinning, and then dissolving and removing most of the modified polyvinyl alcohol resin from the composite long fiber with water and drying, and then modifying polyvinyl alcohol A part of the obtained ultrafine long fiber nonwoven fabric remains.
  • Patent Document 1 does not describe a pleated shape protruding from a specific elliptical shape. Moreover, since there is a description that the outer sheath is removed by washing with a solvent, it is assumed that the outer sheath is completely removed by washing. That is, Patent Document 1 does not intend to make the surface of a high surface area fiber made of a hydrophobic polymer hydrophilic by a sheath component, and further, by making the surface hydrophilic, it is an effective filter medium as a water treatment filter. There is no suggestion that
  • Patent Documents 2 to 3 are obtained by removing the polymer component Y to obtain a fiber having a groove structure on the surface, but the main use is for clothing having a feeling of creaking, The tip is sharp. Therefore, the contact portions between the single fibers are engaged to form an associated state, the contact resistance between the fibers is increased, and the liquid flow resistance is too high for use as a water treatment filter.
  • these documents describe that when used as a battery separator, a hydrophilic treatment is separately performed. Therefore, in this document as well, the surface of the polymer component Y is to be hydrophilized with the polymer component X. There is no intention.
  • Patent Document 4 discloses that the Y component is removed from the fiber in which the X component and the Y component are combined in a radial split type.
  • this fiber since the center part of the fiber needs to be divided, there is no technical idea that a specific shape is given to the center part of the fiber after the Y component is removed. Therefore, there is no suggestion about a pleated structure extending from the fiber center to both sides.
  • an ultra-thin fiber non-woven fabric is constructed from the fibers from which the Y component has been removed, and this non-woven fabric is used as a liquid filter.
  • such a filter structure has a large pressure loss and traps trapped particles There is a problem that efficiency is not high.
  • the present inventors have ensured the shape stability of the filter fiber layer when immersed in water by (i) forming the filter fiber from a hydrophobic polymer, and (ii) having a specific shape with respect to the fiber.
  • a hydrophobic polymer for example, in water treatment etc.
  • a first configuration of the present invention is a filter fiber having a plurality of pleated projections, which is composed of a hydrophobic polymer,
  • a cross section of the fiber (a) an elliptical part having a substantially elliptical shape; (b) a plurality of protruding parts with rounded ends extending from the elliptical part on both sides; and (c) the protruding part and the protruding part. It is the fiber comprised from the groove part formed between parts.
  • a hydrophilic polymer is attached to the surface of the fiber, and the fiber surface maintains water wettability when subjected to hot water treatment at 95 ° C.
  • this fiber may have, for example, the following characteristics singly or in combination of two or more.
  • the fiber has a fineness of 6 dtex or less.
  • the elliptical part is composed of a long axis part and a short axis part, and the width of the short axis part is 3 to 30 ⁇ m.
  • the protrusion has a width of 0.5 to 4 ⁇ m.
  • the groove has a depth of 1 to 4 ⁇ m.
  • the width of the major axis of the ellipse is the width (major axis) of the longest part in the straight line passing through the center of the ellipse, and the part of the short axis is the shortest in the straight line passing through the center of the ellipse. This means the width (minor axis).
  • the ratio of the width of the major axis portion to the width of the minor axis portion is, for example, 1.1 to 6.0, preferably 1.1 to 4.0.
  • the ratio of the depth of the groove to the width of the elliptical short axis is 0.02 to 3. Is preferred.
  • the protrusion may have a width of 0.5 to 4 ⁇ m, and the depth of the groove is a ratio of the width of the protrusion (depth of the groove / width of the protrusion). , 1/1 to 4/1 may be used. Further, the groove portion may have a depth of 1 to 4 ⁇ m.
  • the ratio of the width of the protrusion to the width of the groove may be 2/1 to 20/1.
  • the hydrophobic polymer is preferably a polyolefin, polyamide or polyester, and the hydrophobic polymer is more preferably polypropylene.
  • the hydrophilic polymer is preferably a heat-meltable and water-soluble ethylene-vinyl alcohol copolymer, and the ethylene-vinyl alcohol copolymer contains 0.1 to 20 mol% of ethylene monomer units.
  • An ethylene-vinyl alcohol copolymer is preferable.
  • the hydrophilic polymer adhering to the filter fiber surface is 0.5% by mass or less (vs. filter fiber).
  • the hydrophilic polymer adheres to the fiber surface.
  • various surface analysis methods such as IR analysis.
  • the fiber is formed from a fiber formed by core-sheath type composite spinning using the hydrophobic polymer as a core layer and the hydrophilic polymer (such as a heat-meltable and water-soluble ethylene-vinyl alcohol copolymer) as a sheath layer.
  • the hydrophilic polymer such as a heat-meltable and water-soluble ethylene-vinyl alcohol copolymer
  • a fiber formed by removing the hydrophilic polymer is preferable.
  • the fiber may have a short fiber or long fiber shape.
  • the second configuration of the present invention is a filter including the filter fiber described above.
  • the filter refers to an apparatus that can remove or remove unnecessary components such as fine particles in water or components to be recovered by filtration.
  • the filter fiber is preferably a filter in which a dry or wet nonwoven fabric is formed.
  • a dry-type nonwoven fabric the nonwoven fabric formed from the fiber in which a single yarn fineness exceeds 0.5 dtex, for example, a spun bond nonwoven fabric, formed by direct spinning may be included.
  • the dry or wet nonwoven fabric is a filter filled in a cartridge.
  • the cartridge refers to a filter formed in a predetermined shape such as a flat plate shape or a cylindrical shape and accommodated in a housing.
  • the filter is suitably used for water treatment.
  • the third configuration of the present invention is a water treatment method for filtering water containing an object to be removed using the filter.
  • the filter fiber of the first configuration is formed of a hydrophobic polymer, and a large number of pleated projections having a specific shape protruding from a specific substantially elliptical columnar portion are arranged on the fiber surface. Therefore, it has rigidity and high surface area as a filter fiber.
  • the hydrophilic polymer is attached to the fiber surface, the fiber surface has water wettability, and for example, the water wettability is maintained even if the hot water treatment at 95 ° C. is performed 15 times. It has characteristics. Therefore, it has a preferable characteristic especially as a filter fiber for water treatment.
  • the filter according to the second configuration is loaded with the filter fiber composed of the hydrophobic polymer, the filter fiber is stable even when immersed in water. is there. Further, the filter fiber has a large number of pleated protrusions having a specific shape protruding from a specific substantially elliptical columnar part, so that the filter fiber has rigidity and a high surface area, and the filter fiber surface has water wettability. Therefore, it is suitably used as a water treatment filter.
  • the particles to be filtered can be efficiently removed or collected, and water treatment with a long filtration life is possible. Can be.
  • the first configuration of the present invention is a filter fiber made of a hydrophobic polymer and having a central portion and a plurality of pleated projections protruding from the central portion, and is specified in a fiber cross section perpendicular to the fiber axis. Further, a hydrophilic polymer is attached to the surface of the fiber, and when the fiber surface is subjected to hot water treatment at 95 ° C. 15 times, the wettability is maintained.
  • the cross section of the fiber includes: (a) an elliptical portion having a substantially elliptical shape; (b) a plurality of rounded protrusions extending from the elliptical part on both sides; and (c) the protruding part and the protruding part.
  • the elliptical part may be composed of a long axis part and a short axis part, and the width of the short axis part may be 3 to 30 ⁇ m, and / or (ii) the protrusion part may have a width of 0.5 to And / or (iii) the groove may have a depth of 1 to 4 ⁇ m.
  • the elliptical part is composed of a long axis part and a short axis part, and the width of the short axis part is 3 to 30 ⁇ m.
  • the filter fiber may have a fineness of 6 dtex or less, and preferably has a fineness of more than 0.5 dtex and 6 dtex or less. Such a filter fiber can be manufactured by a method described later.
  • the filter fiber of the present invention is formed by extruding a hydrophobic polymer as a core part and extruding a hydrophilic polymer as a sheath part to form a core-sheath type composite spun fiber, and after forming the composite fiber, the hydrophilic polymer in the sheath part It can be obtained by dissolving and removing the hydrophilic polymer so that at least a part of the polymer remains. More specifically, when a core-sheath type composite spun fiber is formed, the melted hydrophobicity from a nozzle capable of forming a composite fiber composed of a core part having a predetermined shape and a sheath part surrounding the core part. A core-sheath type composite spun fiber is formed by extruding a polymer for core formation and a melted hydrophilic polymer for sheath formation.
  • the core portion having a predetermined shape can be formed by using a composite spinning nozzle in which nozzle parts are adjusted so as to form an elliptical portion having a predetermined shape and a projection portion having a predetermined shape in the fiber cross section.
  • a nozzle component can be appropriately selected so as to have a shape corresponding to the cross-sectional shape of the core portion.
  • the spinning temperature is not particularly limited as long as the polymers forming the core and the sheath can each be maintained in a molten state.
  • the hydrophilic polymer in the sheath part is dissolved and removed within a predetermined range, so that (a) an elliptical part having a substantially elliptical shape in the fiber cross section, and (b) the above-mentioned It is composed of a plurality of protrusions with rounded tips extending from the ellipse on both sides, and (c) a groove formed between the protrusions and the protrusions.
  • the sheath may be removed after the core-sheath composite spun fiber is once formed into a predetermined shape such as a nonwoven fabric.
  • the hydrophilic polymer in the sheath is removed using hot water at a predetermined temperature in accordance with the solubility of the hydrophilic polymer, but not all of the hydrophilic polymer is removed, and at least a part of the hydrophilic polymer is removed. Polymer remains in the filter fibers.
  • the temperature of hot water may be, for example, 70 to 120 ° C., and preferably about 80 to 110 ° C. Since the composite fiber has an ellipse at the core, it has high rigidity and can be treated with hot water without gradually increasing the water temperature (that is, directly combined with hot water having a predetermined temperature). Fiber).
  • the removal of the hydrophilic polymer may be performed by leaving the conjugate fiber in hot water, or in order not to remove all the hydrophilic polymer in order to shorten the time required for the removal process, You may carry out by giving a physical irritation
  • stimulation for example, stirring process etc.
  • a pleated projection is formed in the core portion. Therefore, even when the removal treatment is performed in a state where physical stimulation is applied, the pleated portion is used. It is possible to leave a hydrophilic polymer.
  • the core-sheath type composite spun fiber obtained after the composite spinning is composed of a core part composed of a hydrophobic polymer and a sheath part composed of a hydrophilic polymer, and the sheath part surrounds the core part.
  • the core portion has substantially the same cross-sectional shape as the filter fiber.
  • the core of the composite spun fiber shown in FIG. 1 has substantially the same cross-sectional shape as the filter fiber shown in FIG.
  • the composite ratio of the hydrophobic polymer and the hydrophilic polymer can be appropriately set as long as the composite spinning is possible.
  • the hydrophobic polymer / hydrophilic property is used from the viewpoint of achieving both spinnability and sheath removability.
  • Polymer (mass ratio) 90/10 to 30/70, preferably about 80/20 to 40/60.
  • the hydrophobic polymer constituting the core part is not particularly limited as long as it is a hydrophobic polymer having fiber forming ability.
  • Polyolefin polyethylene, polypropylene, etc.
  • polyester polyethylene terephthalate, polybutylene terephthalate, etc.
  • polyamide nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, etc.
  • polyurethane for example, thermoplastic polyurethane (TPU), etc.
  • TPU thermoplastic polyurethane
  • the hydrophilic polymer constituting the sheath portion is not particularly limited as long as it is a hydrophilic polymer having fiber forming ability, but is preferably an ethylene-vinyl alcohol copolymer (ethylene copolymer ratio: 0.1 to 40). Mol%), hydroxyl group-containing polymers such as polyvinyl alcohol and polyhydroxybutyrate.
  • the hydrophilic polymer is preferably excellent in melt spinnability together with the hydrophobic polymer, and also excellent in removability from the composite fiber after spinning (particularly in hot water treatment).
  • an ethylene-vinyl alcohol copolymer having an ethylene copolymerization ratio of 0.1 to 20 mol%, preferably 3 to 15 mol% achieves both melt spinnability and removability with hot water. Therefore, it is particularly preferably used as the hydrophilic polymer in the present invention.
  • a preferred ethylene-vinyl alcohol copolymer may have a saponification degree of 88 to 99, preferably 90 to 98, for example.
  • the viscosity average degree of polymerization may be, for example, 300 to 2000, preferably 400 to 1700.
  • the saponification degree and the viscosity average polymerization degree can be appropriately set by those skilled in the art according to the type of hydrophobic polymer constituting the core, the fineness required of the composite fiber, and the like.
  • the core / sheath portion is polyolefin / ethylene-vinyl alcohol copolymer, polyester / ethylene-vinyl alcohol copolymer, polyamide / ethylene-vinyl alcohol copolymer, polyurethane / ethylene-vinyl alcohol copolymer. And so on.
  • a fiber having a fineness of 6 dtex or less preferably a fiber having a fineness of more than 0.5 dtex and 6 dtex or less by removing the sheath as described above, for example, a core-sheath type composite
  • the fineness of the spun fiber may be, for example, 15 dtex or less, preferably 0.7 to 15 dtex, and more preferably 0.7 to 10 dtex.
  • Example 1 a fiber having a fineness of 3.3 dtex of a core-sheath type composite spun fiber (core part: 60% by mass of polypropylene; sheath part: 40% by mass of ethylene-vinyl alcohol copolymer) As a result, a filter fiber having a fineness of 2.2 dtex was obtained.
  • the fiber surface area (BET) in this case was 1.94 m 2 / g. Further, in the result of analyzing the fiber surface after removal of the sheath portion by XPS analysis, the hydrophilic polymer remains because oxygen can be confirmed on the fiber surface.
  • the filter fiber of the present invention is used as a filter fiber for water treatment in particular, the fiber is formed from a hydrophobic polymer, but the fiber surface needs to have water wettability. For this reason, after removing the hydrophilic polymer from the core-sheath type composite spun fiber having the hydrophobic polymer as the core and the hydrophilic polymer as the sheath, a small amount of the hydrophilic polymer remains on and adheres to the fiber surface. The fiber surface maintains water wettability (water absorption) after being subjected to hot water treatment at 95 ° C. 15 times.
  • the adhesion amount of the hydrophilic polymer 99% by mass or more and less than 100% by mass of the hydrophilic polymer may be removed from the core-sheath composite fiber.
  • the hydrophilic polymer may be attached to the fiber in a minute amount. It is preferable that it exceeds 0.5 mass% and exceeds 0.5 mass%. If the adhesion amount is too large, the hydrophilic polymer tends to fall off during use as a filter. The remaining trace amount of hydrophilic polymer retains the wettability of the filter fiber over a long period of time.
  • the trace amount may be an amount in which the hydrophilic polymer remains to the extent that the water wettability of the filter fiber is maintained.
  • the remaining of the hydrophilic polymer (for example, ethylene-vinyl alcohol copolymer) is considered as follows. A part of radicals at the time of polymer production (polymerization) is trapped in the polymer, and at the time of heat melting for fiber formation, a polymer in which the trapped radicals are combined to form a large molecule (including crosslinking) is formed, A small amount of this polymer having a large molecular weight is contained in the hydrophilic polymer layer of the fiber, and it remains on the fiber surface without being removed when the hydrophilic polymer is removed.
  • ethylene-vinyl alcohol copolymer for example, ethylene-vinyl alcohol copolymer
  • the hydrophilic polymer may be subjected to repeated hot water treatment. It is considered that a very small amount is adhered without being completely removed, and the water wettability of the fiber surface is maintained by this adhesion.
  • a filter fiber obtained from a core-sheath composite spun fiber formed with a hydrophilic polymer for example, an ethylene-vinyl alcohol copolymer having an ethylene copolymerization ratio of 0.1 to 20 mol% as a sheath is made of hot water Since the water wettability is maintained even when the treatment is repeated 15 times or more, it is suitably used as a filter material for water treatment.
  • a hydrophilic polymer for example, an ethylene-vinyl alcohol copolymer having an ethylene copolymerization ratio of 0.1 to 20 mol
  • a hydrophilic polymer is attached to the surface of the filter fiber, and the fiber surface is subjected to a hot water treatment at 95 ° C. for 30 minutes at a bath ratio of 1:20 with respect to the fiber amount. It is necessary that the wettability is maintained even when the drying treatment at 60 ° C. for 10 minutes is set as one set and this treatment is carried out 15 times. If water wettability cannot be maintained after less than 15 times, the filter fiber may lose water wettability during use, and may not function as a filter fiber over a long period of time.
  • the single fiber fineness of the filter fiber may be 6 dtex or less, for example, more than 0.5 dtex and 6 dtex or less, and preferably 1 dtex to 4 dtex.
  • a filter layer formed from fibers with too small fineness is disadvantageous in terms of strength, and is not suitable as a filter fiber because the pressure loss increases.
  • the fineness is too large, the filter layer becomes coarse and it becomes difficult to filter fine particles, which makes it unsuitable as a filter fiber.
  • the surface area (BET) of the filter fiber is, for example, 0.8 to 4.0 m 2 / g from the viewpoint of imparting wettability by adhering the hydrophilic polymer to the fiber surface made of the hydrophobic polymer. It may be 1.2 to 3.0 m 2 / g.
  • the filter fiber has, in cross-sectional shape, (a) an elliptical part having a substantially elliptical shape, (b) a plurality of protruding parts with rounded ends extending from the elliptical part on both sides, and (c) the protruding part. And a groove formed between the protrusions.
  • the elliptical part is preferably a solid-filled elliptical part from the viewpoint of rigidity.
  • the width of the short axis part of the ellipse may be in the range of 3 ⁇ m to 30 ⁇ m, and preferably in the range of 4.0 ⁇ m to 20 ⁇ m.
  • the filter fibers have a flat shape, so that the density of the filter layer formed by laminating the filter fibers becomes too high, which tends to be unsuitable in terms of pressure loss. Moreover, since a fiber cross section will approximate circular when the width becomes too large, it becomes difficult to form a large number of protrusions.
  • the ratio of the long axis portion to the short axis portion may be, for example, in the range of 1.1 to 5.0, preferably in the range of 1.1 to 4.0, more preferably 1 It may be in the range of 0.5 to 4.0, more preferably in the range of 2.1 to 4.0. If the ratio is too large, the fiber shape becomes flat, which may cause the above-mentioned problems. If the ratio is too small, the fiber approaches a circle and it is difficult to form many protrusions. .
  • the plurality of protrusions may protrude adjacent to each other across the groove from the ellipse, and both sides from the ellipse (upper and lower sides with the major axis of the ellipse being axisymmetric). On both sides), preferably on the entire circumference of the ellipse.
  • the trapping property by the groove is effectively utilized by utilizing the gentle curvature of the substantially ellipse. It can be effectively used to achieve both improvement in strength and strength of the protrusion.
  • the width of the protrusion may be, for example, in the range of 0.5 to 4 ⁇ m, and preferably in the range of 1 to 3 ⁇ m. If the width is too narrow, the strength of the protrusion becomes too weak and the protrusion is easily chipped, which is not suitable. On the other hand, if the width is too large, it is difficult to arrange many protrusions. It is.
  • the number of protrusions per filter fiber is, for example, 5 to 50, preferably 10 to 40, more preferably 20 to 35. If the number of protrusions is too small, the surface area of the fiber surface increases. If the effect is not sufficient and the number of protrusions is too large, the width of one protrusion is narrowed, and the strength of the protrusion tends to be insufficient.
  • the tip of the protruding portion protruding from the elliptical portion needs to be rounded (see, for example, FIG. 1).
  • the tip of the protrusion is not rounded but is tapered toward the tip (see FIGS. 2 and 4 of Patent Document 3), the tip tends to be damaged, which is not preferable as a filter fiber.
  • the depth of the groove is, for example, in the range of 1 to 4 ⁇ m, preferably in the range of 1.5 to 3.6 ⁇ m, and more preferably in the range of 2 to 3.2 ⁇ m. It is within the range. If the groove is too shallow, the filter fiber particles may not be sufficiently captured. By increasing the depth of the groove portion, the surface area of the filter fiber according to the present invention is increased and the effect of imparting water wettability is increased. On the other hand, even if the groove portion is too deep, particles contained in the treated water It does not contribute to the capture property.
  • the width of the groove is, for example, 0.1 ⁇ m to 2.0 ⁇ m, more preferably 0.1 to 1.0 ⁇ m, still more preferably 0.1 to 0.5 ⁇ m, and particularly preferably 0.1 to 0.18 ⁇ m. It is preferable from the viewpoint of particle trapping properties.
  • the ratio of the width of the protruding portion to the width of the groove portion is preferably 2 / The range may be from 1 to 20/1, more preferably from 5/1 to 15/1.
  • the ratio of the groove depth to the groove width is preferably 1/2 to 40/1, more preferably 1/1 to 20/1.
  • the depth of the groove is, for example, the same as the width of the protrusion, and less than 4 times, and preferably 1.2 times to 3.5 times the width of the protrusion. It is preferable in terms of balance with the strength of the protruding portion.
  • the bottom of the groove between the protrusions is rounded.
  • the adhesiveness to the groove part of a hydrophilic polymer can be improved.
  • the ratio of the depth of the groove and the width of the elliptical short axis (depth of the groove / width of the elliptical short axis) May be about 0.02 to 3, more preferably about 0.1 to 2.5, and still more preferably about 0.5 to 1.5.
  • the filter fiber may be directly used as various shapes, for example, a short fiber (cut fiber) or a long fiber (filament), as long as it can be used for a filter device. May be used by forming it into a fabric shape, for example, a nonwoven fabric (wet, dry, spunbonded, etc., directly-coupled type).
  • a nonwoven fabric wet, dry, spunbonded, etc., directly-coupled type.
  • the filter fiber is preferably used in the form of a nonwoven fabric, and a spunbonded nonwoven fabric is particularly preferred.
  • the nonwoven fabric may be subjected to post-processing such as embossing treatment as necessary.
  • the basis weight of the filter fiber nonwoven fabric is, for example, preferably 20 to 300 g / m 2 , preferably 30 to 200 g / m 2 , and more preferably 40 to 100 g / m 2 . If the basis weight of the nonwoven fabric is too small, the strength will be too low and it will break during processing during filter molding. Moreover, when the fabric weight of a nonwoven fabric is too large, the tension
  • the basis weight of the core-sheath type composite spun fiber nonwoven fabric before removing the sheath component is, for example, 30 to 500 g / m 2 , preferably 50 to 350 g / m 2 , more preferably 60 to 200 g / m 2. Also good.
  • the filter cartridge used in the present invention may be any of known filter cartridges, for example, a thread wound cartridge in which filter fibers are wound around a core material, a filter in which a dry or wet nonwoven fabric composed of filter fibers is filled in the cartridge It may be.
  • a flat plate cartridge in which a plurality of flat filter units formed by arranging two rectangular filter media facing each other, a pleated cartridge having a structure in which filter media are folded into a pleat shape, and the like are illustrated. can do.
  • a filter medium mounted on a pleated cartridge filter is folded by pleating, and the folded filter medium is wound around a core body, inserted into a cylindrical container, and used for water filtration.
  • the filter fiber of the present invention can be suitably used as various filter materials that require hydrophilicity.
  • the filter fiber of the present invention can be suitably used as a filter material for water treatment, and specifically, water filtration that removes or collects the foreign matter from the water in which the foreign matter is mixed (for example, It can be suitably used as a water treatment filter in water and circulation filtration of pools and hot springs, and water filtration in seawater desalination plants.
  • FIG. 3 shows a state after the water is filtered using the filter fiber according to the present invention. It can be seen that the substance to be filtered in water is caught by the groove formed between the protrusions of the filter fiber of the present invention.
  • this invention may include the following embodiments as filter fiber.
  • each characteristic described in the following embodiments may conform to each characteristic described above.
  • the fibers have a fineness of 6 dtex or less;
  • the ratio of the width of the major axis portion to the width of the minor axis portion is 1.1 to 6.0,
  • a filter fiber made of a hydrophobic polymer and having a plurality of pleated projections, wherein the cross section of the fiber is (a) an elliptical part having a substantially elliptical shape, and (b) extending from the elliptical part to both sides.
  • the fiber has a groove depth of 1 to 4 ⁇ m, and a ratio of the groove depth to the width of the elliptical short axis portion (depth of the groove portion / width of the elliptical short axis portion) is 0.02 to 3 Yes,
  • a filter fiber having a ratio of the width of the protrusion to the width of the groove (width of the protrusion / width of the groove) of 2/1 to 20/1.
  • a ratio of a width of the major axis portion to a width of the minor axis portion is 1.1 to 6.0.
  • any one of the aspects 1 to 5 wherein the ratio of the depth of the groove portion to the width of the elliptical short axis portion (depth of the groove portion / width of the elliptical short axis portion) is 1/10 to 4/1.
  • [Aspect 7] 7 The filter fiber according to any one of aspects 1 to 6, wherein in the filter fiber, the protrusion has a width of 0.5 to 4 ⁇ m, and the groove has a depth of 1 to 4 ⁇ m.
  • the fiber is formed by removing the hydrophilic polymer from a fiber formed by core-sheath type composite spinning using the hydrophobic polymer as a core layer and the hydrophilic polymer as a sheath layer.
  • BET method Evaluation of specific surface area of fiber (BET method)> It evaluated using the flow method BET 1-point method specific surface area measuring apparatus (Monosorb made from Quantachrome). In the pretreatment attached to the apparatus, deaeration was performed at room temperature for 30 minutes in an N 2 gas atmosphere. In the measurement, a mixed gas (N 2 30%, He 70%) was allowed to flow through the U-shaped cell containing the sample, the sample chamber was cooled to liquid nitrogen temperature (77K), and only the N 2 gas was adsorbed on the surface of the sample.
  • N 2 30%, He 70% a mixed gas
  • the cross section of the filter fiber was photographed with a scanning electron microscope (magnification: 5000 times), and the printed image was used to determine the width of the minor axis of the ellipse, the ratio of the width of the major axis to the minor axis, and the protrusion The width of the part and the depth of the groove part were measured.
  • the width of the protrusions for the ten protrusions randomly selected from the image, the width at the point between the tip part and the root part of the protrusion part is measured, and the average value is obtained. The width of the part.
  • the protrusions were basically selected by excluding the protrusions protruding from the end of the major axis, and the protrusions were selected from the protrusions protruding from within 80% of the major axis width around the minor axis.
  • tip part of a protrusion part and a root part was measured about ten randomly selected protrusion parts, the average value was calculated
  • the width of the groove from the image, for 10 randomly selected grooves, the width at the point between the tip and the root of the groove is measured, and the average value is obtained. did.
  • the ellipse part it is a part excluding the protruding part in the fiber cross section, and in the straight line passing through the center of the ellipse from the printed image, the longest part is the long axis part, and in the straight line passing through the center of the ellipse
  • the portion having the shortest width was defined as the short axis portion, and the major axis that was the width of the major axis portion and the minor axis that was the width of the minor axis portion were each calculated from the average value of ten measurement results.
  • the center of the circumscribed circle of the portion excluding the protruding portion in the fiber cross section is the center of the ellipse.
  • the shortest portion in the straight line passing through the center of the circumscribed circle is the short axis portion, and the short axis portion On the straight line passing through the center, the longest portion was defined as the longest width portion.
  • PP polypropylene
  • EXC ethylene copolymerization ratio
  • the fineness of the core-sheath type composite spun fiber was 3.3 dtex, and the basis weight of the fiber accumulation sheet was 120 g / m 2 .
  • the nonwoven fabric was immersed in hot water at 95 ° C. for 30 minutes, and the ethylene-vinyl alcohol copolymer was removed from the core-sheath composite spun fiber to obtain a filter fiber having a cross section shown in FIG. .2 dtex).
  • the basis weight of the spunbonded nonwoven fabric formed by hot embossing the accumulated sheet after the hot water treatment was 72 g / m 2 .
  • the fiber surface area (BET) was 1.94 m 2 / g.
  • the fiber cross section was substantially oval at the center, and the protrusion protruded from the center, and the tip of each of the protrusions was rounded.
  • the width of the short shaft portion is 4 ⁇ m
  • the ratio of the width of the long shaft portion to the short shaft portion is 3.7
  • the number of the protrusion portions is 30,
  • the width of the protrusion portions is 1.5 ⁇ m
  • the width of the groove portion is 0.
  • the depth of the groove portion was 3 ⁇ m
  • the ratio of the groove depth to the groove width (groove depth / groove width) was 20/1.
  • the adhesion amount of the ethylene-vinyl alcohol copolymer from the composite spun fiber was 0.43% by mass (vs. the mass of the nonwoven fabric).
  • the surface of the obtained spunbond nonwoven fabric was analyzed by XPS analysis, and the surface oxygen content was measured. The results are shown in FIG. As a result of analyzing the fiber surface after removal of the sheath by XPS analysis, oxygen can be confirmed on the fiber surface, so that a hydrophilic polymer remains. Water drops were dropped on the obtained spunbond nonwoven fabric sample, and the spread of the water drops was observed. The result is shown in FIG. 5A. Further, the nonwoven fabric sample is immersed in hot water at 95 ° C. for 30 minutes (bath ratio: 1:20), taken out after immersion, cooled and dried (60 ° C., 10 minutes), and then again in 95 ° C. hot water. This treatment was repeated 15 times to measure the droplet absorption rate, and the results are shown in FIG.
  • a spunbonded nonwoven fabric (weight per unit area: 80 g / m 2 ) made of polypropylene fiber (single filament: 3.3 dtex) is mixed with an ethylene-vinyl alcohol copolymer (ethylene copolymerization ratio: 8.7 mol%) aqueous solution (polymer concentration: (0.4% by mass) to prepare a sample coated with 0.4% by mass (filter fiber mass) of ethylene-vinyl alcohol copolymer.
  • Example 1 Since the ethylene-vinyl alcohol copolymer was present in a smaller amount than in Example 1, such a phenomenon was not observed. From the results shown in FIG. 6, in the filter fiber according to the present invention (Example 1), water absorption is immediately observed, whereas in the case of Comparative Example 1, as the number of hot water treatments increases, It takes time to absorb the water droplets, and it is shown that the ethylene-vinyl alcohol copolymer is being detached from the fiber surface as the number of hot water treatments is increased.
  • Example 2 The filter fiber according to the present invention (after hydrothermal treatment and before nonwoven fabric formation) was evaluated using a micromer (latex particle) having a different particle diameter (manufactured by Micromod) as an evaluation dust and using the apparatus shown in FIG.
  • the sample sample (4) was attached to the sample holder (3), and the test liquid prepared by adjusting the solid content concentration of the evaluation dust to 0.125 mg / L was passed through 2 L at a flow rate of 350 ml / min.
  • the number of particles was evaluated by measuring the number of each particle diameter with a particle counter (manufactured by PARTICLE MEASURING SYSTEMS: MODEL LS-200).
  • a particle counter manufactured by PARTICLE MEASURING SYSTEMS: MODEL LS-200
  • the hollow fiber filter (2) is for removing dust contained in the filter cleaning water in the filter cleaning.
  • the dust collection efficiency was evaluated according to the following procedure.
  • Collection efficiency calculation Collection efficiency 100-([4]-[2]) ⁇ ([3]-[1]) x 100 After the step (c) and immediately before the end of the step (e), the measurement was performed with a pressure gauge installed in the apparatus shown in FIG.
  • the dust trapping property was evaluated using evaluation dusts having different diameters for a 2 g column packed only with filter fibers (diameter: 17 ⁇ m, 2.2 dtex) according to the present invention. The results are shown in FIG.
  • ⁇ Comparative Example 3> Polypropylene (PP) and ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., ethylene copolymerization ratio: 8.7 mol%) (sometimes abbreviated as EXC) as separate fibers for comparison It is supplied to a machine and melted and discharged from a composite fiber forming nozzle having a pleat number of 32 at a ratio of PP / EXC 60/40 (mass ratio), and a core-sheath type composite spun fiber (core: A core-sheath composite spun fiber composed of polypropylene; sheath: ethylene-vinyl alcohol copolymer) was formed, and hydrothermal treatment was performed in the same manner as in Example 1 to obtain a filter fiber (fineness: 3.2 dtex).
  • core A core-sheath composite spun fiber composed of polypropylene; sheath: ethylene-vinyl alcohol copolymer
  • the fiber cross section was substantially oval at the center, and the protrusion protruded from the center, and the tip of each of the protrusions was rounded.
  • the width of the short shaft portion is 1.5 ⁇ m
  • the ratio of the width of the long shaft portion to the short shaft portion is 17.6
  • the number of protrusions is 32
  • the width of the protrusions is 1.3 ⁇ m
  • the root of the protrusions The width of the part was 1.3 ⁇ m
  • the depth of the groove part was 6 ⁇ m. Dust collecting property was evaluated in the same manner as in Example 2.
  • ⁇ Comparative example 4> As a comparative fiber, a dust collecting property was evaluated in the same manner as described above for a polypropylene fiber having a circular cross section (diameter: 17.5 ⁇ m, 2.2 dtex).
  • a core-sheath type composite spun fiber composed of a core-sheath type composite spun fiber (core part: polypropylene; sheath part: polylactic acid) is formed by discharging from a fiber forming nozzle and placed in 10% sodium hydroxide at 80 ° C.
  • the polylactic acid component was removed by dipping to obtain filter fibers (fineness: 2.2 dtex). When the obtained fiber was subjected to hot water treatment at 95 ° C. 15 times, the wettability was not maintained.
  • the obtained filter fiber cross section had the same shape as in Example 1, and the dust collecting property was evaluated in the same manner as in Example 2.
  • the results obtained in Example 2 and Comparative Examples 2 to 5 are shown in Table 1.
  • Example 2 has a pleated protrusion protruding from an elliptical columnar part having a predetermined shape, and also has water wettability derived from a hydrophilic polymer. In addition to exhibiting dust collection efficiency, it is possible to maintain the pressure at the time of passing a fluid at a low value. That is, in Example 2, not only the initial pressure is a low value of 15 Kpa, but also the post-evaluation pressure at the end of the filtration test can be maintained at a low pressure of 20 Kpa.
  • Comparative Example 2 is advantageous in terms of trapping properties because it has a fineness of about 1/30 that of the filter fiber of Example 2.
  • the initial pressure in the filtration test is an extremely high pressure of 55 Kpa.
  • the pressure is further increased, and the post-evaluation pressure shows an extremely high value of 85 Kpa.
  • Comparative Example 3 although it is derived from a hydrophilic polymer and has water wettability, the fiber does not have the predetermined shape defined in the present invention, and thus exhibits satisfactory characteristics in terms of collection.
  • the initial pressure in the filtration test is 30 Kpa, which is twice as high as that in Example 2.
  • the pressure is further increased, and the post-evaluation pressure is 45 Kpa, which is twice as high as that of the example.
  • Comparative Example 4 the fineness is similar to that of the filter fiber of Example 2, but the cross-sectional shape is a round cross section and does not have water wettability, so the collection efficiency is extremely low at 0.1% or less. The value is low.
  • Comparative Example 5 although the fibers have a predetermined shape defined in the present invention, the collection efficiency is inferior to that of Example 2 because it is derived from the hydrophilic polymer and does not have water wettability.
  • the initial pressure in the filtration test is 25 Kpa, which is higher than that at the end of the filtration test of Example 2. At the end of the filtration test, the pressure was further increased, and the post-evaluation pressure was 30 Kpa, 1.5 times higher than Example 2.
  • the filter fiber of the present invention is formed from a hydrophobic polymer, the surface has many pleated projections, a high surface area, and the surface has water wettability, so that the water treatment is particularly effective. Since it is useful as a filter fiber for industrial use, it has industrial applicability.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Filtering Materials (AREA)
  • Nonwoven Fabrics (AREA)
  • Filtration Of Liquid (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Multicomponent Fibers (AREA)

Abstract

La présente invention concerne une fibre pour filtre qui est formée d'un polymère hydrophobe et présente une mouillabilité à l'eau. La fibre est formée d'un polymère hydrophobe et comporte des protubérances de type ruche multiples, la section transversale de la fibre étant formée de (a) une partie ovale ayant une forme approximativement ovale, (b) des protubérances multiples qui s'étendent sur les deux côtés depuis la partie ovale et dont chacune a une extrémité arrondie et (c) des rainures dont chacune est formée entre deux des protubérances adjacentes. Un polymère hydrophile est amené à adhérer sur la surface de la fibre, et la mouillabilité à l'eau de la surface de la fibre est maintenue lorsqu'un traitement avec de l'eau chaude est conduit à 95 °C dans 15 cycles.
PCT/JP2015/086405 2014-12-26 2015-12-25 Fibre pour filtre, filtre, et procédé de traitement de l'eau WO2016104784A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019203216A (ja) * 2018-05-23 2019-11-28 東レ株式会社 湿式不織布
EP3518652A4 (fr) * 2016-09-30 2020-07-01 Jutta M. Gietl Systèmes et procédés d'irrigation souterraine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62289668A (ja) * 1986-06-05 1987-12-16 ユニチカ株式会社 扁平複合ポリエステル繊維
JP2010509517A (ja) * 2006-11-03 2010-03-25 アラッソ・インダストリーズ・インコーポレーテッド 改良された高表面積繊維及びそれから製造されるテキスタイル
JP2014073442A (ja) * 2012-10-03 2014-04-24 Daiwabo Holdings Co Ltd フィルターおよびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62289668A (ja) * 1986-06-05 1987-12-16 ユニチカ株式会社 扁平複合ポリエステル繊維
JP2010509517A (ja) * 2006-11-03 2010-03-25 アラッソ・インダストリーズ・インコーポレーテッド 改良された高表面積繊維及びそれから製造されるテキスタイル
JP2014073442A (ja) * 2012-10-03 2014-04-24 Daiwabo Holdings Co Ltd フィルターおよびその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3518652A4 (fr) * 2016-09-30 2020-07-01 Jutta M. Gietl Systèmes et procédés d'irrigation souterraine
JP2019203216A (ja) * 2018-05-23 2019-11-28 東レ株式会社 湿式不織布
JP7047593B2 (ja) 2018-05-23 2022-04-05 東レ株式会社 湿式不織布

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