WO2022065239A1 - Fibre composite pouvant subir un thermoliage, son procédé de production, et non-tissé utilisant une fibre composite pouvant subir un thermoliage - Google Patents
Fibre composite pouvant subir un thermoliage, son procédé de production, et non-tissé utilisant une fibre composite pouvant subir un thermoliage Download PDFInfo
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- WO2022065239A1 WO2022065239A1 PCT/JP2021/034354 JP2021034354W WO2022065239A1 WO 2022065239 A1 WO2022065239 A1 WO 2022065239A1 JP 2021034354 W JP2021034354 W JP 2021034354W WO 2022065239 A1 WO2022065239 A1 WO 2022065239A1
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- 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
- D04H1/5412—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
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- 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
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- 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
- D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
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- 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
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- 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
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- 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
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/004—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by heating fibres, filaments, yarns or threads so as to create a temperature gradient across their diameter, thereby imparting them latent asymmetrical shrinkage properties
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
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- 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
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- 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
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- 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
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- 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
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
Definitions
- the present invention relates to a heat-adhesive composite fiber, and more specifically, a non-woven fabric having excellent bulkiness and texture, and having excellent shapeability to follow processing with a complicated shape and high fiber deformation stress.
- the present invention relates to the obtained heat-adhesive composite fiber. More specifically, it is bulky suitable for applications such as absorbent articles for sanitary materials such as diapers, napkins and pads, medical hygiene materials, life-related materials, general medical materials, bedding materials, filter materials, nursing care products, and pet products.
- the present invention relates to a heat-adhesive composite fiber capable of obtaining a non-woven fabric having excellent properties, texture and shapeability, a method for producing the same, and a non-woven fabric using the heat-adhesive composite fiber.
- heat-adhesive composite fibers that can be molded by heat fusion using hot air or heat energy of a heating roll can easily obtain a non-woven fabric having excellent bulkiness and flexibility. Therefore, diapers and napkins. , Widely used for sanitary materials such as pads, and industrial materials such as daily necessities and filters. In particular, sanitary materials are extremely important for their bulkiness and flexibility because they come into direct contact with human skin and need to quickly absorb liquids such as urine and menstrual blood.
- There are two main methods for obtaining bulkiness and flexibility of non-woven fabric one is a method using bulky or flexible fibers, and the other is processing that can obtain bulkiness and flexibility in the state of non-woven fabric. This is a method of performing (formation processing).
- Patent Document 1 proposes a method of imparting an uneven shape to a nonwoven fabric by performing gear processing, which is one of the shaping processes, to give the nonwoven fabric bulkiness and flexibility. Strong stress is applied to the fibers during such processing, but if fibers with low elongation are used at this time, the fibers will break and become fluff on the surface of the non-woven fabric, which will cause deterioration of the tactile sensation. On the other hand, a fiber with high elongation that has followability is required.
- the undrawn yarn of the heat-fused composite fiber is placed at a temperature higher than both the glass transition point of the main crystalline thermoplastic resin of the heat-fused resin component and the glass transition point of the fiber-forming resin component.
- a fiber with high elongation by heat-treating at a constant length of 5 to 1.3 times and then heat-treating at a temperature 5 ° C. or higher higher than the constant-length heat treatment temperature under no tension.
- such a fiber has a problem that it becomes a non-woven fabric having a small fiber rigidity and a low bulk because the draw ratio is small.
- Patent Document 3 excellent bulkiness is realized by stretching the unstretched fiber of the heat-adhesive composite fiber at a breaking draw ratio of 75 to 95%.
- such fibers have an elongation of 50 to 120%, have insufficient followability to processing with a complicated shape and high fiber deformation stress, and have a problem that shaping processing is difficult.
- An object of the present invention is based on the above-mentioned prior art, and it is possible to maintain the stability of crimping even when a high elongation is left, and the non-woven fabric has excellent bulkiness and a complicated shape. It is an object of the present invention to provide a heat-adhesive composite fiber having a shape-forming processability that follows processing with a high fiber deformation stress, a method for producing the heat-adhesive composite fiber, and a nonwoven fabric using the heat-adhesive composite fiber. ..
- the present inventor has conducted extensive research in order to solve the above problems.
- a composite fiber having an eccentric sheath core type structure composed of a first component containing a polyester resin and a second component containing a polyolefin resin is produced, and is manufactured under appropriate drawing conditions and heat treatment conditions. It is possible to maintain the stability of crimping even when high elongation is left, and it has excellent bulkiness for non-woven fabrics and shaping workability that follows processing with complicated shapes and high fiber deformation stress. They have found that a heat-adhesive composite fiber to be given can be obtained, and have completed the present invention.
- the fiber cross section is composed of a first component containing a polyester resin and a second component containing a polyolefin resin having a melting point of 15 ° C. or higher lower than the melting point of the polyester resin, and is orthogonal to the length direction of the fiber.
- a heat-adhesive composite fiber having a breaking elongation of 200% or more, having a three-dimensional actual crimp, and having a crimp elastic modulus of 85 to 100%.
- Thermal adhesiveness including a step of melt-spinning so as to have a core-shaped cross-sectional shape to obtain undrawn fibers, a step of stretching the unstretched fibers to obtain drawn fibers, and a step of heat-treating the drawn fibers. It is a method for manufacturing composite fibers.
- Stretching efficiency (%) ⁇ Fiberity of unstretched fiber (dtex) / Stretching magnification (times) / Fineness of heat-adhesive composite fiber (dtex) ⁇ x 100
- the heat treatment step is performed at a high temperature of 10 to 70 ° C. or higher, which is the glass transition temperature of the polyester resin constituting the first component, and in a temperature range lower than the melting point of the polyolefin resin constituting the second component.
- the nonwoven fabric according to [9] which has an elongation of 90 to 150% and a specific volume of 30 to 75 cm 3 / g.
- the heat-adhesive composite fiber of the present invention can maintain the stability of crimping even when a high elongation is left, it has excellent bulkiness and is suitable for processing with a complicated shape and high fiber deformation stress. It is also possible to produce a non-woven fabric having a shape-forming processability that follows the above.
- FIG. 1 is a schematic view showing a drawing machine used for the heat-adhesive composite fiber of the present invention.
- FIG. 2 is an optical micrograph showing a two-dimensional mechanical crimp of a heat-adhesive composite fiber.
- FIG. 3 is a scanning electron micrograph showing a three-dimensional actual crimp of the heat-adhesive composite fiber of the present invention.
- the heat-adhesive composite fiber of the present invention is composed of a first component containing a polyester resin and a second component containing a polyolefin resin having a melting point of 15 ° C. or higher lower than the melting point of the polyester resin, and the length of the fiber.
- the polyester-based resin constituting the first component of the present invention is not particularly limited, and polyalkylene terephthalates such as polyethylene terephthalate, polytrimethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate, polylactic acid, and polybutylene succi. Examples thereof include biodegradable polyesters such as nate and polyglycolic acid, and copolymers of these with other ester-forming components.
- the other ester-forming component is not particularly limited, and examples thereof include glycols such as diethylene glycol and polymethylene glycol, and aromatic dicarboxylic acids such as isophthalic acid and hexahydroterephthalic acid.
- the copolymerization composition is not particularly limited, but it is preferable that the copolymerization component does not significantly impair the crystallinity, and from this viewpoint, the copolymerization component is used. It is more preferably 10% by mass or less, more preferably 5% by mass or less. These may be used alone or in combination of two or more types without any problem. Among them, at least one polyester resin selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polylactic acid, and polybutylene succinate, considering the cost of raw materials and the thermal stability of the obtained fiber. It is preferable that the polymer is an unmodified polymer composed only of polyethylene terephthalate.
- the first component is not particularly limited as long as it contains a polyester resin, but preferably contains 80% by mass or more of the polyester resin, and more preferably 90% by mass or more of the polyester resin. That is to be done.
- additives such as plasticizers may be added as needed.
- the polyolefin-based resin constituting the second component of the present invention is not particularly limited as long as it satisfies the condition that it has a melting point of 15 ° C. or higher lower than the melting point of the polyester-based resin constituting the first component, and the density is low.
- An acid-modified product, poly4-methylpenten-1 can be exemplified.
- low-density polyethylene linear low-density polyethylene, high-density polyethylene, and polypropylene are used from the viewpoint of suppressing the phenomenon that the polyolefin resins exposed on the fiber surface are not completely cooled and solidified during spinning and are fused. It is preferably at least one selected from the above group, and more preferably composed of only high-density polyethylene.
- the melt mass flow rate (hereinafter abbreviated as MFR) of the polyolefin-based resin that can be preferably used is not particularly limited as long as it can be spun, but is preferably 1 to 100 g / 10 minutes, more preferably. Is 5 to 70 g / 10 minutes.
- Physical properties of polyolefins other than the above MFR, such as Q value (weight average molecular weight / number average molecular weight), Rockwell hardness, number of branched methyl chains, and the like are not particularly limited as long as they satisfy the requirements of the present invention.
- the second component is not particularly limited as long as it contains a polyolefin-based resin, but preferably contains 80% by mass or more of the polyolefin-based resin, and more preferably 90% by mass or more of the polyolefin-based resin. That is to be done. As long as the effect of the present invention is not impaired, the additives exemplified in the first component may be contained as appropriate.
- the combination of the first component and the second component in the composite fiber of the present invention is a condition that the polyolefin-based resin constituting the second component has a melting point 15 ° C. or higher lower than the melting point of the polyester-based resin constituting the first component.
- the present invention is not particularly limited, and the first component and the second component described above can be selected and used.
- the first component is a mixture of two or more kinds of polyester-based resins and / or the second component is a mixture of two or more kinds of polyolefin-based resins, "the polyolefin-based resin constituting the second component".
- it has a melting point of 15 ° C.
- the combination of the first component / the second component include polyethylene terephthalate / polypropylene, polyethylene terephthalate / high-density polyethylene, polyethylene terephthalate / linear low-density polyethylene, and polyethylene terephthalate / low-density polyethylene. A more preferred combination of these is polyethylene terephthalate / high density polyethylene.
- the composite fiber of the present invention has an eccentric sheath core type structure in which the second component occupies the outer periphery of the fiber in the fiber cross section orthogonal to the length direction of the fiber.
- the eccentric sheath core type structure may be an eccentric sheath core solid type composite fiber or an eccentric sheath core hollow type composite fiber.
- the eccentric sheath core type refers to a state in which the center of gravity of the core side and the sheath side are different in the fiber cross section orthogonal to the length direction of the fiber, and the eccentric ratio is spinnability or three-dimensional actual crimping (hereinafter referred to as “three-dimensional”).
- the eccentricity ratio is expressed by the following formula described in JP-A-2006-97157.
- Eccentric ratio d / R
- d and R are as follows.
- d Distance between the center point of the composite fiber and the center point of the first component constituting the core
- R Radius of the composite fiber
- the cross-sectional shape of the core can be not only circular but also irregular, for example, star-shaped or elliptical. Variants such as shapes, triangles, quadrangles, pentagons, polylobes, arrays, T-shapes and horseshoe shapes can be mentioned.
- the cross-sectional shape on the core side is preferably circular, semi-circular or elliptical from the viewpoint of the manifestation of three-dimensional actual crimping, and particularly preferably circular from the viewpoint of the strength of the nonwoven fabric.
- the composite fiber of the present invention has a composite ratio of the first component (core component) and the second component (sheath component) in a fiber cross section orthogonal to the length direction thereof in a volume fraction of 10/90 to 90/10. It is preferably 30/70 to 70/30, and particularly preferably 40/60 to 50/50.
- the composite ratio greatly affects the elongation of unstretched fibers and the strength of fiber adhesion when processed into a non-woven fabric.
- the ratio of the first component By increasing the ratio of the first component, the elongation of the undrawn fibers can be suitably left, and the elongation of the drawn fibers obtained in the drawing step can be increased, so that the shapeability of the nonwoven fabric is preferably improved. Obtainable.
- the fiber adhesive strength when processed into a nonwoven fabric can be improved, and a nonwoven fabric that is hard to break can be preferably obtained.
- the fineness of the composite fiber of the present invention is not particularly limited, but is preferably in the range of 0.9 to 8.0 dtex. Specifically, for fibers used as sanitary materials, 1. It is more preferably 7 to 6.0 dtex, and even more preferably in the range of 2.6 to 4.4 dtex.
- the fineness of the composite fiber is 0.9 dtex or more, it is easy to obtain a composite fiber with high elongation, and when it is 8.0 dtex or less, it is easy to obtain a composite fiber having excellent crimping shape stability. preferable.
- By setting the fineness in such a range it is possible to have both high elongation and shape stability of crimping, and it becomes easy to achieve both excellent bulkiness and followability in shaping processing.
- the breaking elongation of the composite fiber of the present invention is 200% or more, preferably 250 to 500%, and more preferably 300 to 450%.
- the breaking elongation of the composite fiber is 200% or more, preferably 250 to 500%, and more preferably 300 to 450%.
- the fiber can be stretched without being cut in the state of being a non-woven fabric, and a non-woven fabric having excellent shapeability that follows a complicated shape can be obtained. can.
- the elongation at break is 500% or less, the strength of the composite fiber and the shape stability of the crimp can be enhanced, the stability of the card passage in the card process and the bulky non-woven fabric can be easily obtained.
- the breaking elongation in the present invention is based on JIS L 1015, and a tensile test is performed using a tensile tester with a sample gripping interval of 20 mm, and the elongation at break is defined as the breaking elongation of the fiber.
- the ratio of the breaking elongation to the fineness of the composite fiber of the present invention is not particularly limited, but is preferably 80% / dtex or more, more preferably 90% / dtex or more, and 100% / dtex or more. It is more preferably dtex or more.
- the ratio of the breaking elongation to the fineness of the composite fiber is 80% / dtex or more, it is possible to obtain a non-woven fabric having an excellent balance between shapeability and texture.
- the breaking strength of the composite fiber of the present invention is not particularly limited, but is preferably 0.5 to 1.5 cN / dtex for fibers used as sanitary materials, for example, and is 0. It is more preferably 7. to 1.4 cN / dtex, and even more preferably 0.9 to 1.3 cN / dtex. If the breaking strength is low, fiber breakage or entanglement may occur when the fiber is transported in the manufacturing process, but if the breaking strength of the composite fiber is 0.5 cN / dtex or more, the strength is sufficient and the fiber. It is possible to suppress cutting and entanglement.
- the breaking strength is generally inversely proportional to the elongation, if it is 1.5 cN / dtex or less, sufficient elongation can be left for processing when the non-woven fabric is formed. By setting the breaking strength within such a range, it is possible to obtain a fiber that does not cause any trouble in each process while maintaining the elongation.
- the ratio of the breaking strength to the breaking elongation (breaking strength [cN / dtex]) / breaking elongation [%] of the composite fiber of the present invention is not particularly limited, but is less than 0.005. Is more preferably less than 0.004, and even more preferably less than 0.0024. A large ratio of breaking strength to breaking elongation means high strength and low elongation, and a small ratio of breaking strength to breaking elongation means low strength and high elongation.
- this ratio is less than 0.005, when shaping the nonwoven fabric, it is preferable.
- the dry heat shrinkage rate of the composite fiber of the present invention at 120 ° C. is not particularly limited, but is preferably 0 to 15%, more preferably 0 to 10%, and 0 to 5%. Is more preferable.
- the dry heat shrinkage rate is 0% or more, the elongation of the fiber improves with shrinkage, and when the dry heat shrinkage rate is 15% or less, the web using the composite fiber of the present invention is heat-treated to be a non-woven fabric. It is preferable because it can secure the thermal dimensional stability at the time of processing. By setting the heat shrinkage in such a range, it is possible to achieve both a sufficient level of shape processing followability and thermal dimensional stability.
- the method for calculating the dry heat shrinkage rate will be described in Examples described later.
- the web heat shrinkage rate of the composite fiber of the present invention at 145 ° C. is not particularly limited, but is preferably 5 to 70%, more preferably 10 to 50%, and 10 to 30%. Is more preferable.
- the web heat shrinkage rate is 5% or more, the elongation of the fiber is improved with the shrinkage, and the shaping followability when the nonwoven fabric is shaped is improved, which is preferable.
- it is preferably 70% or less.
- the composite fibers of the present invention have three-dimensional manifest crimps.
- Three-dimensional actual crimping means having a three-dimensional crimping shape such as a spiral or an ohm shape (a shape in which the shape of a mountain valley is rounded and twisted in three dimensions instead of an acute angle), and is a kind of single three-dimensional curling. It may be a reduced shape or a mixed three-dimensional crimped shape, and is not particularly limited. Having such a three-dimensional crimped shape makes it easy to obtain a bulky and flexible non-woven fabric.
- the crimped shape of the composite fiber of the present invention is mainly three-dimensional actual crimping, but two-dimensional mechanical crimping having a planar zigzag structure (bent shape) may be mixed.
- the number of three-dimensional actual crimps preferably occupies 50% or more, and more preferably 80% or more.
- the number of crimps of the composite fiber of the present invention is not particularly limited, but is preferably 6 to 20 ridges / 2.54 cm, and more preferably 8 to 16 ridges / 2.54 cm. By setting the number of crimps within this range, the card passability in the card process in the nonwoven fabric processing process is stable, and it becomes easy to obtain a bulky and flexible nonwoven fabric.
- the number of crimps in the present invention is the total of the three-dimensional actual crimps and the two-dimensional mechanical crimps.
- the crimp ratio of the composite fiber of the present invention is not particularly limited, but is preferably 5 to 25%, more preferably 6 to 20%.
- the card passability is at a sufficient level, and when the crimp ratio is 6% or more, more suitable card passability can be obtained.
- the crimp ratio is 25% or less, the texture uniformity at the time of forming the web can be obtained, and when the crimp ratio is 20% or less, more suitable texture uniformity can be obtained, which is preferable.
- the crimp elastic modulus of the composite fiber of the present invention is 85 to 100%, preferably 90 to 100%, and more preferably 95 to 100%.
- the shape of the crimp can be maintained in the non-woven fabric making step, whereby a bulky nonwoven fabric can be obtained.
- the composite fiber having such a crimp elastic modulus can be obtained, for example, by appropriately changing the stretching temperature and the stretching ratio in the stretching step described later.
- the crimp elastic modulus in JIS L 2080, "the difference between the length when the crimp of the fiber is stretched and the length after loosening it and leaving it for a predetermined time, the length when stretched and the original length Percentage of the difference between the two.
- the specific measurement method is specified in JIS L 1015.
- a drape feeling and a smooth touch feeling derived from its own weight are given within a range that does not interfere with the effect of the present invention, and flexibility by forming voids inside and outside the fiber such as voids and cracks.
- Inorganic fine particles may be added as needed in order to obtain excellent fibers.
- the amount of the inorganic fine particles added to the fiber is preferably 0 to 10% by mass, more preferably 0.1 to 10% by mass, and further preferably 1 to 5% by mass.
- the inorganic fine particles are not particularly limited as long as they have a high specific density and are unlikely to aggregate in the molten resin, but to give an example, titanium oxide (specific density 3.7 to 4.3) and zinc oxide (specific gravity 5). .2-5.7), barium titanate (specific density 5.5-5.6), barium carbonate (specific gravity 4.3-4.4), barium sulfate (specific density 4.2-4.6), zirconium oxide (Specific density 5.5), zirconium silicate (specific density 4.7), alumina (specific density 3.7 to 3.9), magnesium oxide (specific density 3.2) or substances having almost the same specific density as these can be mentioned. Of these, titanium oxide is preferably used.
- inorganic fine particles are added to fibers and used for the purpose of concealing property, antibacterial property, deodorant property and the like.
- the inorganic fine particles used are preferably of a particle size and shape that do not cause problems such as yarn breakage in the spinning process and the drawing process.
- a method of adding the inorganic fine particles a method of directly adding the powder of the inorganic fine particles into the first component or the second component, or a method of kneading the inorganic fine particles into a resin and making a masterbatch into the first component or the second component.
- the method of addition and the like can be mentioned.
- the resin used for masterbatch is most preferably the same resin as the first and second components, but is not particularly limited as long as it satisfies the requirements of the present invention, and a resin different from the first and second components can be used. You may use it.
- the second component comprises a first component containing a polyester resin and a second component containing a polyolefin resin having a melting point of 15 ° C. or higher lower than the melting point of the polyester resin.
- a step of melt-spinning so as to have an eccentric sheath core type cross-sectional shape that occupies the outer periphery of the fiber to obtain an unstretched fiber (hereinafter, may be referred to as a spinning step), and a step of drawing the unstretched fiber under specific conditions.
- a step of obtaining drawn fibers (hereinafter, may be referred to as a drawing step) and a step of heat-treating the drawn fibers (hereinafter, may be referred to as a heat treatment step) are included. It can be manufactured by adjusting the stretching efficiency to be in the range of 40 to 75%.
- Stretching efficiency (%) ⁇ Fiberity of unstretched fiber (dtex) / Stretching magnification (times) / Fineness of heat-adhesive composite fiber (dtex) ⁇ x 100
- a fiber having a relatively high elongation can be obtained by stretching (flow stretching) a polyester-based unstretched fiber at a temperature higher than the glass transition point, but the fiber rigidity is low and the fiber is crimped. Due to the low shape stability, the non-woven fabric obtained by using this fiber has a low bulk.
- the present inventor has found that by further heat-treating the flow-stretched composite fiber, the elongation is further increased and the shape stability of the crimp is improved.
- the polyester-based resin constituting the first component is increased in elongation by heat-relaxing the orientation from a low-crystal, high-orientation state by heat-treating after flow-stretching. Further, it is considered that the fiber rigidity is improved by the orientation and crystallization of the polyolefin resin constituting the second component. It is considered that this effect is based on the phenomenon that the fineness is increased and the fiber is contracted in the length direction by the heat treatment after the fluid drawing.
- the fineness of the drawn fiber after the heat treatment is 120% or more, preferably 125% or more, and more preferably 130% or more with respect to the fineness of the drawn fiber before the heat treatment.
- the upper limit is not particularly limited, but is actually 200% or less.
- the length of the drawn fiber after the heat treatment is 90% or less, preferably 85% or less, and more preferably 80% or less with respect to the length of the drawn fiber before the heat treatment.
- the lower limit is not particularly limited, but is actually 50% or more. That is, the composite fibers obtained with a draw efficiency of 40 to 75%, more preferably 50 to 75%, and even more preferably 60 to 75% have high elongation and crimp shape stability. Therefore, it is possible to produce a non-woven fabric having excellent bulkiness and excellent shapeability that can follow processing with a complicated shape and high fiber deformation stress.
- the above-mentioned effects are not predicted in the prior art, and are novel effects found in the present invention.
- the stretching efficiency can be controlled by appropriately selecting the spinning temperature, spinning speed, stretching ratio, stretching temperature, heat treatment temperature and the like, which will be described later.
- spinning temperature The temperature at the time of melt spinning (hereinafter, may be referred to as spinning temperature) is not particularly limited as long as it is a temperature at which the first component and the second component can be melted, but is above the melting point of the first component. It is more preferable that the melting point of the first component is + 30 ° C. or higher, and it is further preferable that the melting point of the first component is + 50 ° C. or higher. When the spinning temperature is + 30 ° C.
- the upper limit of the temperature is not particularly limited as long as it is a temperature at which spinning is possible.
- the spinning speed is not particularly limited as long as undrawn fibers can be obtained, but is preferably 300 to 1500 m / min, and more preferably 550 to 1000 m / min. When the spinning speed is 300 m / min or more, the single-hole discharge amount when trying to obtain undrawn fibers having an arbitrary fineness is increased, and satisfactory productivity can be obtained, which is preferable.
- the fineness of the undrawn fiber is not particularly limited, but is preferably 5 to 12 dtex, more preferably 6 to 11 dtex, and further preferably 7 to 10 dtex.
- the fineness of the unstretched fiber is 5 dtex or more, sufficient elongation can be ensured with the stretched fiber, and the shapeability when processed into a nonwoven fabric can be suitably obtained.
- the fineness of the stretched fiber can be sufficiently thinned, and a sufficient texture can be ensured when the non-woven fabric is processed, which is preferable.
- the unstretched fiber obtained under the above conditions is stretched in the stretching step.
- the stretching step by changing the temperature and stretching ratio to control the orientation and crystallinity of the molecular chains of the first component and / or the second component, the physical properties such as strength, elongation, and heat resistance of the composite fiber are controlled. Can be controlled.
- the stretching ratio in the stretching step of the present invention is not particularly limited, but is preferably 1.5 times or more, more preferably 2 to 5 times, and 3.6 to 4. It is more preferably in the range of 5 times.
- the draw ratio is 1.5 times or more, the crimp elastic modulus of the composite fiber is high and the shape stability of the crimp can be improved. Therefore, when it is 5 times or less, the elongation of the composite fiber is preferable.
- the stretching temperature is not particularly limited, but is as high as 10 to 70 ° C. or higher, which is the glass transition temperature of the polyester resin constituting the first component, and the melting point of the polyolefin resin constituting the second component.
- the temperature range is preferably less than, preferably 35 to 60 ° C. or higher, which is the glass transition temperature of the polyester resin constituting the first component, and 5 ° C. or lower, which is the melting point of the polyolefin resin constituting the second component.
- the temperature range is more preferably 40 to 50 ° C. or higher, which is the glass transition temperature of the polyester resin constituting the first component, and 10 ° C. or lower, which is the melting point of the polyolefin resin constituting the second component. It is more preferable to have.
- the stretching temperature is + 10 ° C. or higher, more preferably + 35 ° C. or higher, and even more preferably + 40 ° C. or higher of the glass transition temperature of the polyester resin constituting the first component, the elongation is high even when stretched at a high magnification.
- the fiber is preferably + 70 ° C. or lower, more preferably + 60 ° C. or lower, still more preferably + 50 ° C. or lower, the cold crystallization of the first component can be suppressed, and the polyolefin-based resins as the second component can be suppressed from each other. It is preferable because it can suppress the destabilization of the stretching process due to the fusion of the above.
- the stretching step of the present invention is not particularly limited as long as the effect of the present invention is not impaired, and even if it is a one-step stretching, it is a two-step stretching in which the fiber once stretched is stretched again. However, it may be multi-stage stretching by repeating the same procedure. When the stretching treatment is performed twice or more, it may be performed continuously.
- the one-step stretching is performed by a stretching machine 10 having a first draw frame 11 composed of a plurality of rolls and a second draw frame 12 composed of a plurality of rolls.
- the speed of the fiber pulled by the second draw frame 12 is made higher than the speed of the fiber sent out by the first draw frame 11, and the fiber F is pulled by the second draw frame 12 to stretch the fiber.
- the physical properties such as strength, elongation, and heat resistance of the composite fiber can be controlled by controlling the orientation and crystallinity of the molecular chain.
- a steam chamber 13 may be provided between the first draw frame 11 and the second draw frame 12.
- the draw ratio of the fiber F is X 2 / X 1 . It is represented by.
- the stretching temperature means the temperature of the fiber at the stretching start position. That is, in the stretching machine 10, it means the temperature of the fiber in the first draw frame 11.
- the two-stage stretching is performed by a stretching machine 20 having a first draw frame 21, a second draw frame 22 composed of a plurality of rolls, and a third draw frame 23 composed of a plurality of rolls. ..
- the speed of the fiber pulled by the second draw frame 22 is made higher than the speed of the fiber delivered by the first draw frame 21, and the speed of the fiber pulled by the second draw frame 22 is higher than the speed of the fiber delivered by the second draw frame 22.
- the fibers are stretched by increasing the speed X3 of the fibers pulled by the draw frame 23. That is, the first stretching is performed between the first draw frame 21 and the second draw frame 22, and the second stretching is performed between the second draw frame 22 and the third draw frame 23.
- Reference numeral 24 is a steam chamber.
- two stretching machines 10 shown in FIG. 1a may be independently arranged and stretched twice.
- the draw ratio of each time is expressed as Xn + 1 / Xn when the fiber velocity by the draw frame on the upstream side is Xn and the fiber velocity by the draw frame on the downstream side is Xn + 1. Is done.
- the total stretch ratio of the two-stage stretching is represented by the product of the first stretching ratio and the second stretching ratio.
- the stretching temperature means the temperature of the fiber at the first stretching start position. That is, in the stretching machine 20, it means the temperature of the fiber in the first draw frame 21.
- the heat treatment step of the present invention is not particularly limited, but may be a heat treatment by heating air or steam, or may be a heat treatment by contact with a hot roll or the like. Further, the heat treatment may be performed in a state where the fibers are constrained to a fixed length, or may be a heat treatment in a relaxed state.
- the heat treatment temperature is not particularly limited, but is as high as 10 to 70 ° C. or higher, which is the glass transition temperature of the polyester resin constituting the first component, and lower than the melting point of the polyolefin resin constituting the second component.
- the temperature range is preferably 30 to 60 ° C. or higher, which is the glass transition temperature of the polyester resin constituting the first component, and 5 ° C or lower, which is the melting point of the polyolefin resin constituting the second component. It is more preferable to have.
- the heat treatment temperature is + 10 ° C. or higher, more preferably + 30 ° C.
- the heat treatment temperature is preferably a temperature equal to or higher than the stretching temperature.
- the heat treatment time is not particularly limited, but is preferably long as long as the operability is not impaired, specifically, 5 seconds or longer, more preferably 30 seconds or longer, still more preferably 3 minutes or longer.
- the expression of the three-dimensional actual crimp of the present invention is derived from the composite structure of the composite fiber and the difference in heat shrinkage between the composite components, and is expressed by the manifestation of the latent crimp inherent in the fiber.
- the actual crimps developed in the heat treatment step have a larger crimp diameter than the actual crimps developed in the stretching step, and the number of manifest crimps can be in an appropriate range.
- two-dimensional mechanical crimping may be applied by a crimper or the like before the heat treatment step.
- Such mechanical crimping has a two-dimensional crimping shape such as a planar zigzag structure (bending shape), and is different from the three-dimensional actual crimping.
- the number of two-dimensional mechanical crimps applied in the crimping step is not particularly limited, and is preferably 5 to 10 peaks / 2.54 cm, preferably 7 to 9 peaks / 2.54 cm. It is more preferable to have.
- the fibers and the non-woven fabric obtained by using the fibers have a hard feel, but 5 to 10 threads / 2.
- the fiber receives heat and strong stress during this mechanical crimp, and its thermodynamic and physical effects are memorized inside the fiber and as the shape of the fiber. ⁇ It will be fixed.
- latent crimps become apparent while dragging the thermodynamic and physical effects that are stored and fixed in advance inside the fiber. Under the influence of the shape, overt crimps with a large crimp diameter are likely to occur.
- the crimp diameter By increasing the crimp diameter, the flexibility of the fiber is improved, and the fiber obtained in the heat treatment step by being subjected to thermodynamic and physical action in advance in the crimping step is particularly the actual winding. It is a fiber with excellent shrinkage shape stability.
- the number of mechanical crimps can be adjusted, for example, by appropriately changing the stuffing box pressure in the push-in type crimper. Furthermore, before applying this mechanical crimp, annealing treatment is performed in an atmosphere of dry heat, moist heat, steam, etc. as necessary to improve the heat history, suppress stress relaxation, and perform heat treatment steps. It is also possible to make fine adjustments to the heat shrinkage of.
- the surface of the composite fiber of the present invention may be treated with various fiber treatment agents, thereby imparting functions such as hydrophilicity, water repellency, antistatic property, surface smoothness and abrasion resistance. be able to.
- a method of adhering the fiber treatment agent with a kiss roll at the time of picking up unstretched fibers and a method of adhering the fiber treatment agent with a touch roll method, a dipping method, a spraying method, etc. at the time of stretching and / or after stretching.
- a method of adhering the fiber treatment agent with a kiss roll at the time of picking up unstretched fibers and a method of adhering the fiber treatment agent with a touch roll method, a dipping method, a spraying method, etc. at the time of stretching and / or after stretching.
- the heat-treated composite fiber may be cut into short fibers.
- the cut length can be selected according to the intended use and is not particularly limited, but is preferably in the range of 20 to 102 mm, more preferably in the range of 30 to 51 mm when the carding process is performed.
- Non-woven fabric Since the non-woven fabric of the present invention uses a composite fiber having both high elongation and shape stability of crimping, it is bulky and has a shaping process that follows processing with a complicated shape and high fiber deformation stress. Excellent in sex. That is, the preferable range of the elongation of the nonwoven fabric is 90 to 150%, and the preferable range of the specific volume is 30 to 75 cm 3 / g.
- the processing conditions for the nonwoven fabric are not particularly limited, and examples thereof include a method of heat-treating a card web obtained by using a roller card machine at a melting point of the second component or higher to form a nonwoven fabric.
- the heat treatment method is not particularly limited, but a through-air processing method or the like is preferable in that the flexibility of the nonwoven fabric can be satisfactorily processed.
- the non-woven fabric produced using the composite fiber of the present invention is, for example, an absorbent article such as a diaper, a napkin, an incontinence pad, a medical hygiene material such as a gown, a surgical gown, a wall sheet, an obstacle paper, an indoor interior material such as a floor material.
- Cover cloth, cleaning wiper, life-related materials such as garbage covers, toiletry products such as disposable toilets and toilet covers, pet products such as pet sheets, diapers for pets, towels for pets, wiping materials, filters, cushions
- It can be used for various textile products that require bulkiness and compression resistance, such as industrial materials such as materials, oil adsorbents, adsorbents for ink tanks, general medical materials, bedding materials, and nursing care products. can.
- ⁇ MFR of polyolefin resin> The measurement was performed according to JIS K 7210. ⁇ Fineness, breaking strength, breaking elongation, ratio of breaking elongation to fineness> According to JIS L 1015, the fineness of undrawn fibers, the fineness of composite fibers, the breaking strength, and the breaking elongation were measured. Further, the ratio of the elongation at break and the fineness was calculated by dividing the elongation at break [%] by the fineness [dtex].
- the heat-adhesive composite fiber was hung on a roller card machine, a web sheet having a basis weight of about 200 g / m 2 was collected, cut out in a square of about 25 cm, and the length A0 in the flow direction of the fiber was measured.
- the heat treatment was performed by leaving it in a hot air circulation dryer heated to 145 ° C.
- Web heat shrinkage rate (%) [(A0-A1) / A0] ⁇ 100 ⁇ Specific volume of non-woven fabric>
- the heat-adhesive composite fiber was hung on a roller card machine, and the obtained web was heat-treated.
- the obtained non-woven fabric was subjected to a load of 3.5 g / cm 2 using a digital indicator (manufactured by Mitutoyo).
- the thickness was measured.
- the specific volume was calculated from the measured thickness using the following formula.
- the cut non-woven fabric sample was pulled by an autograph AGS-J manufactured by Shimadzu Corporation at a sample length of 100 mm and a test speed of 100 m / min, and the elongation when the nonwoven fabric was broken was defined as the elongation of the nonwoven fabric.
- the heat-adhesive composite fiber was hung on a roller card machine, and the obtained web was heat-treated, and the obtained non-woven fabric was cut into a size of 15 cm ⁇ 5 cm with the machine direction as the long side.
- the cut non-woven fabric sample was stretched by Autograph AGS-J manufactured by Shimadzu Corporation.
- a sample for evaluation of followability was prepared by performing a stretching treatment of 10 cm with a sample length of 10 cm and a tensile speed of 100 m / min.
- the followability of the obtained sample was determined in the following three stages. ⁇ Evaluation criteria ⁇ ⁇ : The non-woven fabric is entirely stretched, and no partial breakage of the non-woven fabric is observed. ⁇ : The non-woven fabric is locally stretched, and no partial breakage of the non-woven fabric is observed. X: The non-woven fabric is broken by the stretching treatment, or the non-woven fabric is partially broken.
- the unstretched fiber having a fineness of 8.0 dtex was obtained under the condition of a spinning speed of 900 m / min. Next, the obtained unstretched fiber was stretched, mechanically crimped, and heat-treated under the conditions shown in Table 1 to obtain a heat-adhesive composite fiber.
- PET Polyethylene terephthalate
- MFR 190 ° C, load 21.18 N
- PE High-density polyethylene
- the undrawn fiber of 8.0 dtex was obtained under the condition of a spinning speed of 600 m / min.
- the obtained unstretched fiber was stretched, mechanically crimped, and heat-treated under the conditions shown in Table 1 to obtain a heat-adhesive composite fiber.
- Table 2 shows the physical characteristics of the composite fibers and the non-woven fabric obtained in Examples 1 to 4 and Comparative Examples 1 to 3.
- Examples 1 to 4 according to the present invention have a breaking elongation of 200% or more, have three-dimensional crimping, and have a crimp elastic modulus of 85 to 100%.
- the non-woven fabric produced using this composite fiber has a large specific volume and a large elongation, and is excellent in bulkiness and followability.
- the composite fibers of Comparative Examples 1 and 2 had a breaking elongation of less than 200%, a non-woven fabric having a small elongation, and poor followability.
- the composite fiber of Comparative Example 3 had a very high breaking elongation, and the non-woven fabric produced using this composite fiber had a high elongation and excellent followability, but three-dimensional actual crimping was exhibited. It was not bulky.
- the heat-adhesive composite fiber of the present invention has both high elongation and shape stability of crimping, it is excellent in bulkiness and has shapeability that can follow the processing of complicated shapes and high fiber deformation stress. It is possible to produce an excellent non-woven fabric. Utilizing these characteristics, it is used for absorbent articles for sanitary materials such as diapers, napkins, pads, medical hygiene materials, life-related materials, general medical materials, bedding materials, filter materials, nursing care products, pet products, etc. Can be suitably used in.
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Abstract
La présente invention aborde le problème de la fourniture : d'une fibre composite pouvant subir un thermoliage qui est apte à maintenir une stabilité de sertissage même si un allongement élevé reste, et qui fournit un non tissé présentant une excellente aptitude au moulage et une excellente aptitude au façonnage qui permet de suivre une forme ou un traitement compliqué à l'aide d'une contrainte de déformation de fibre élevée ; d'un procédé de production de cette fibre composite pouvant subir un thermoliage ; et d'un non tissé qui utilise cette fibre composite pouvant subir un thermoliage. La solution selon l'invention concerne une fibre composite pouvant subir un thermoliage qui comprend un premier composant qui contient une résine à base de polyester et un second composant qui contient une résine à base de polyoléfine ayant un point de fusion qui est inférieur au point de fusion de la résine à base de polyester de 15 °C ou plus, et qui a une structure noyau-gaine excentrique dans laquelle, dans une section transversale de la fibre perpendiculaire à la direction longitudinale, le second composant occupe la périphérie externe de la fibre. Cette fibre composite pouvant subir un thermoliage présente un allongement à la rupture supérieur ou égal à 200 %, un sertissage apparent tridimensionnel et un module élastique de sertissage de 85 % à 100 %.
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EP21872368.2A EP4219809A1 (fr) | 2020-09-24 | 2021-09-17 | Fibre composite pouvant subir un thermoliage, son procédé de production, et non-tissé utilisant une fibre composite pouvant subir un thermoliage |
US18/027,116 US20230332337A1 (en) | 2020-09-24 | 2021-09-17 | Heat-bondable composite fiber, method for producing same and nonwoven fabric using heat-bondable composite fiber |
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JP4820211B2 (ja) * | 2006-05-12 | 2011-11-24 | 帝人ファイバー株式会社 | 自己伸長性熱接着性複合繊維及びその製造方法 |
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CN108350609A (zh) * | 2017-03-31 | 2018-07-31 | 艺爱丝维顺(苏州)纤维有限公司 | 热熔接性复合纤维和使用其的无纺布 |
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2020
- 2020-09-24 JP JP2020159357A patent/JP6916360B1/ja active Active
- 2020-11-20 CN CN202011309106.1A patent/CN112458559B/zh active Active
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2021
- 2021-09-17 US US18/027,116 patent/US20230332337A1/en active Pending
- 2021-09-17 EP EP21872368.2A patent/EP4219809A1/fr active Pending
- 2021-09-17 WO PCT/JP2021/034354 patent/WO2022065239A1/fr unknown
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JP2006097157A (ja) | 2004-09-28 | 2006-04-13 | Chisso Corp | 潜在捲縮性複合繊維及びこれを用いた繊維構造物、吸収性物品 |
JP2007204901A (ja) | 2006-02-06 | 2007-08-16 | Teijin Fibers Ltd | 熱接着性複合繊維およびその製造方法 |
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CN112458559B (zh) | 2022-03-25 |
EP4219809A1 (fr) | 2023-08-02 |
CN112458559A (zh) | 2021-03-09 |
US20230332337A1 (en) | 2023-10-19 |
JP2022052859A (ja) | 2022-04-05 |
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