EP2229474B1 - Conjugate fiber having low-temperature processability, nonwoven fabric and formed article using the conjugate fiber - Google Patents
Conjugate fiber having low-temperature processability, nonwoven fabric and formed article using the conjugate fiber Download PDFInfo
- Publication number
- EP2229474B1 EP2229474B1 EP08863375.5A EP08863375A EP2229474B1 EP 2229474 B1 EP2229474 B1 EP 2229474B1 EP 08863375 A EP08863375 A EP 08863375A EP 2229474 B1 EP2229474 B1 EP 2229474B1
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- EP
- European Patent Office
- Prior art keywords
- component
- fiber
- conjugate fiber
- nonwoven fabric
- conjugate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
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- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 239000012510 hollow fiber Substances 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- 229920000223 polyglycerol Polymers 0.000 description 1
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Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- 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
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/04—Supporting filaments or the like during their treatment
- D01D10/049—Supporting filaments or the like during their treatment as staple fibres
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/32—Side-by-side structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
-
- 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
- D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
-
- 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
- D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed 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
- D04H13/00—Other non-woven fabrics
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/04—Heat-responsive characteristics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/608—Including strand or fiber material which is of specific structural definition
Definitions
- the present invention relates to a conjugate fiber that demonstrates low-temperature processability during heat processing and excellent heat adhesiveness without shrinking significantly.
- the present invention also relates to a nonwoven fabric and formed article that use the conjugate fiber and have excellent bulkiness and excellent feeling.
- conjugate fibers having low-temperature processability have conventionally been proposed, and ethylene - ⁇ -olefin copolymer has been used as a component forming these conjugate fibers, for the reason that the melting point of the component can be easily controlled by using it.
- a sheath-core and side-by-side conjugate fiber in which a "mixture" of a polyethylene resin having a low melting point of 90 to 125°C and a polyethylene resin having a high melting point of 120 to 135°C is used as one of conjugate components (see, for example, Patent Literature 1).
- the conjugate fiber proposed in Patent Literature 1 does not necessarily have sufficient low-temperature processability because the polyethylene resin having a low melting point of 90 to 125°C is used and at the same time the polyethylene resin having a high melting point of 120 to 135°C is "mixed" into the abovementioned low-melting point polyethylene resin in an amount of, substantially, 30 % by weight or more in order to achieve stable productivity, and because the mixture of these polyethylene resins is used as one component of the conjugate fiber.
- Patent Literature 2 which relates to a latently crimpable conjugate fiber that utilizes a characteristic that the conjugate fiber containing an ethylene- ⁇ -olefin copolymer as a component shrinks easily during heat processing, such a latently crimpable conjugate fiber is not suitable for obtaining a nonwoven fabric that does not shrink but has excellent uniformity.
- such a latently crimpable conjugate fiber utilizes a difference in shrinkage characteristics between the plurality of constituents, and hence pealing occurs easily in these components after heat processing.
- the melting adhesive component and the other non-melting component are pealed when processing the latently crimpable conjugate fiber into a nonwoven fabric, the fiber composed of the adhesive component and the fiber composed of the other non-melting component are almost mixed within the nonwoven fabric.
- the strength of the nonwoven fabric cannot be exhibited.
- An object of the present invention is to provide a conjugate fiber, which has low-temperature processability, is prevented from shrinking, has excellent heat adhesiveness and excellent card passability when processing the conjugate fiber into a nonwoven fabric and particularly when performing card processing, and is capable of obtaining a bulky nonwoven fabric with excellent uniformity
- Another object of the present invention is to provide bulky nonwoven fabric and formed article of them having excellent uniformity and excellent low-temperature processability.
- a conjugate fiber that forms a specific side-by-side cross section that has a first component containing a specific ethylene - ⁇ -olefin copolymer as a component for contributing to low-temperature processability of the conjugate fiber, i.e., a component having a lower melting point and softened and molten when heated, in a specific amount or more, and a second component containing a crystalline polypropylene.
- the present invention is a conjugate fiber as specified in claim 1.
- examples of the ethylene - ⁇ -olefin copolymer to be used include an ethylene - ⁇ -olefin copolymer having a molecular weight distribution (Mw/Mn) of 1.5 to 2.5, a density of 0.87 to 0.91 g/cm 3 , and a melt index (MI) of 10 to 35 g/10 min as measured under conditions with a temperature of 190°C and a load of 21.2 N based on ASTM D-1238.
- Mw/Mn molecular weight distribution
- MI melt index
- the above conjugate fiber can show a heat shrinkage percentage of 50% or lower when subjected to heat processing at 100°C for five minutes.
- the conjugate fiber of the present invention can be processed into a nonwoven fabric to produce a nonwoven fabric, and the conjugate fiber of the present invention can be processed or the nonwoven fabric obtained from the conjugate fiber of the present invention can be processed to obtain a shaped article.
- the present invention is also intended for a nonwoven fabric obtained by processing the conjugate fiber into a nonwoven fabric, a formed article obtained using the conjugate fiber, and a formed article obtained using the nonwoven fabric.
- Examples of the processing into a nonwoven fabric include a hot-air adhesion method and a hot-water adhesion method.
- the conjugate fiber of the present invention has a side-by-side cross section in which a first component containing 75 % by weight of an ethylene - ⁇ -olefin copolymer having a melting point of 70 to 100°C accounts for 55 to 90% of an outer periphery of the fiber in a fiber cross section perpendicular to a fiber axis, a borderline between the first component and the second component forms a curve bulging toward the first component, and in which an area ratio between the first component and the second component (first component/second component) is in a range of 70/30 to 30/70.
- the first component containing the ethylene - ⁇ -olefin copolymer covers mainly the surface of the fiber, the first component shows an excellent heat adhesiveness at a heat processing temperature of 100°C or lower. Specifically, excellent low-temperature processability is obtained. Furthermore, because the second component containing a crystalline polypropylene is exposed to a part of the surface of the fiber, the second component can reduce the intensity of the surface friction particular to the ethylene - ⁇ -olefin copolymer, and can also be produced stably in a fiber manufacturing process even without adding lubricant at all or by adding a little lubricant. Particularly when performing card processing, excellent fiber passability can be obtained during the card processing.
- a problem in the cross-sectional shape of a general two-component side-by-side conjugate fiber having a combination of half-moon-shaped components is the pealing of the components.
- the side-by-side cross section of the conjugate fiber of the present invention is configured such that the first component containing ethylene - ⁇ -olefin copolymer accounts for 55 to 90% of the length of the outer periphery, the borderline between the first component and the second component forms a curve bulging toward the first component, and such that the area ratio between the first component and the second component (first component/second component) is in a range of 70/30 to 30/70.
- the conjugate fiber of the present invention can effectively prevent shrinkage by adopting a specific fiber cross-sectional shape with a specific ethylene - ⁇ -olefin copolymer used as the first component.
- the nonwoven fabric obtained using the conjugate fiber of the present invention is bulky and soft, has less width reduction (reduction of the width in relation to a direction of flow of the nonwoven fabric) due to small shrinkage when subjected to heat processing, hence excellent productivity and excellent uniformity can be achieved.
- the conjugate fiber of the present invention has, as an effective component, a component that contains an ethylene - ⁇ -olefin copolymer having a melting point of 70 to 100°C, heat processing can be performed thereon at 100°C or lower.
- a medium such as steam and hot water also can be used so that appropriate conditions for obtaining a nonwoven fabric or a formed article can be selected from a wide range of choice in accordance with the use application, environment and circumstances.
- FIG. 1 A schematic diagram showing an example of the side-by-side cross-sectional shape of a conjugate fiber of the present invention.
- the conjugate fiber of the present invention has a first component containing an ethylene - ⁇ -olefin copolymer.
- This ethylene ⁇ -olefin. copolymer comprises ethylene and ⁇ -olefin units.
- the ⁇ -olefin include, specifically, linear ⁇ -olefins such as propylene, butene-1, pentene-1, hexene-1, heptene-1, and octene-1. Butene-1 and octene-1 are preferred but octene-1 is more preferred.
- the ⁇ -olefin content of the ethylene - ⁇ -olefin copolymer is 20 mol% or less.
- the ⁇ -olefin content is normally 1 mol% or more.
- the content in this case is expressed in molar ratio percentage (( ⁇ -olefin)/( ⁇ -olefin + ethylene)).
- Excessive ⁇ -olefin content delays solidification during the fiber manufacturing process and causes fusion between fibers and thereby a possible damage the productivity.
- the ⁇ -olefin content is 30 mol% or less, sufficient rigidity of the fiber can be obtained and, particularly when performing card processing, excellent fiber passability can be obtained during the card processing.
- the melting point of the ethylene - ⁇ -olefin copolymer to be used is 70 to 100°C, and preferably 80 to 100°C.
- the melting point of at least 70 °C can prevent fusion between fibers, and, for example, when drying an antistatic agent or other treatment agent applied to the surface of the fiber during the fiber manufacturing process, fusion between the fibers can be prevented and excellent productivity can be exerted.
- the melting point of 100°C or lower not only is it possible to set the temperature for processing the fiber into a nonwoven fabric or a formed article at 100°C or lower, but also a medium such as steam and hot water can be used for heat processing, and a processing method in which a comparatively low-temperature medium is used can be selected.
- this 100°C or less melting point is preferred as it is not necessary to concern about the influence on other components of the fiber that are essentially not molten.
- the melting point described here is a melting peak temperature that is obtained when the ethylene - ⁇ -olefin copolymer is measured using a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- the molecular weight distribution (Mw/Mn), which is the ratio between the weight-average molecular weight (Mw) of the ethylene - ⁇ -olefin copolymer and the number average molecular weight (Mn), is preferably 1.5 to 2.5 and more preferably 1.7 to 2.3.
- Mw/Mn the molecular weight distribution
- Mw/Mn the molecular weight distribution is in a range of 1.5 to 2.5, excellent spinnability is obtained in the fiber manufacturing process, and thus this molecular weight distribution is preferred in terms of the fabric property in order to obtain a strong conjugate fiber.
- the density of the ethylene - ⁇ -olefin copolymer is preferably 0.87 to 0.91 g/cm 3 and particularly preferably 0.88 to 0.90 g/cm 3 .
- the density of the ethylene - ⁇ -olefin copolymer is at least 0.87 g/cm 3 , appropriate surface viscosity can be obtained when processing the copolymer into a fiber, and agglutination hardly occurs during fiber manufacture. Therefore, this density is suitable for using the ethylene - ⁇ -olefin copolymer as a main component of the fiber.
- the density is 0.91 g/cm 3 or lower
- the melting point of the ethylene - ⁇ -olefin copolymer is comparatively as low as 100°C or lower, and thus this ethylene - ⁇ -olefin copolymer is suitable as the ethylene - ⁇ -olefin copolymer to be used in the present invention.
- the melt index (MI) of the ethylene - ⁇ -olefin copolymer is preferably 10 to 35 g/10 min and more preferably 15 to 30 g/10 min in consideration of achieving stable production during the fiber manufacturing process.
- the MI described here is a value that is measured under conditions with a temperature of 190°C and a load of 21.2 N based on ASTM D-1238.
- the ethylene - ⁇ -olefin copolymer to be used may be a mixture of one kind or two or more types.
- additives can be compounded into the ethylene ⁇ -olefin copolymer used in the present invention.
- Preferred examples of the additives include lubricant, heat-resistant stabilizer, antioxidant, weatherproof stabilizer, antistatic agent, colorant and the like.
- Preferred used as a lubricant includes fatty acid amides such as oleic amide and erucic acid amide, fatty acid esters such as butyl stearate, polyolefin waxes such as polyethylene wax and polypropylene wax, and metallic soap such as calcium stearate, and the like. More preferred examples include fatty acid amides such as oleic amide, erucic acid amide, stearic acid amide, behen acid amide and the like.
- the first component contained in the conjugate fiber of the present invention needs to include the abovementioned ethylene - ⁇ -olefin copolymer in an effective amount so as to be involved in heat adhesion at low temperature and so that steam or hot water can be used as a heat medium particularly when processing the conjugate fiber into a nonwoven fabric or performing the processing of formed article.
- the ethylene - ⁇ -olefin copolymer content is 100% as a resin raw material. It is preferred that the ethylene - ⁇ -olefin copolymer be at least 75% in the first component so that the performance of the ethylene - ⁇ -olefin copolymer can be realized subjectively.
- low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, propylene copolymer and the like can be the resin raw materials that the first component may contain in addition to the ethylene - ⁇ -olefin copolymer under the condition that at least 75% of the ethylene - ⁇ -olefin copolymer is contained in relation to the weight of the first component.
- the conjugate fiber of the present invention contains a crystalline polypropylene as the second component.
- This crystalline polypropylene is a propylene homopolymer or a copolymer of propylene and a small amount of ⁇ -olefin (normally 2 % by weight or less), and examples of such a crystalline polypropylene include a general-purpose polypropylene that is obtained by using a Ziegler-Natta catalyst or a metallocene catalyst.
- MFR melt mass flow rate
- the second component forming the conjugate fiber of the present invention which contains the crystalline polypropylene, a mixture of the crystalline polypropylene and propylene - ⁇ -olefin copolymer, or a mixture of crystalline polypropylenes having different properties such as the melt mass flow rate (MFR) and molecular weight distribution (Mw/Mn) can be used suitably as long as the effect of the conjugate fiber is not damaged significantly.
- MFR melt mass flow rate
- Mw/Mn molecular weight distribution
- the first component containing the ethylene - ⁇ -olefin copolymer and the second component containing the crystalline polypropylene form a side-by-side cross section having a specific structure.
- the first component containing the ethylene - ⁇ -olefin copolymer accounts for 55 to 90% of an outer periphery of the fiber
- the second component containing the crystalline polypropylene accounts for 45 to 10% of the same. Because the first component containing a specific ethylene - ⁇ -olefin copolymer accounts for 55% or more of the outer periphery of the fiber, heat processing can be performed at 100°C or lower.
- the second component containing the crystalline polypropylene accounts for 10% or more of the outer periphery of the fiber, the crystalline polypropylene continuously appear on the fiber, not only is it possible to reduce the friction between fibers or friction to a metal but also viscosity that occurs when the ethylene - ⁇ -olefin copolymer is used on the surface of the fiber, and excellent spinnability and card processability can be obtained when performing the card processing. It is particularly preferred that the first component containing the ethylene - ⁇ -olefin copolymer account for 60 to 80% of the outer periphery of the fiber and that the second component containing the crystalline polypropylene account for 40 to 20% of the same.
- the borderline between the first component and the second component forms a curve bulging toward the first component.
- the borderline between the first component and the second component becomes longer compared to the conjugate fiber having a general side-by-side cross-sectional structure where half-moon-shaped components are joined together. Specifically, the joint area between the both components is increased and, by providing the conjugate fiber of the present invention with a structure where the first component wraps the second component, the second component can be prevented from being released from this conjugate fiber.
- the fiber cross section perpendicular to the fiber axis has a structure where the borderline forms a curve bulging toward the first component such that the relationship between the length of a segment cd and a segment ce satisfy a relationship of cd ⁇ 0.8 ce.
- cd ⁇ ce more preferably cd ⁇ 1.5 ce, or particularly preferably cd ⁇ 2ce, excellent un-releasability between the conjugate components and heat shrinkability are obtained when performing heat processing and forming processing.
- the borderline between the first component and the second component that forms a curve bulging toward the first component is considered to take up a part of the outer periphery of a circle or an ellipse formed by an outer periphery of the second component, it is preferred that the length (g) of the borderline exceed 50% or more preferably at least 60% of the entire outer peripheral length (h) of the circle or ellipse formed by the second component.
- the conjugate fiber of the present invention can be manufactured using a conventionally known side-by-side conjugate spinneret.
- the conjugate fiber of the present invention can be manufactured using a side-by-side conjugate spinneret, for example, Japanese Patent Application Publication S48-11417 or Japanese Patent Application Publication S52-74011 .
- the flowability (viscosity) thereof that is measured when melting it at some temperature selected in the range about 190°C, and a temperature range in which the flowability (viscosity) enabling the fiber to be manufactured is selected based on fluctuation of melt flowability (melt viscosity) to obtain an extrusion temperature as the fiber manufacturing condition.
- the second component containing the crystalline polypropylene when the flowability (viscosity) thereof is measured by melting the second component at about 230°C, to select an extrusion temperature.
- the cross-sectional configuration of the conjugate fiber of the present invention can be formed easily when the ratio of the melt index (MI) of the first component to the melt mass flow rate (MFR) of the second component is 1.5 to 3 times, although it is not possible to say definitely because temperature dependence of the flowability (uptrend of viscosity) varies depending on the resins used. More preferably, this ratio is in a range of 1.8 to 2.5.
- the proportion of the first component and the second component on the fiber cross section in relation to the outer periphery of the fiber can be increased or decreased even if the extrusion temperature and the melt viscosity are not changed.
- a treatment agent may be applied to a surface of the conjugate fiber of the present invention in order to improve processing stability when manufacturing the fiber.
- the treatment agent is mainly an antistatic agent, but is also a hydrophilic agent capable of improving wettability of the surface of the fiber.
- examples of the components of these antistatic agent and hydrophilic agent include alkyl phosphate, ethylene oxide adduct thereof, sorbitan fatty acid ester ethylene oxide adduct, polyglycerol fatty acid ester, polyoxyethylene modified silicone and the like.
- a single component selected from these components or a mixture of any of the components is used as the treatment agent.
- the heat shrinkage percentage of the conjugate fiber of the present invention that is obtained when heat-processing the conjugate fiber at 100°C for five minutes is 50% or lower, preferably 30% or lower, and more preferably 20% or lower.
- the heat shrinkage percentage described here which is expressed in percentage (%), is a difference in size (reduced amount) between the conjugate fibers that are and are not subjected to heat processing, the conjugate fibers being obtained by inserting the conjugate fiber of the present invention, staple fiber, into a card machine, cutting the fibrous web that is thus extracted from a card outlet (the web is in the form of a sheet with entangled fibers) into a certain shape, and then performing the heat processing thereon at 100°C for five minutes.
- the heat shrinkage percentage of the present invention is obtained by cutting the conjugate fiber of the present invention into any length such as 30 to 65 mm to obtain a staple fiber, and inserting this staple fiber into a miniature card machine to create a fibrous web having a mass per unit area of 200 g/m 2 .
- This fibrous web is cut along a pattern of 250 mm ⁇ 250 mm in a flow direction (MD) of the fiber and a direction perpendicular to this flow direction (CD).
- MD flow direction
- CD direction perpendicular to this flow direction
- This fibrous web is left stand for ten minutes, thereafter the length of the MD of this cut fibrous web is measured immediately before performing the heat processing, and then the fibrous web is subjected to the heat processing in a circulating hot air oven at 100°C for five minutes.
- the length of MD is measured again, and the value of the heat shrinkage percentage is obtained by the following equation.
- Heat Shrinkage Percentage % L 0 ⁇ L / L 0 ⁇ 100
- the lower this value the smaller the shrinkage of the fibrous web when processing the conjugate fiber into a nonwoven fabric, hence stable processing can be performed and a nonwoven fabric with excellent uniformity can be obtained.
- conditions for measuring the heat shrinkage described here are not specified/limited to the conditions for processing the conjugate fiber of the present invention, the heat processing conditions, the conditions for processing the conjugate fiber into a nonwoven fabric, and usage of the conjugate fiber.
- crimps are generated easily during the heat processing for manufacturing the fiber, due to the cross-sectional structure of the conjugate fiber and the resin configuration thereof, hence, as a result, the effect of improving bulkiness of the fiber can be exerted.
- the fibrous web for use in processing the conjugate fiber into a nonwoven fabric the fibrous web being an assembly of fibers that are cut into a predetermined length to process the conjugate fiber into a nonwoven fabric, when performing the heat processing, the fiber itself shrinks easily, because of existing freely each other in the web.
- the part that shrinks easily pulls and gathers the fibers existing in the surroundings to form a clump, and the part that has lost fibers due to this gathering is reduced in mass per unit area, whereby weight unevenness becomes extremely noticeable in the entire nonwoven fabric, making it difficult to obtain a nonwoven fabric having excellent uniformity.
- the conjugate fiber of the present invention has the side-by-side cross-sectional structure composed of two components, but has a cross-sectional shape in which the first component containing the ethylene - ⁇ -olefin copolymer accounts for 55 to 90% of the outer periphery of the fiber and wraps the second component containing the crystalline polypropylene.
- an ethylene - ⁇ -olefin copolymer having a melting point of 70 to 100°C or preferably an ethylene ⁇ -olefin copolymer having a molecular weight distribution (Mw/Mn) of 1.5 to 2.5, a density of 0.87 to 0.91 g/cm 3 , and a melt index (MI) of 10 to 35 g/10 min
- Mw/Mn molecular weight distribution
- MI melt index
- the conjugate fiber of the present invention that has a combination of a specific resin structure and a specific conjugate structure. It is unexpected that, while surprisingly preventing shrinkage by using the specific ethylene - ⁇ -olefin copolymer and combining it with the crystalline polypropylene to obtain a fiber that further has a specific fiber cross-sectional configuration, it is possible to obtain a nonwoven fabric that has excellent bulkiness, which is generally considered to be a conflicting performance, excellent feeling, and excellent heat processing properties at a low temperature of 100°C.
- the fineness of the conjugate fiber of the present invention is not particularly limited.
- a conjugate fiber that is suitably processed into a nonwoven fabric or formed article may be selected in consideration of the properties of the components forming the conjugate fiber and of processing stability when manufacturing the fiber.
- a fiber having a fineness of 1 to 5 dtex is preferably selected when using the conjugate fiber in a powder puff or a medicine sheet that comes into direct contact with a human skin.
- a fiber having a fineness of 1 to 10 dtex is suitable for use in a liquid retaining material such as an ink cartridge of a printer.
- a fiber having a fineness of 1 to 20 dtex is suitable for use in a liquid volatizing material such as an aromatic substance core of home fragrance.
- the length of the conjugate fiber of the present invention is not particularly limited, and hence may be long or short.
- the cut length can be appropriately selected in accordance with the fineness of the conjugate fiber, the method of processing the conjugate fiber, and the use application of the conjugate fiber.
- the staple fiber When the staple fiber is subjected to the card processing, it is preferred that the staple fiber be cut into 20 to 125 mm. In order to obtain excellent card passability and uniformity of the fibrous web, it is preferred that the staple fiber be cut into 25 to 75 mm.
- the conjugate fiber be chopped into 3 to 25 mm with the air-laid method.
- the conjugate fiber of the present invention preferably has crimps in order to spread the fiber bundle and obtain a bulky fibrous web and nonwoven fabric.
- the number of crimps to be obtained or the type of crimps can be selected appropriately in accordance with the fineness and cut length of the conjugate fiber, the method for processing the conjugate fiber, and the use application of the conjugate fiber. For example, when a conjugate fiber (staple fiber) having a fineness of 3.3 to 6.6 dtex and a cut length of 38 to 45 mm is processed into a fibrous web by a carding method, it is preferred that the number of crimps be 10 to 25 peaks/25 mm.
- the number of crimps be 5 to 15 peaks/25 mm.
- the crimps can be, for example, in a zigzag shape or a spiral structure.
- the fibrous web is formed first, the heat processing is performed thereon, and then the method for processing into a nonwoven fabric is used.
- a fibrous web formation method include a carding method for passing a card machine and an air-laid method for inserting fibers into a cylindrical drum provided with a slit and accumulating the fibers on a belt conveyor by rotating the drum, but the fibrous web formation method is not limited to these methods.
- other fibers can be blended as long as the effects of the present invention are not impaired significantly.
- the fibers that can be blended include rayon and cotton for improving the water retention ability, polyethylene terephthalate for making an obtained nonwoven fabric bulkier, and other hollow fibers.
- a span lace method or a needle punching method for etangling the fibers within the fibrous web by means of a water stream, compressed air, a needle or the like can be used before performing the heat processing, to improve the strength of the fibrous web and change the feeling.
- the heat processing method examples include a hot-air adhesion method, a hot-water adhesion method, hot-roll adhesion method and the like. Above all, the hot-air adhesion method or the hot-water adhesion method is preferred as the heat processing method to be performed after forming the conjugate fiber of the present invention into the fibrous web.
- the hot-air adhesion method is a method for softening and melting a low-melting point component of the conjugate fiber by passing heated air through the fibrous web and adhering the fibers at their contact point. Because this adhesion method does not impair the bulkiness by compressing a certain area unlike the hot-roll adhesion method, this adhesion method is suitable for providing a bulky nonwoven fabric having excellent uniformity and excellent feeling, which is the object of the present invention.
- This hot-air adhesion method is suitable for obtaining a bulky nonwoven fabric having excellent feeling. Therefore, particularly when the hot-air adhesion method is used to heat-process a conjugate fibrous web that has short fibers each having a general side-by-side cross section with two half-moon-shaped components, large shrinkage occur easily compared to when other adhesion methods are used, due to high freedom of the fibrous web on the conveyor, and thus a nonwoven fabric with excellent uniformity and excellent feeling cannot be obtained easily.
- the conjugate fiber of the present invention is designed to effectively prevent shrinkage caused by heat-processing the conjugate fiber into a nonwoven fabric, and thus can be used suitably in this hot-air adhesion method in particular. Therefore, the conjugate fiber of the present invention can provide a nonwoven fabric having an excellent feeling, while keeping the advantage of bulkiness that is essentially provided by the hot-air adhesion method.
- the hot-water adhesion method is a method for softening and melting a low-melting point component of the conjugate fiber by passing heated water or steam through the fibrous web and adhering the fibers at their contact point.
- a hot-water adhesion method that performs the heat processing at 100°C or lower can be essentially applied. Hot water, steam or other comparatively inexpensive medium that does not require any special equipment is used in this adhesion method.
- the treatment agent applied onto the surface of the conjugate fiber of the present invention can be washed away while processing the conjugate fiber into a nonwoven fabric.
- the treatment agent applied onto the surface of the fiber is essential in the conjugate fiber (staple fiber, chop for air-laid method and the like) manufacturing process, but is not necessary or is rather an obstruction after processing the fiber into a nonwoven fabric or formed article, depending on the use application.
- Examples of said use application include a food protection sheet such as a packing material and a plastic tray that come into direct contact with food, a powder puff impregnated in a cosmetic item, and a stick for applying a medical agent to an affected part of the body.
- a method for configuring the treatment agent of the fiber surface by selecting a safe element such as a food additive or a corresponding component, or a method for performing cleansing to wash away the treatment agent after forming the fiber into a nonwoven fabric or formed article.
- configuring the treatment agent using a human-friendly component does not eliminate the effect of the treatment agent on the cosmetic item or medical agent, and thus it is desired that the treatment agent does not remain on the nonwoven fabric or formed article in order to keep the stable performance.
- performing the cleansing after processing the fiber into a nonwoven fabric or formed article requires equipment and time and thus is disadvantageous in terms of cost.
- the conjugate fiber of the present invention in which the hot-water adhesion method can be adopted is industrially very significant because the present invention can efficiently provide, for the abovementioned use application and at low cost, a bulky nonwoven fabric or formed article that has almost no treatment agent thereon or on which the amount of the treatment agent attached to the fiber is so small that it does not cause the above problems. It is most preferred that the conjugate fiber of the present invention be processed into a nonwoven fabric or formed article by means of the hot-water adhesion method, or that a heat-processed nonwoven fabric obtained by the hot-air adhesion method be processed into a formed article by means of the hot-water adhesion method.
- the mass per unit area of the nonwoven fabric that is obtained when processing the conjugate fiber of the present invention into a nonwoven fabric can be appropriately selected based on the purpose of use.
- the mass per unit area is preferably in a range of 20 to 50 g/m 2 for a food packing material, 30 to 150 g/m 2 for a powder puff or a medicine sheet, and 50 to 250 g/m 2 for a stick for applying a medical agent.
- the bulkiness of the nonwoven fabric that is obtained when processing the conjugate fiber of the present invention into a nonwoven fabric can be calculated based on a specific volume and can be easily at least 20 cm 3 /g, or preferably at least 30 cm 3 /g.
- conjugate fiber of the present invention is processed into a nonwoven fabric
- another nonwoven fabric a fibrous web, thermoplastic film, sheet or the like may be stacked on this nonwoven fabric, depending on the purpose.
- a breathable film, a porous film, a porous nonwoven fabric may be laminated to the nonwoven fabric
- an elastic nonwoven fabric composed of elastomer or other ethylene - ⁇ -olefin copolymer may be stacked on the nonwoven fabric.
- formed article means a finished product that is obtained using the conjugate fiber of the present invention without processing the conjugate fiber into a nonwoven fabric, and a finished product that is obtained by processing the conjugate fiber into a nonwoven fabric.
- a fibrous web of a desired mass per unit area that is obtained by the carding method or the like can be formed into a sliver, which is then placed in a specific mold and subjected to heat processing, whereby the "formed article" can be obtained.
- the conjugate fiber of the present invention is formed into fibrous webs of a desired mass per unit area by means of the carding method or air-laid method or the like, which are then processed into a nonwoven fabric by means of the hot-air adhesion method or the like.
- nonwoven fabrics are stacked, cut or combined to have a desired mass per unit area and thickness, and the resulting fabric can be integrated into the "formed article" by means of the hot-air adhesion method or hot-water adhesion method.
- the obtained nonwoven fabric can be stacked, cut or combined to have a desired mass per unit area and thickness, which is then placed in a specific mold and subjected to heat processing, whereby the "formed article" can be obtained.
- Additional processing can be easily performed on the "formed article" obtained using the conjugate fiber of the present invention, for example, by cutting a part of the formed article or heat-processing the formed article.
- the conjugate fiber of the present invention can be suitably used for use applications as a powder puff, medicine sheet, a sheet for cooling fever, a food plastic tray, a cushion material, a buffer material, an aromatic substance core of home fragrance, a liquid retaining material such as a humidifier, a nursery sheet, a wiper, and the like.
- MI Measurement was performed under conditions with a temperature of 190°C and a load of 21.2 N based on ASTM D-1238.
- Measurement was performed using DSC "Q-10" produced by TA Instruments. The resin was cut to have a weight of 4.20 to 4.80 mg, which is then put into a sample pan and a cover is placed thereon. Measurement was performed thereon at a rate of temperature increase 10 °C/min in an N 2 purge between 30°C to 200°C, to obtain a melt chart. The chart was analyzed to obtain a melting peak temperature.
- Measurement was performed under conditions with a temperature of 230°C and a load of 21.2 N based on JIS K7210.
- the thickness of a fiber calculated from the weight per length. (Unit: dtex)
- each fiber is longer than 60 mm, a bundle of fibers is cut into 60 mm, and the weight of 150 cut fibers was measured using "AEL-40SM," an electronic balance produced by Shimadzu Corporation. The obtained numeric value was multiplied by 1111 to obtain fineness of the resulting fibers. When the length of the fibers was not sufficient, the fibers were observed through a scanning electron microscope. One hundred fibers were selected from the obtained image, and the diameter of each fiber was measured. The fineness was calculated from the average value of the diameters and the specific gravity of the fibers.
- Results obtained were: the proportion (%) of the first component to the length of the outer periphery of the fiber in the fiber cross section perpendicular to the fiber axis; the ratio of the length of a fiber cd to the length of a fiber ce (cd/ce) when supposing that two intersections of the outer periphery of the fiber and the borderline between the first component and the second component are taken as point a and point b, the borderline forming a curve bulging toward the first component, and that a point where the segment ab is halved is taken as point c, and a point where the borderline between the first component and the second component intersects with a straight line that extends in a direction perpendicular to a line ab through point c is taken as point d, and a point where said straight line that extends in a direction perpendicular to a line ab through point c intersects with the outer periphery of the fiber on the second component side as point e; the ratio of the length g of
- the fibrous web of 200 g/m 2 that was inserted into a miniature card machine was cut along a pattern of 250 mm ⁇ 250 mm in a flow direction (MD) of the fiber and a direction perpendicular to this flow direction (CD).
- the obtained fiber was left stand for ten minutes, and then the cut fibrous webs were placed on a piece of craft paper (350 mm ⁇ 700 mm) to measure the length thereof in MD.
- the craft paper was folded into two to slightly cover the top of the fibrous webs, which is then put into a 100-degree convection oven (circulating hot air oven) produced by SANYO Electric Co., Ltd., to heat process it for five minutes.
- the processed product was taken out from the dryer and cooled at room temperature for five minutes, and the length thereof in MD was measured.
- the weight per unit area of the nonwoven fabric and fibrous web calculated from the weight of the nonwoven fabric or fibrous web cut into a certain area. (Unit: g/m 2 )
- the weight of the nonwoven fabric that was cut into 250 mm ⁇ 250 mm was measured by "HF-200," an electronic scale balance produced by A&D Company. The obtained numeric value was multiplied by 16 to calculate the mass per unit area.
- the thickness of the nonwoven fabric was measured using "Digi-Thickness Tester” produced by Toyo Seiki Seisaku-Sho, Ltd., under conditions with an anvil load of 2g/cm 2 and a speed of 2 mm/sec, and calculated from the obtained numeric value (mm) and mass per unit area (g/m 2 ).
- the uniformity of the appearance, softness by hand touch, stiffness, bulging and the like of the nonwoven fabric were determined comprehensively.
- the first component was an ethylene - ⁇ -olefin copolymer polymerized using a metallocene catalyst, wherein ⁇ -olefin was octene-1 and contained in the copolymer in an amount of 10 mol%.
- the density was 0.880, the melting point 72°C, the melt index (MI) 18 g/10 min, and the molecular weight distribution (Mw/Mn) 1.9.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 8 g/10 min and a melting point of 160°C.
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above.
- the results are shown in the section corresponding to components on Table 1.
- the obtained conjugate fiber (staple fiber) was measured using the measuring methods of (6) and (7) described above.
- the results are shown in the section corresponding to yarn quality on Table 1 along with schematic diagrams. Peeling of the components was not observed in the fiber cross section in the direction perpendicular to the fiber axis.
- 100g of the obtained conjugate fiber (staple fiber) was inserted into a 500mm-wide miniature card machine to form a fibrous web.
- the fiber passability was good during the card processing.
- the heat shrinkage percentage of this fibrous web was measured using the measuring method of (8) described above.
- the results are shown in the section corresponding to yarn quality on Table 1.
- 50g of the obtained conjugate fiber (staple fiber) were inserted into a 500mm-wide miniature card machine to form a fibrous web.
- This fibrous web was processed using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.8 m/sec, and a processing time of 12 seconds.
- the property of thus obtained through-air nonwoven fabric was measured and evaluated using the measuring methods of (9) to (11) described above.
- the results are shown in the section corresponding to nonwoven fabric property on Table 1.
- the heat shrinkage percentage of the fibrous web in which the obtained conjugate fiber (staple fiber) is used was as low as 15%, a bulky nonwoven fabric with excellent uniformity and excellent feeling was obtained even when the hot-air adhesion method was used.
- the first component was an ethylene - ⁇ -olefin copolymer polymerized using a metallocene catalyst, wherein ⁇ -olefin was octene-1 and contained in the copolymer in an amount of 9 mol%.
- the density was 0.885, the melting point 78°C, the melt index (MI) 30 g/10 min, and the molecular weight distribution (Mw/Mn) 2.0.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 16 g/10 min and a melting point of 160°C.
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above.
- the results are shown in the section corresponding to components on Table 1.
- the obtained conjugate fiber (staple fiber) was measured using the measuring methods of (6) and (7) described above.
- the results are shown in the section corresponding to yarn quality on Table 1 along with schematic diagrams. Peeling of the components was not observed in the fiber cross section in the direction perpendicular to the fiber axis.
- 100g of the obtained conjugate fiber (staple fiber) was inserted into a 500mm-wide miniature card machine to form a fibrous web.
- the fiber passability was good during the card processing.
- the heat shrinkage percentage of this fibrous web was measured using the measuring method of (8) described above.
- the results are shown in the section corresponding to yarn quality on Table 1.
- 50g of the obtained conjugate fiber (staple fiber) were inserted into a 500mm-wide miniature card machine to form a fibrous web.
- This fibrous web was processed using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.8 m/sec, and a processing time of 12 seconds.
- the property of thus obtained through-air nonwoven fabric was measured and evaluated using the measuring methods of (9) to (11) described above.
- the results are shown in the section corresponding to nonwoven fabric property on Table 1.
- the heat shrinkage percentage of the fibrous web in which the obtained conjugate fiber (staple fiber) is used was as low as 17%, a bulky nonwoven fabric with excellent uniformity and excellent feeling was obtained even when the hot-air adhesion method was used.
- the first component was an ethylene - ⁇ -olefin copolymer polymerized using a metallocene catalyst, wherein ⁇ -olefin was octene-1 and contained in the copolymer in an amount of 5 mol%.
- the density was 0.902, the melting point 98°C, the melt index (MI) 30 g/10 min, and the molecular weight distribution (Mw/Mn) 2.1.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 16 g/10 min and a melting point of 160°C.
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above.
- the results are shown in the section corresponding to components on Table 1.
- the obtained conjugate fiber (staple fiber) was measured using the measuring methods of (6) and (7) described above.
- the results are shown in the section corresponding to yarn quality on Table 1 along with schematic diagrams. Peeling of the components was not observed in the fiber cross section in the direction perpendicular to the fiber axis.
- 100g of the obtained conjugate fiber (staple fiber) was inserted into a 500mm-wide miniature card machine to collect a fibrous web.
- the fiber passability was good during the card processing.
- the heat shrinkage percentage of this fibrous web was measured using the measuring method of (8) described above.
- the results are shown in the section corresponding to yarn quality on Table 1.
- 50g of the obtained conjugate fiber (staple fiber) were inserted into a 500mm-wide miniature card machine to form a fibrous web.
- This fibrous web was processed using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.8 m/sec, and a processing time of 12 seconds.
- the property of thus obtained through-air nonwoven fabric was measured and evaluated using the measuring methods of (9) to (11) described above.
- the results are shown in the section corresponding to nonwoven fabric property on Table 1.
- the heat shrinkage percentage of the fibrous web in which the obtained conjugate fiber (staple fiber) is used was as low as 28%, a bulky nonwoven fabric with excellent uniformity and excellent feeling was obtained even when the hot-air adhesion method was used.
- the first component was an ethylene- ⁇ -olefin copolymer, wherein ⁇ -olefin was octene-1 and contained in the copolymer in an amount of 2 mol%.
- the density was 0.913, the melting point 107°C, the melt index (MI) 30 g/10 min, and the molecular weight distribution (Mw/Mn) 3.0.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 16 g/10 min and a melting point of 160°C.
- an antistatic agent that has ethylene oxide additives of sorbitan fatty acid ester and lauryl phosphate potassium salt as the main components is attached to these components. Good spinnability was obtained.
- spun conjugate filament having a fineness of 11.5 dtex was drawn 3.3 times by using a 70°C heating device provided with a heating roll, and crimped by means of a crimping device. Thereafter, the filament was cut into 38 mm to obtain a conjugate fiber (staple fiber) having a fineness of 3.8 dtex (fiber diameter of 23.2 ⁇ m).
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above.
- the results are shown in the section corresponding to components on Table 2.
- the obtained conjugate fiber (staple fiber) was measured using the measuring methods of (6) and (7) described above.
- 100g of the obtained conjugate fiber (staple fiber) was inserted into a 500mm-wide miniature card machine to form fibrous webs.
- the fiber passability was good during the card processing.
- the heat shrinkage percentage of these fibrous webs was measured using the measuring method of (8) described above. The results are shown in the section corresponding to yarn quality on Table 2.
- 50g of the obtained conjugate fiber (staple fiber) were inserted into a 500mm-wide miniature card machine to form a fibrous web.
- These fibrous webs were processed using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.8 m/sec, and a processing time of 12 seconds.
- Comparative Example 1 is significantly different from Example 3 in that the melting point is 107°C in this example, but the same method as that of Example 3 was used to produce a nonwoven fabric.
- the processing temperature enable to be adopted for the obtained conjugate fiber was not low enough to adopt the hot-water adhesion method, and thus the conjugate fiber could not be processed into a nonwoven fabric or a formed article. Therefore, evaluation of the shrinkage percentage of the fibrous webs at 100°C according to the low-temperature processing ended up meaningless.
- the first component was an ethylene - ⁇ -olefin copolymer, wherein ⁇ -olefin was propylene and butene that are contained in the copolymer in an amount of 3 mol% and 3 mol%.
- the density was 0.897, the melting point 81°C, the melt index (MI) 4 g/10 min, and the molecular weight distribution (Mw/Mn) 2.0.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 8 g/10 min and a melting point of 160°C.
- an antistatic agent that has ethylene oxide additives of sorbitan fatty acid ester and lauryl phosphate potassium salt as the main components is attached to these components.
- agglutination was observed.
- spun conjugate filament having a fineness of 9.8 dtex was drawn 1.7 times by using a 60°C heating device provided with a heating roll to provide the filament with crimps by means of a crimping device. Thereafter, the filament was cut into 38 mm to obtain a conjugate fiber (staple fiber) having a fineness of 6.8 dtex (fiber diameter of 31.1 ⁇ m).
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above.
- the results are shown in the section corresponding to components on Table 2.
- the obtained conjugate fiber (staple fiber) was measured using the measuring methods of (6) and (7) described above.
- the results are shown in the section corresponding to yarn quality on Table 2 along with schematic diagrams. Because the melt index (MI) of the first component is low, the borderline between the first component and the second component in the fiber cross section in the direction perpendicular to the fiber axis formed a curve bulging toward the second component. Therefore, cd/ce, f, and g/h could not be measured. Also, peeling was observed between the components.
- 100g of the obtained conjugate fiber (staple fiber) was inserted into a 500mm-wide miniature card machine to form a fibrous web.
- the fiber passability was not good during the card processing because unevenness occurred in the fiber dischargeablity.
- the heat shrinkage percentage of this fibrous web was measured using the measuring method of (8) described above. The results are shown in the section corresponding to yarn quality on Table 2.
- 50g of the obtained conjugate fiber (staple fiber) were inserted into a 500mm-wide miniature card machine to form fibrous webs. These fibrous webs were processed using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.8 m/sec, and a processing time of 12 seconds.
- large shrinkage was observed and the strength of the nonwoven fabric was low, and thus a nonwoven fabric with excellent uniformity and excellent feeling was not obtained.
- the heat shrinkage percentage of each fibrous web in which the obtained conjugate fiber was used was as high as 55%.
- the first component was an ethylene - ⁇ -olefin copolymer, wherein ⁇ -olefin was propylene that is contained in the copolymer in an amount of 15 mol%.
- the density was 0.863, the melting point 50°C, the melt index (MI) 21 g/10 min, and the molecular weight distribution (Mw/Mn) 2.0.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 16 g/10 min and a melting point of 160°C.
- the melt index (MI) of the first component is significantly low in relation to the melt mass flow rate (MFR) of the second component
- MFR melt mass flow rate
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above. The results are shown in the section corresponding to components on Table 2.
- a mixture of two resins was used as the first component.
- One of the resins was an ethylene - ⁇ -olefin copolymer, wherein ⁇ -olefin was propylene that is contained in the copolymer in an amount of 12 mol%.
- the density was 0.870, the melting point 75°C, the melt index (MI) 1 g/10 min, and the molecular weight distribution (Mw/Mn) 1.9.
- the other resin was a propylene- ⁇ -olefin copolymer, wherein - ⁇ -olefin was ethylene and butene-1 that are contained in the copolymer in an amount of 1 mol% each.
- the melting point was 128°C and the melt mass flow rate (MFR) was 16 g/10 min.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 8 g/10 min and a melting point of 160°C.
- an antistatic agent that has ethylene oxide additives of sorbitan fatty acid ester and lauryl phosphate potassium salt as the main components is attached to these components. Good spinnability was obtained.
- spun conjugate filament having a fineness of 9.7 dtex was drawn 2.6 times by using a 60°C heating device provided with a heating roll to provide the filament with crimps by means of a crimping device. Thereafter, the filament was cut into 38 mm to obtain a conjugate fiber (staple fiber) having a fineness of 4.4 dtex (fiber diameter of 25.1 ⁇ m).
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above.
- the results are shown in the section corresponding to components on Table 2.
- the property of the obtained conjugate fiber (staple fiber) was measured using the measuring methods of (6) and (7) described above.
- the results are shown in the section corresponding to yarn quality on Table 2 along with schematic diagrams.
- cd/ce 0.2 and g/h ⁇ 0.5.
- 100g of the obtained conjugate fiber (staple fiber) was inserted into a 500mm-wide miniature card machine to form a fibrous web.
- the fiber passability was good during the card processing.
- the heat shrinkage percentage of this fibrous web was measured using the measuring method of (8) described above. The results are shown in the section corresponding to yarn quality on Table 2.
- 50g of the obtained conjugate fiber (staple fiber) were inserted into a 500mm-wide miniature card machine to form a fibrous web.
- This fibrous web was processed using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.8 m/sec, and a processing time of 12 seconds.
- the heat shrinkage percentage of the fibrous web in which the obtained conjugate fiber is used was as high as 65%.
- a mixture of two resins was used as the first component.
- One of the resins was a low-density polyethylene. The density thereof was 0.918, the melting point 105°C, the melt index (MI) 24 g/10 min, and the molecular weight distribution 7.0.
- the other resin was an ethylene-vinyl acetate copolymer. The density thereof was 0.939, the melting point 92°C, the melt index (MI) 20 g/10 min, and the molecular weight distribution (Mw/Mn) 5.0. These two resins were mixed at a weight ratio of 75/25. Note that Table 3 shows the property of the ethylene-vinyl acetate copolymer, which is a resin having a lower melting point.
- the second component is a crystalline polypropylene having a melt mass flow rate (MFR) of 8 g/10 min and a melting point of 160°C.
- an antistatic agent that has ethylene oxide additives of sorbitan fatty acid ester and lauryl phosphate potassium salt as the main components is attached to these components. A number of broken yarns were observed during spinning.
- spun conjugate filament having a fineness of 9.7 dtex was drawn 2.6 times by using a 60°C heating device provided with a heating roll to provide the filament with crimps by means of a crimping device. Thereafter, the filament was cut into 38 mm to obtain a conjugate fiber (staple fiber) having a fineness of 3.3 dtex (fiber diameter of 21.5 ⁇ m).
- the density, melting point, melt index (MI), and molecular weight distribution (Mw/Mn) of the first component were measured using the measuring methods of (1) to (4) described above.
- the melting point and melt mass flow rate (MFR) of the second component were measured using the measuring methods of (4) and (5) described above.
- the results are shown in the section corresponding to components on Table 3.
- the property of the obtained conjugate fiber (staple fiber) was measured using the measuring methods of (6) and (7) described above.
- the results are shown in the section corresponding to yarn quality on Table 3 along with schematic diagrams.
- 100g of the obtained conjugate fiber (staple fiber) was inserted into a 500mm-wide miniature card machine to form a fibrous web.
- the fiber passability was not good during the card processing because unevenness occurred when discharging the fiber.
- the heat shrinkage percentage of this fibrous web was measured using the measuring method of (8) described above. The results are shown in the section corresponding to yarn quality on Table 3.
- 50g of the obtained conjugate fiber (staple fiber) were inserted into a 500mm-wide miniature card machine to form fibrous webs.
- These fibrous webs were processed using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.8 m/sec, and a processing time of 12 seconds.
- large shrinkage was observed and the strength of the nonwoven fabric was low, and thus a nonwoven fabric with excellent uniformity and excellent feeling was not obtained.
- the heat shrinkage percentage of each fibrous web in which the obtained conjugate fiber was used was as high as 60%.
- the conjugate fiber (staple fiber) obtained in Example 3 was processed into a fibrous web by means of the carding method, and this fibrous web was formed into a rod-like sliver.
- the fibrous web formed into a sliver was placed into a cylindrical mold (10 mm ⁇ 10 mm ⁇ 60 mm) made from a 20-mesh metallic wire having a wire diameter of 0.29 mm, which is then subjected to hot-air adhesion processing by means of a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, hot air velocity of 1.2 m/sec, and a processing time of 12 seconds, to obtain a cubical fiber formed article.
- the obtained fiber formed article has excellent cushioning characteristics.
- the conjugate fiber (chop for air-laid) obtained in Example 4 was processed into a fibrous web having a mass per unit area of 50 g/m 2 by means of the air-laid method, and this fibrous web was subjected to hot-air adhesion processing by using a through-air processing device of hot-air circulation type under conditions with a preset temperature of 98°C, a hot air velocity of 0.38 m/sec, and a processing time of 14 seconds.
- the obtained through-air nonwoven fabric was placed into a glass tube having an inner diameter of 8 mm, which is then immersed into boiled water and boiled for two minutes.
- the through-air nonwoven fabric was then cooled after the boiling, to obtain a cylindrical fiber formed article.
- the obtained fiber formed article is moderately soft and has less fluctuation in fiber density. Therefore, this fiber formed article is suitable for retaining fluid and the like.
- the conjugate fiber of the present invention in which the first component containing an ethylene - ⁇ -olefin copolymer of a specific property and the second component containing a crystalline polypropylene form the side-by-side cross section, has low-temperature processability and low heat shrinkage percentage. Therefore, this conjugate fiber is useful in producing bulky nonwoven fabric and formed articles having excellent uniformity and excellent feeling at a heat processing temperature of 100°C or lower.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
Applications Claiming Priority (2)
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JP2007323616 | 2007-12-14 | ||
PCT/JP2008/073148 WO2009078479A1 (en) | 2007-12-14 | 2008-12-15 | Conjugate fiber having low-temperature processability, nonwoven fabric and formed article using the conjugate fiber |
Publications (3)
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EP2229474A1 EP2229474A1 (en) | 2010-09-22 |
EP2229474A4 EP2229474A4 (en) | 2011-03-02 |
EP2229474B1 true EP2229474B1 (en) | 2017-06-07 |
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EP08863375.5A Active EP2229474B1 (en) | 2007-12-14 | 2008-12-15 | Conjugate fiber having low-temperature processability, nonwoven fabric and formed article using the conjugate fiber |
Country Status (8)
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US (1) | US20100261399A1 (ja) |
EP (1) | EP2229474B1 (ja) |
JP (1) | JP5535911B2 (ja) |
KR (1) | KR101259968B1 (ja) |
CN (1) | CN101939470B (ja) |
BR (1) | BRPI0819934B1 (ja) |
TW (1) | TW200934897A (ja) |
WO (1) | WO2009078479A1 (ja) |
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JP5233053B2 (ja) * | 2008-05-19 | 2013-07-10 | Esファイバービジョンズ株式会社 | エアレイド不織布製造用複合繊維及び高密度エアレイド不織布の製造方法 |
JP5842353B2 (ja) * | 2010-04-13 | 2016-01-13 | Jnc株式会社 | 嵩高性不織布 |
JP6083239B2 (ja) * | 2012-05-23 | 2017-02-22 | 東レ株式会社 | 繊維強化プラスチックおよびその製造方法 |
CN102978724B (zh) * | 2012-12-21 | 2015-05-13 | 东华大学 | 一种双组份并列复合纤维及其制备方法 |
JP6222997B2 (ja) * | 2013-05-31 | 2017-11-01 | Esファイバービジョンズ株式会社 | 柔軟性に優れた熱接着性複合繊維とこれを用いた不織布 |
TWI550147B (zh) * | 2013-11-20 | 2016-09-21 | Fabrication method and finished product of juxtaposed polypropylene crimp telescopic fiber | |
US10463222B2 (en) | 2013-11-27 | 2019-11-05 | Kimberly-Clark Worldwide, Inc. | Nonwoven tack cloth for wipe applications |
EP3215086B1 (en) | 2014-11-06 | 2020-03-18 | The Procter and Gamble Company | Crimped fiber spunbond nonwoven webs / laminates |
WO2016073736A1 (en) | 2014-11-06 | 2016-05-12 | The Procter & Gamble Company | Apertured webs and methods for making the same |
JP6614679B2 (ja) * | 2015-08-21 | 2019-12-04 | 株式会社タイキ | 化粧品 |
EP4223920B1 (en) * | 2016-11-14 | 2024-10-02 | Fare' S.p.A. a Socio Unico | Filament for spunbond non woven fabric |
US20180229216A1 (en) | 2017-02-16 | 2018-08-16 | The Procter & Gamble Company | Absorbent articles with substrates having repeating patterns of apertures comprising a plurality of repeat units |
JP2019070207A (ja) * | 2017-10-06 | 2019-05-09 | 三菱ケミカル株式会社 | 低融点熱融着性繊維 |
WO2019146726A1 (ja) * | 2018-01-24 | 2019-08-01 | 旭化成株式会社 | 偏心鞘芯型複合繊維を少なくとも片方の面に用いた複合長繊維不織布 |
US12127925B2 (en) | 2018-04-17 | 2024-10-29 | The Procter & Gamble Company | Webs for absorbent articles and methods of making the same |
KR102152393B1 (ko) * | 2019-07-11 | 2020-09-04 | 도레이첨단소재 주식회사 | 권축형 복합섬유의 부직포와 그의 적층체, 및 물품 |
JP7567478B2 (ja) * | 2019-07-16 | 2024-10-16 | 東レ株式会社 | スパンボンド不織布及び積層不織布 |
JP7168125B1 (ja) * | 2021-03-18 | 2022-11-09 | 東レ株式会社 | スパンボンド不織布および積層不織布、これらの製造方法ならびに衛生材料 |
KR20240113599A (ko) * | 2022-01-05 | 2024-07-22 | 파이버텍스 퍼스널 케어 에이/에스 | 크림프된 다성분 섬유를 포함하는 부직포 |
EP4209629A1 (en) * | 2022-01-05 | 2023-07-12 | Borealis AG | Use of polymer composition on making soft nonwoven fabrics |
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JPS5212830B2 (ja) * | 1972-11-25 | 1977-04-09 | ||
US4189338A (en) * | 1972-11-25 | 1980-02-19 | Chisso Corporation | Method of forming autogenously bonded non-woven fabric comprising bi-component fibers |
JPS5734145A (en) * | 1980-08-07 | 1982-02-24 | Mitsui Petrochem Ind Ltd | Ethylene-alpha-olefin copolymer composition |
JPH0819570B2 (ja) * | 1986-09-12 | 1996-02-28 | チッソ株式会社 | 熱接着性複合繊維及びその製造方法 |
JP2682130B2 (ja) * | 1989-04-25 | 1997-11-26 | 三井石油化学工業株式会社 | 柔軟な長繊維不織布 |
US6448355B1 (en) * | 1991-10-15 | 2002-09-10 | The Dow Chemical Company | Elastic fibers, fabrics and articles fabricated therefrom |
US5382400A (en) * | 1992-08-21 | 1995-01-17 | Kimberly-Clark Corporation | Nonwoven multicomponent polymeric fabric and method for making same |
JP3246787B2 (ja) * | 1993-03-10 | 2002-01-15 | 宇部日東化成株式会社 | 多孔質繊維を用いた不織布およびその製造方法 |
US5780155A (en) * | 1994-08-11 | 1998-07-14 | Chisso Corporation | Melt-adhesive composite fibers, process for producing the same, and fused fabric or surface material obtained therefrom |
JP3569972B2 (ja) * | 1994-08-11 | 2004-09-29 | チッソ株式会社 | 熱融着性複合繊維および熱融着不織布 |
US6001752A (en) * | 1994-08-11 | 1999-12-14 | Chisso Corporation | Melt-adhesive composite fibers, process for producing the same, and fused fabric or surface material obtained therefrom |
JP2000008244A (ja) * | 1998-06-18 | 2000-01-11 | Hagiwara Kogyo Kk | 強化積層用フラットヤーンクロス |
US6454989B1 (en) * | 1998-11-12 | 2002-09-24 | Kimberly-Clark Worldwide, Inc. | Process of making a crimped multicomponent fiber web |
US6355348B1 (en) * | 1998-12-16 | 2002-03-12 | Mitsui Chemicals, Inc. | Composite-fiber nonwoven fabric |
CN1270013C (zh) * | 1999-12-21 | 2006-08-16 | 金伯利-克拉克环球有限公司 | 热塑性聚合物织物及其制法 |
MY139729A (en) * | 2002-11-25 | 2009-10-30 | Mitsui Chemicals Inc | Nonwoven fabric capable of being elongated and composite nonwoven fabric comprising said nonwoven fabric laminated |
CN100436667C (zh) * | 2003-08-28 | 2008-11-26 | 大和纺织株式会社 | 潜在卷曲性复合纤维及其制造方法、和纤维集合物、以及无纺布 |
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- 2008-12-10 TW TW97148048A patent/TW200934897A/zh unknown
- 2008-12-15 EP EP08863375.5A patent/EP2229474B1/en active Active
- 2008-12-15 WO PCT/JP2008/073148 patent/WO2009078479A1/en active Application Filing
- 2008-12-15 US US12/808,009 patent/US20100261399A1/en not_active Abandoned
- 2008-12-15 CN CN2008801265290A patent/CN101939470B/zh active Active
- 2008-12-15 KR KR1020107015013A patent/KR101259968B1/ko active IP Right Grant
- 2008-12-15 BR BRPI0819934-5A patent/BRPI0819934B1/pt active IP Right Grant
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WO2009078479A1 (en) | 2009-06-25 |
TW200934897A (en) | 2009-08-16 |
KR101259968B1 (ko) | 2013-05-02 |
EP2229474A4 (en) | 2011-03-02 |
CN101939470B (zh) | 2012-10-03 |
CN101939470A (zh) | 2011-01-05 |
KR20100090720A (ko) | 2010-08-16 |
JP5535911B2 (ja) | 2014-07-02 |
US20100261399A1 (en) | 2010-10-14 |
TWI367967B (ja) | 2012-07-11 |
JP2011506778A (ja) | 2011-03-03 |
BRPI0819934B1 (pt) | 2019-07-09 |
BRPI0819934A2 (pt) | 2015-05-26 |
EP2229474A1 (en) | 2010-09-22 |
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