EP4043623A1 - Sheath-core composite fiber and multifilament - Google Patents

Sheath-core composite fiber and multifilament Download PDF

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Publication number
EP4043623A1
EP4043623A1 EP20874251.0A EP20874251A EP4043623A1 EP 4043623 A1 EP4043623 A1 EP 4043623A1 EP 20874251 A EP20874251 A EP 20874251A EP 4043623 A1 EP4043623 A1 EP 4043623A1
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EP
European Patent Office
Prior art keywords
fiber
core
component
sheath
multifilament
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.)
Pending
Application number
EP20874251.0A
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German (de)
English (en)
French (fr)
Inventor
Tomohiko Matsuura
Masato Masuda
Shinya Kawahara
Kazuya Fujita
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Toray Industries Inc
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Toray Industries Inc
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Publication date
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Publication of EP4043623A1 publication Critical patent/EP4043623A1/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • 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
    • 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
    • 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
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor

Definitions

  • the present invention relates to a core-sheath composite fiber and a multifilament that are suitable for producing a light, flexible, and resilient textile having a natural silk-like luxurious gloss.
  • Synthetic fibers made of polyester, polyamide, etc. have excellent mechanical properties and high dimensional stability, and accordingly they are used in various fields ranging from clothing to non-clothing.
  • Synthetic fibers made of polyester, polyamide, etc. have excellent mechanical properties and high dimensional stability, and accordingly they are used in various fields ranging from clothing to non-clothing.
  • many industries including clothing production are requiring advanced textures and functions that are not realized with conventional synthetic fibers.
  • natural silk which is the highest level natural material. They include polymer techniques for designing of fibers with special cross-sectional shapes and spinning techniques that use mixtures of different types of fibers.
  • polyester fibers which can reflect light relatively strongly, have an irregular cross section of a multilobar shape, they can give amplified light reflection due to the irregularity of the multilobar shape, resulting in a mild gloss in combination with high brightness to imitate natural silk.
  • Such fibers are now produced in large quantities as a typical silky material.
  • a variety of fiber techniques have been disclosed with the aim of producing composite fibers that have more complicated cross-sectional shapes to realize natural silk-like textures.
  • Patent document 1 proposes a composite fiber that is characterized of a multilobar fiber cross section in which an easily dissolvable component is located at each apex of the multilobar shape in a tapered manner toward the interior of the fiber.
  • the easily dissolvable component is subjected to dissolution treatment to produce grooves in the apex portions of the multilobar shape, thereby enhancing the light reflection by the multilobar shape and also increasing the frictional force by the groove portions.
  • This document stipulates that this serves to realize not only luxurious gloss and dry touch of natural silk, but also scroop, which is characteristic feature of textiles made of natural silk.
  • Patent document 2 proposes a composite fiber that has a fiber cross section in which several hardly dissolvable components are separated by an easily dissolvable component.
  • the composite fiber is subjected to dissolution treatment to dissolve out the easily dissolvable component, the single composite fiber is divided into a plurality of fibers having irregular cross sections and the combined effect of the decreased fiber diameter and the irregular cross-sectional shape acts to give a soft texture in addition to natural silk-like luxurious gloss and dry touch.
  • Patent document 3 proposes a shrinkage-varying combined-fiber multifilament containing at least two types of fibers with different thermal shrinkage rates produced by the spinning-combining method.
  • the shrinkage-varying combined-fiber multifilament contains a fiber of copolymer polyester as a component. When it is heated, there occur differences in length among the groups of fibers that differ in shrinkage rate, and this serves to produce cloth with fluffiness, resulting in a silky material.
  • the approach of mixing fibers having different shrinkage rates to produce cloth with fluffiness is actually effective in terms of the formation of cloth having lightness brought about by the fluffiness, but the fibers cannot be mixed uniformly in some cases because the mixing of different types of fibers occurs during the take-up step or the yarn processing step. If such uneven fiber mixing occurs, the cloth may fail to develop a sufficiently flexible texture because, for example, it suffers clogging in portions where fibers with higher shrinkage rates are localized densely.
  • the main object of the present invention is to solve the above problems with the prior art technology and to provide a core-sheath composite fiber and a multifilament that are suitable for producing a good textile that can be a match for natural silk.
  • This object of the present invention can be achieved by the following approach. Specifically, it provides:
  • the use of the core-sheath composite fiber or multifilament according to the present invention serves to form a unique space structure in which fine interfiber spaces with fiber-to-fiber distances of less than 5 ⁇ m and coarse interfiber spaces with fiber-to-fiber distances of 10 ⁇ m or more coexist uniformly in a multifilament as in natural silk, and this serves to produce a light, flexible, and resilient textile having a natural silk-like luxurious gloss.
  • natural silk contains fine interfiber spaces with fiber-to-fiber distances of less than 5 ⁇ m and coarse interfiber spaces with fiber-to-fiber distances of 10 ⁇ m or more coexist uniformly between single fibers whereas in conventional materials, only either interfiber spaces of less than 5 ⁇ m or those of 10 ⁇ m or more can be formed, and this difference in space formation has significant influence on the characteristics of the resulting woven and knitted fabrics.
  • interfiber spaces As the size of interfiber spaces increases up to 10 ⁇ m or more, fibers fixed at tying points in the woven or knitted fabric become movable, the fabric increases in flexibility and it also enhances in lightness as a result of a decrease in apparent density brought about by an increase in space proportion, whereas interfiber spaces with sizes of 5 ⁇ m or more cause a decrease in bending rigidity and, in turn, a decrease in resilience. Accordingly, there occurs a trade-off relation between lightness/flexibility and resilience in the case of conventional materials in which only either interfiber spaces of less than 5 ⁇ m or interfiber spaces of 10 ⁇ m or more can be formed.
  • the present invention is constructed based on this idea. To produce such unique interfiber spaces characteristic of natural silk as described above, it is important for the composite fiber according to the present invention to be a core-sheath composite fiber including two or more types of polymers and having a cross section in which the core component possesses a multilobar shape with three or more convex portions and the sheath component surrounds it completely, which is the first requirement of the present invention.
  • a core-sheath composite fiber as referred to for the present invention is one including two or more types of polymers and having a cross section perpendicular to the fiber axis in which the sheath component is arranged so that it surrounds the core component.
  • the core-sheath composite fiber according to the present invention will be high in processability if both the core component and the sheath component included therein are thermoplastic polymers, and accordingly, the polymers to use to form the fiber are preferably selected from the groups of, for example, polyester based, polyethylene based, polypropylene based, polystyrene based, polyamide based, polycarbonate based, polymethyl methacrylate based, and polyphenylene sulfide based polymers, as well as copolymers thereof.
  • thermoplastic polymers contained in the core-sheath composite fiber are polymers belonging to the same polymer group or copolymers thereof.
  • the polymers may contain inorganic substances such as titanium oxide, silica, and barium oxide; coloring agents such as carbon black and other dyes and pigments; and other various additives such as flame retardant, fluorescent brightening agent, antioxidant, and ultraviolet absorber.
  • the use of plant derived biopolymers and recycled polymers is desirable for the present invention as well from the viewpoint of reducing the environmental load.
  • the polymers listed above that serve for the present invention may be recycled polymers that are recycled by any of useful techniques including chemical recycling, material recycling, and thermal recycling.
  • polyester based resins show suitable polymer characteristics to allow the features of the present invention to be realized in a noticeable manner and, as described above, they serve to achieve a bending rigidity close to that of natural silk and good color development. From this viewpoint, the use of recycled polyesters is preferred for the present invention.
  • the core-sheath composite fiber according to the present invention is designed to provide a multifilament formed of the core component, which is produced by subjecting the fiber to high-order processing such as weaving and knitting and then dissolving out the sheath component.
  • the core component and the sheath component are hardly dissolvable and easily dissolvable, respectively, in the solvent used to dissolve out the sheath component, and therefore, a good approach is to first select a core component suitable for the purpose and then identify a sheath component from among the above polymers in consideration of useful solvents.
  • the ratio in the rate of dissolution in the solvent between the hardly dissolvable component (core component) and the easily dissolvable component (sheath component) adopted for use in combination is desirable for the ratio in the rate of dissolution in the solvent between the hardly dissolvable component (core component) and the easily dissolvable component (sheath component) adopted for use in combination to be as high as possible, and it is favorable to adopt polymers having a ratio in dissolution rate of up to about 3,000.
  • the sheath component it is preferable to select a polymer from among those which are melt-moldable and higher in solubility than the other components, such as polyester and copolymers thereof, polylactic acid, polyamide, polystyrene and copolymers thereof, polyethylene, and polyvinyl alcohol.
  • the sheath component is preferable for the sheath component to be a copolymer polyester, polylactic acid, polyvinyl alcohol, etc., that are easily dissolvable in aqueous solvents, hot water, etc., and in particular, a polyester copolymerized with 5 mol% to 15 mol% of 5-sodium sulfoisophthalic acid or a polyester copolymerized not only with the above 5-sodium sulfoisophthalic acid but also with 5 wt% to 15 wt% of a polyethylene glycol with a weight average molecular weight of 500 to 3,000 can be cited as particularly preferred polymers because they show solubility in aqueous solvents such aqueous alkali solutions while maintaining crystallinity and fusion bonding etc. between composite fibers can be prevented in the false-twisting step etc. in which the polymer suffers abrasion while being heated, thereby
  • coarse interfiber spaces of 10 ⁇ m or more can be formed by the dissolution of the sheath in the concave portions of the multilobar shape where the sheath has a larger thickness while fine interfiber spaces of less than 5 ⁇ m are formed in the convex portions where the sheath has a smaller thickness. This serves to achieve resilience in addition to a light and flexible texture peculiar to natural silk.
  • concave and convex portions along the fiber surface also acts to amplify the reflection of light and this serves to allow the fiber surface to have dry touch due to the concave and convex portions formed along the fiber surface in addition to the luxurious gloss such as bright, mild gloss like natural silk.
  • the luxurious gloss such as bright, mild gloss like natural silk.
  • the substantial upper limit of the number of convex portions contained is six.
  • the ratio of S min /D between the minimum thickness S min of the sheath component and the fiber diameter D of the composite fiber be 0.01 or more.
  • a multifilament of the core-sheath composite fiber according to the present invention is embedded in an embedding material such as epoxy resin, and its cross section perpendicular to the fiber axis is photographed by transmission electron microscopy (TEM) at a magnification where 10 or more fibers can be observed.
  • TEM transmission electron microscopy
  • metal dyeing will serve to dye the different polymers to different degrees, thereby enhancing contrast at the boundaries between the core and sheath components. Fibers were selected at random in each image of the photographed images, and their diameters were measured in ⁇ m to the first decimal place.
  • a straight line is drawn from the center of gravity G1 of the core component 1, which exists in the fiber cross section, to an arbitrary fiber surface as described in, for example, Fig. 2(a) and Fig. 5(a) , and the distance S1-F from the intersection S1 of the perimeter of the core component 1 and the straight line to the intersection F of the fiber surface and the straight line is measured to the first decimal place, and the minimum among the measurements taken is determined.
  • This procedure was repeated to take measurements from 10 randomly selected fibers, and the arithmetic number average of the results was calculated and rounded off to a whole number to give a value to represent the minimum thickness S min ( ⁇ m) of the sheath component.
  • the arithmetic number average of the ratio of S min /D was calculated and rounded off to the second decimal place to give a value to represent the ratio of S min /D.
  • the sheath component is arranged in such a manner that the ratio of S min /D between the minimum thickness S min of the sheath component and the fiber diameter D is 0.01 or more, this is preferable because a woven or knitted fabric that has fine interfiber spaces of less than 5 ⁇ m to permit movements of fibers fixed at tying points can be produced by dissolving out the sheath component, thereby allowing a flexible texture to be developed.
  • a larger S min /D ratio allows fine interfiber spaces of less than 5 ⁇ m to increase in size to make fibers more movable, and accordingly a S min /D ratio of 0.03 or more causes a larger increase in flexibility to develop better natural silk-like drape property peculiar to natural silk.
  • the upper limit is substantially 0.1 for the present invention.
  • the core component In order to eliminate the trade-off relation in which an improvement in flexibility and lightness achieved by an increased size of interfiber spaces causes a deterioration in resilience, it is important for the core component to have a multilobar shape in which the concave portions of the multilobar shape, where the sheath thickness is large, contain coarse interfiber spaces of 10 ⁇ m or more that are formed by dissolving out the sheath component whereas the convex portions, where the sheath thickness is small, contain fine interfiber spaces of less than 5 ⁇ m, and it is also important to control the maximum and minimum sizes of the interfiber spaces.
  • the present inventors made intensive studies, and as a result, it was found that if the ratio between the maximum and minimum interfiber space sizes is increased to above a certain level, there will be a sufficient difference between the two groups of interfiber spaces to develop a texture having such a prominently light, flexible, and resilient texture as is peculiar to natural silk.
  • the second requirement is that the ratio of S max /S min between the maximum thickness Smax and the minimum thickness S min of the sheath component should be 5.0 or more.
  • a straight line is drawn from the center of gravity G1 of the core component 1, which exists in the fiber cross section, to an arbitrary fiber surface as described in, for example, Fig. 2(a) and Fig. 5(a) , and the distance S1-F from the intersection S1 of the perimeter of the core component 1 and the straight line to the intersection F of the fiber surface and the straight line is measured to the first decimal place, and the maximum among the measurements taken is determined.
  • This procedure was repeated to take measurements from 10 randomly selected fibers, and the arithmetic number average of the results was calculated and rounded off to a whole number to give a value to represent the minimum thickness S max ( ⁇ m) of the sheath component.
  • a texture having such a prominently light, flexible, and resilient texture as is peculiar to natural silk can be developed sufficiently if the ratio of S max /S min between the maximum thickness Smax of the sheath component, which is related with the coarse interfiber spaces of 10 ⁇ m or more, and the minimum thickness S min which is related with the fine interfiber spaces of less than 5 ⁇ m, is 5.0 or more. If the ratio of S max /S min is increased to 10.0 or more, furthermore, interfiber spaces with a size peculiar to natural silk can be formed to achieve natural silk-like lightness, and therefore, this can be cited as a more preferable range.
  • S max /S min a larger value of S max /S min is more desirable from the viewpoint of such lightness, but if the value of S max /S min is too large, the irregular cross-sectional shape of the fiber formed by the dissolution of the sheath component will increase in the degree of shape irregularity so largely that cloth produced therefrom may suffer high-order problems such as glare and stripes.
  • the upper limit of S max /S min is substantially 30.0.
  • the area proportion of the sheath component in the core-sheath composite fiber according to the present invention is preferably 10% to 50%. As the proportion of the area occupied by the sheath component increases, the dissolution of the sheath component works more effectively in forming interfiber spaces, and it is preferably 10% or more, and more preferably 20% or more. On the other hand, although a higher area proportion of the sheath component is more preferred from the viewpoint of interfiber spaces, excessive dissolution of the sheath component can occur to cause a decrease in strength or lengthening of the dissolution treatment step, and therefore, the upper limit is substantially 50%.
  • the fiber cross section should be a perfect circle or an ellipse, and it is preferable that the relation of 1.0 ⁇ R B /R A ⁇ 2.5 hold wherein R A is the diameter of the inscribed circle of the fiber (diameter of A in Fig. 4(a) ) and R B is the diameter of the circumscribed circle (diameter of B in Fig. 4(a) ). It is noted that the ratio of R B /R A represents the degree of shape irregularity of the fiber.
  • the core-sheath composite fiber it is important that different interfiber spaces coexist as a result of the formation of a multilobar shape by the dissolution of the sheath component and it is preferable that the core-sheath composite fiber is perfectly circular as illustrated in Fig. 2(a) and (b) , Fig. 4(b) and (c) , and Fig. 5(a) or elliptic as illustrated in Fig. 4(a) and Fig. 5(b) and contains a multilobar shaped core component, rather than such core-sheath composite fibers as shown in Fig.
  • the ratio of R B /R A that represents the degree of shape irregularity preferably satisfies the relation of 1.0 ⁇ R B /R A ⁇ 2.5 because when the core-sheath composite fiber according to the present invention is in the form of a multifilament, closest packing can be achieved easily and interfiber spaces can be formed uniformly without unevenness by the dissolution of the sheath component, which is preferable from the viewpoint of quality control.
  • a groove extending toward the center of gravity of the core component be formed at the apex of each convex portion in the multilobar shaped core component and that the ratio of GN/GM between the distance GM from the center of gravity G of the core component to the bottom M of the groove and the distance GN from the center of gravity G of the core component to the apex N of the convex portion be 1.1 to 1.5.
  • the distance GM referred to for the present invention which is measured from the center of gravity G of the core component to the bottom M of the groove, is determined by calculating the distance from the center of gravity G1 of the core component, which is the intersection of two arbitrary straight lines each dividing the area of the core component into halves, to the bottom M1 of the groove, which is the point on the groove surface located nearest to the center of gravity G1 of the core component. In this instance, if there were two or more core component regions, the largest value among these core component regions was adopted.
  • the distance GN referred to for the present invention which is measured from the center of gravity G of the core component to the apex N of a convex portion, is determined by calculating the distance from the center of gravity G1 of the core component to the apex N1 of the convex portion, which is the point on the groove surface located farthest from the center of gravity G1 of the core component. In this instance, if there were two or more core components, the largest value among these core components was adopted.
  • the arithmetic number average of the ratio of GN/GM was calculated and rounded off to the second decimal place to give a value to represent the ratio of GN/GM.
  • the relation of GN/GM 1.0 was adopted.
  • a groove extending toward the center of gravity of the core component and having a depth that gives a GN/GM ratio of 1.1 or more be formed at the apex of each convex portion by dissolving out the sheath component because the surface of the groove can come in point contact with the skin, thereby serving to increase the friction force and enhance the dry touch.
  • the groove has a depth that gives a GN/GM ratio of 1.3 or more, diffused reflection of light occurs to develop a mild gloss in addition to dry touch and this also acts to suppress the fading that may be caused by regular reflection of light, leading to improved color development in the dyeing step. Therefore, this can be cited as a more preferable range. If the depth of the groove is increased excessively, however, the friction force will become too large, possibly leading to fibrillation etc. that can cause a deterioration in wear resistance. Accordingly, the upper limit of the GN/GM ratio is substantially 1.5.
  • the core-sheath composite fiber according to the present invention there are two or more regions of the core component separated from each other by the sheath component and that each separated region of the core components has a multilobar shape as described above.
  • Raw silk as produced from silkworm cocoons, which is to be processed into natural silk has a cross section containing two triangular regions containing fibroin (a in Fig. 1 ), which is the hardly dissolvable component, surrounded by sericin (b in Fig. 1 ), which is the easily dissolvable components.
  • fibroin a in Fig. 1
  • sericin b in Fig. 1
  • the core-sheath composite fiber it is preferable that there are two or more regions of the core component separated from each other by the sheath component and that each separated region of the core component has a multilobar shape.
  • the number of separated regions is not particularly limited as long as it is two or more, and for example, there may be six separated core component regions as illustrated in Fig. 4(c) .
  • the upper limit of the number of separated regions is substantially 10.
  • coarser interfiber spaces for the present invention, it is preferable that polymers with different melting points are located next to each other in the fiber cross section so that the difference in melting point causes a difference in shrinkage rate during heat treatment to develop crimps in the core-sheath composite fiber or causes a difference in fiber length after dissolving out the sheath component from the core-sheath composite fiber. If coarser interfiber spaces can be formed, not only diffused reflection of light will occur more intensely to bring about a luxurious gloss and high-grade color development, but also the space proportion will increase to cause a decrease in apparent density, thereby realizing enhancement in lightness.
  • the core component region 1 for example c1 in Fig. 4(a), (b), and (c)
  • the core component region 2 for example c2 in Fig. 4(a), (b), and (c)
  • polymers having different melting points mean a combination of polymers that are selected from melt-moldable polymers including polyester based, polyethylene based, polypropylene based, polystyrene based, polyamide based, polycarbonate based, polymethyl methacrylate based, polyphenylene sulfide based, and other similar polymers as well as copolymers thereof, and that differ in melting point by 10°C or more.
  • a difference in shrinkage rate among core components is utilized with the aim of forming a core-sheath composite fiber having crimps or developing a difference in fiber length after dissolving out the sheath component from the core-sheath composite fiber, and therefore, a good combination of core-component polymers with different melting points can be formed by adopting a polymer with a higher shrinkage rate and a lower melting point as the a core component 1 and a polymer with a lower shrinkage rate and a higher melting point as the core component 2.
  • polyester based ones such as copolymer polyethylene terephthalate/polyethylene terephthalate, polybutylene terephthalate/polyethylene terephthalate, polytrimethylene terephthalate/polyethylene terephthalate, thermoplastic polyurethane/polyethylene terephthalate, polyester based elastomer/polyethylene terephthalate, and polyester based elastomer/polybutylene terephthalate; polyamide based ones such as nylon 66/nylon 610, nylon 6-nylon 66 copolymer/nylon 6 or 610, PEG copolymerized nylon 6/nylon 6 or 610, and thermoplastic polyurethane/nylon 6 or 610; and polyolefin based ones such as ethylene-propylene-rubber-finely-dispersed polypropylene/polypropylene, and propylene- ⁇ -
  • the use of a combination of polyester based polymers for the separated core components is particularly preferable from the viewpoint of realizing not only a bending rigidity close to that of natural silk but also high-grade color development in the dyeing step.
  • good copolymerization components for the copolymer polyethylene terephthalate include, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid, and it is preferable to use a polyethylene terephthalate copolymerized with 5 mol% to 15 mol% of isophthalic acid from the viewpoint of maximizing the difference in shrinkage rate compared to polyethylene terephthalate.
  • the ratio of the core component 1 to the core component 2 is preferable for the ratio of the core component 1 to the core component 2 to be in the range of 70%/30% to 30%/70%.
  • the ratio is in this range, it will be possible to form crimps in the core-sheath composite fiber by making use of the difference in shrinkage rate or develop a difference in fiber length by dissolving out the sheath component from the core-sheath composite fiber, while preventing the hardening of the texture from being caused by an influence of clogging that may occur when the polymer with a lower melting point is shrunk to a high degree in the heat treatment step. This brings about the development of coarser interfiber spaces.
  • the core-sheath composite fiber according to the present invention is processed first into a sheet-like fiber structure such as woven or knitted fabric, nonfabric, paper, or other various forms, and then the sheath component is dissolved out to produce a multifilament mainly containing the core component.
  • the multifilament has natural silk-like textural features such as luxurious gloss, dry touch, lightness, flexibility, and resilience that result from the unique fiber's cross-sectional shape and interfiber spaces.
  • the key point is that a space structure in which fine interfiber spaces with fiber-to-fiber distances of less than 5 ⁇ m and coarse interfiber spaces with fiber-to-fiber distances of 10 ⁇ m or more coexist uniformly as seen in natural silk are formed in the multifilament.
  • a specimen of multifilament cloth is observed by scanning electron microscopy (SEM) to photograph the cloth's cross section perpendicular to the length direction of the cloth and also perpendicular to the fiber axis direction of the multifilament at a magnification where 10 or more fibers can be observed.
  • SEM scanning electron microscopy
  • a perfect circle that contains 10 fibers is drawn as illustrated in Fig. 8(b) , and a fiber is selected arbitrarily from the 10 fibers existing in the perfect circle.
  • a longer average interfiber space distance brings about larger spaces in which fibers fixed on the tying points of woven or knitted fabrics can move to achieve higher flexibility, and accordingly, it is necessary for the average interfiber space distance to be 5 ⁇ m or more. If the average interfiber space distance is 10 ⁇ m or more, furthermore, the fiber improves in bulkiness and can form cloth with a decreased apparent density, which leads to improved lightness as well. Accordingly, a natural silk-like light, flexible texture can be developed, indicating that the above range can be cited as a more preferable range.
  • the upper limit of the average interfiber space distance is substantially 30 ⁇ m.
  • interfiber spaces with interfiber space distances of less than 5 ⁇ m it is necessary for the interfiber spaces with interfiber space distances of less than 5 ⁇ m to account for 10% or more so that a longer average space distance serves to prevent a decrease in bending rigidity and maintain a required resilience. If the interfiber spaces with interfiber space distances of less than 5 ⁇ m account for 20% or more, furthermore, the trade-off relation between lightness/flexibility and resilience can be eliminated, and a light, flexible, and resilient texture can be developed in a good balance, indicating that the above range can be cited as a more preferable range.
  • the upper limit of the proportion of spaces with interfiber space distances of less than 5 ⁇ m is substantially 50%.
  • the multifilament according to the present invention prefferably has a space structure in which the space proportion is 30 to 80%.
  • a specimen of multifilament cloth is observed by scanning electron microscopy (SEM) to photograph the cloth's cross section perpendicular to the length direction of the cloth and also perpendicular to the fiber axis direction of the multifilament at a magnification where 10 or more fibers can be observed.
  • SEM scanning electron microscopy
  • a perfect circle that contains 10 fibers was drawn as illustrated in Fig. 8(b) , and the total cross-sectional area of the 10 fibers existing in the perfect circle was subtracted from the cross-sectional area of the perfect circle.
  • a fiber was included in the calculation if 1/2 or more of its area existed inside the perfect circle, and the area of each cross section was measured in ⁇ m 2 to the first decimal place. Subsequently, the calculated value was divided by the cross section of the perfect circle, multiplied by 100, and rounded off to a whole number to give a value to represent the space proportion (%).
  • the multifilament prefferably has a space structure with a space proportion of 30% or more because it brings about larger spaces in which fibers fixed to the tying points in woven or knitted fabrics can move to achieve higher flexibility.
  • the space structure has a space proportion of 50% or more, furthermore, the fiber wit such a high space proportion can form cloth with a decreased apparent density, which leads to improved lightness as well. Accordingly, a natural silk-like light, flexible texture can be developed, indicating that the above range can be cited as a more preferable range.
  • lightness and flexibility improve as the average interfiber space distance and space proportion increase as described above, it has less effect in preventing a decrease in bending rigidity in the interfiber spaces of less than 5 ⁇ m that coexist uniformly in the multifilament and it tends to lead to a decreased resilience.
  • the upper limit of the space proportion in the space structure is substantially 80%.
  • the multifilament according to the present invention contains two or more types of crimped fibers that are formed of polymers having different melting points and that these crimped fibers coexist uniformly.
  • a crimped fiber as referred to for the present invention means a fiber having curled crimps as illustrated in in Fig.7 .
  • crimped fibers coexist uniformly means that for a crimped fiber X selected arbitrarily in a multifilament as illustrated in Fig. 8(a) , at least one crimped fiber Y that is formed of a polymer different from that of the crimped fiber X exists among all crimped fibers located adjacent to the crimped fiber X.
  • adjacent used for the present invention implies that no other crimped fiber exists on the straight line connecting between the center of gravity of the crimped fiber X and that of an arbitrary crimped fiber.
  • two or more core-sheath composite fibers as illustrated in Fig. 2(a) and Fig. 5(a) are bound together, followed by dissolving out the sheath component, or two or more mutually adjacent core-sheath composite fibers each containing core component regions of polymers with different melting points as illustrated in Fig. 4(a), (b), and (c) are bound together, followed by dissolving out the sheath component to divide them and then developing a difference in fiber length by heat treatment.
  • two or more core-sheath composite fibers each containing two core component regions c1 and c2 formed of polymers with different melting points as illustrated in Fig. 10(a) and (b) , which are divided by the sheath component d in the fiber's cross section, are bound together and subjected heat treatment to develop crimps, followed by dissolving the sheath component so that the crimps of polymers are separated from each other. This allows crimped fibers formed of different polymers to coexist uniformly.
  • crimps are formed by heat-treating core-sheath composite fibers, thereby forming coarse interfiber spaces of 10 ⁇ m or more.
  • the sheath component exists between the core component regions, and by dissolving out the sheath component, interfiber spaces of less than 5 ⁇ m can be formed more stably between mutually adjacent crimped fibers formed of polymers with different melting points. Consequently, the resulting multifilament can contain fine interfiber spaces of less than 5 ⁇ m and coarse interfiber spaces of 10 ⁇ m or more that coexist uniformly.
  • the multifilament according to the present invention to contain two or more types of crimped fibers formed of polymers with different melting points, with these crimped fibers coexisting uniformly, which serves to realize enhanced natural silk-like textural features such as luxurious gloss, dry touch, lightness, flexibility, and resilience that result from the fiber's unique cross-sectional shape and space structure.
  • the multifilament according to the present invention prefferably contains crimped fibers having five or more crimps per centimeter.
  • the interfiber excluded volume effect is achieved sufficiently to form coarse interfiber spaces of several tens of micrometers. If the rate is 10 crimps/cm or more, furthermore, the interfiber excluded volume effect is enhanced to further increase the size of the interfiber spaces, thereby developing a natural silk-like light and flexible texture, indicating that this range can be cited as a more preferable range.
  • the steric hindrance effect of the crimps exceeds the excluded volume effect, possibly causing interfiber entanglement and a decrease in flexibility.
  • the upper limit of the number of crimps is 100 crimps/cm.
  • the two or more types of crimped fibers formed of different polymers have a fiber length difference of 3% or more. If the fiber length difference is 3% or more, the crimped fiber formed of polymers with different melting points, which is in a crimped form, can develop 10 crimps/cm or more. If the fiber length difference is too large, however, the number of crimps increases accordingly. As a result, the steric hindrance effect of the crimps can exceed the excluded volume effect, possibly causing interfiber entanglement and a decrease in flexibility. Thus, the upper limit of the fiber length difference is 20%.
  • the crimped fiber it is preferable for the crimped fiber to be formed of homopolymers. If the crimped fiber is formed of homopolymers, mutually adjacent crimped fibers can be synchronized in phase as a core-sheath composite fiber containing mutually adjacent polymers with different melting points is heat-treated to develop crimps, making it possible to form fine interfiber spaces of less than 5 ⁇ m. If it is formed of two or more different polymers, on the other hand, the center of gravity in the cross section of the polymer differs in different composite cross sections and accordingly, mutually adjacent fibers formed of polymers with different melting points form crimped fibers having crimps of different shapes after dissolving out the sheath component. As a result, their crimp phases are not synchronized, making stable production of fine interfiber spaces of less than 5 ⁇ m difficult.
  • Each fiber contained in the multifilament according to the present invention preferably has a fiber cross section of a multilobar shape with three or more convex portions.
  • the fiber surface will have concave and convex portions along the fiber surface that act to amplify the reflection of light.
  • concave and convex portions along the fiber surface that act to amplify the reflection of light.
  • the formation of an irregular fiber surface acts to increase friction, leading to dry touch.
  • the above argument suggests that better gloss and dry touch can be developed by increasing the number of convex portions, but as the number of concave and convex portions is increased excessively, the distances between the concave and convex portions become shorter to cause the cross section to gradually become rounder.
  • the upper limit of the number of convex portions contained in a fiber is substantially six.
  • R C is the diameter of the inscribed circle (diameter of C in Fig. 9(a) ) and R D is the diameter of the circumscribed circle (diameter of D in Fig. 9(a) ).
  • the ratio of R D /R C represents the degree of shape irregularity of the fiber. A value in this range is preferable from the viewpoint of quality control because the light that undergoes amplified reflection on the concave and convex portions of the multilobar shape is reflected uniformly without glare.
  • the multifilament according to the present invention is embedded in an embedding material such as epoxy resin, and its cross section perpendicular to the fiber axis is photographed by scanning electron microscopy (SEM) at a magnification where 10 or more fibers can be observed.
  • SEM scanning electron microscopy
  • the distance MN measured from the bottom M of a groove which is the point on the groove surface located nearest to the center of gravity G, i.e., the intersection of two arbitrary straight lines each dividing the cross-sectional area of the crimped fiber into halves in the fiber cross section, to the apex N of the convex portion, which is the point located farthest therefrom, as illustrated in Fig. 9 , was calculated.
  • the diameter of the fiber was also determined in ⁇ m to the first decimal place. In this instance, if the fiber cross section perpendicular to the fiber axis was not a perfect circle, its area was measured, and the diameter calculated therefrom assuming a circle was adopted.
  • a fiber contained in the multifilament according to the present invention it is preferable for a fiber contained in the multifilament according to the present invention to have a groove with a depth that gives a MN/D ratio of 0.04 or more because the surface of the groove can come in point contact with the skin and this serves to increase the friction and enhance dry touch. Furthermore, if the groove has a depth that gives a MN/D ratio of 0.10 or more, diffused reflection of light occurs to develop a mild gloss in addition to dry touch and this acts to suppress the fading that may be caused by regular reflection of light, leading to improved color development in the dyeing step. Therefore, this can be cited as a more preferable range. If the depth of the groove is increased excessively, however, the friction will become too large, possibly leading to fibrillation etc. that can cause a deterioration in wear resistance. Accordingly, the upper limit of the MN/D ratio is substantially 0.20.
  • the fiber diameter is 15 ⁇ m or less from the viewpoint of further enhancing the flexibility of the texture. If the fiber diameter is 12 ⁇ m or less, the single fiber fineness comes closer to that of natural silk, i.e., about 10 ⁇ m, to realize more natural silk-like touch. Thus, this can be cited as a preferable range for the production of general clothing such as inner wear, shirts, and blouses that are used in contact with the skin.
  • the fiber diameter is preferably 8 ⁇ m or more because if the fiber diameter is too small, bending recovery will decrease, possibly leading not only to a decrease in resilience, which represents a feature of the texture of natural silk, but also to a deterioration in color development.
  • the core-sheath composite fiber and the multifilament according to the present invention it is possible to form a unique space structure in which fine interfiber spaces with fiber-to-fiber distances of less than 5 ⁇ m and coarse interfiber spaces with fiber-to-fiber distances of several tens of micrometers coexist uniformly as seen in natural silk. Therefore, fiber materials formed at least partially of the core-sheath composite fiber or the multifilament according to the present invention will have various natural silk-like textural features.
  • Useful methods to produce the core-sheath composite fiber according to the present invention that contains two or more polymers include the melting spinning method designed for production of long fibers, solution spinning methods such as for wet and dry-jet wet spinning, melt-blowing method, which is suitable for producing sheet-like fiber structures, and spun-bonding method, of which the melting spinning method is preferred from the viewpoint of high productivity.
  • the melting spinning method may be used with a composite spinneret as described later, and spinning should be performed at a temperature at which mainly the high melting point one or high viscosity one among all polymer species used show flowability.
  • the temperature where such a polymer show flowability may be set between its melting point and a temperature 60°C above the melting point to ensure stable production.
  • the spinning speed may be set at about 500 to 6,000 m/min and adjusted according to the physical properties of the polymer or purposes of the fiber. From the viewpoint of ensuring a high degree of orientation and improved mechanical characteristics, in particular, it is preferable to perform spinning at 500 to 4,000 m/min, followed by stretching, to produce a fiber that is strongly oriented uniaxially.
  • the stretching step it is preferable to set an appropriate preheating temperature on the basis of the temperature at which the polymer can soften, such as its glass transition temperature.
  • the upper limit of preheating temperature is preferably set at a temperature where unstable thread passage is not caused by spontaneous stretching of the fiber during preheating. In the case of PET, for example, which has a glass transition temperature of about 70°C, the preheating temperature is commonly set at about 80°C to 95°C.
  • the discharge rate per single hole of the spinneret is about 0.1 to 10 g/min•hole.
  • the polymer flow discharged is cooled for solidification, supplied with a lubricant, and taken up on a roller with a prescribed circumferential speed. Subsequently, it is stretched by heated rollers to form an intended core-sheath composite fiber.
  • the core-sheath composite fiber according to the present invention that contains two or more polymers, furthermore, it is preferable to use polymers with a melt viscosity ratio of less than 5.0 and a solubility parameter difference of less than 2.0 because a composite polymer flow can be formed stably and a fiber having a desirable composite cross section can be produced.
  • the composite spinneret used to produce the core-sheath composite fiber according to the present invention that contains two or more polymers is preferably a composite spinneret as described in Japanese Unexamined Patent Publication (Kokai) No. 2011-208313 .
  • the composite spinneret illustrated in Fig. 12 in the present Application is composed mainly of the three members of a measuring plate 1, a distribution plate 2, and a discharge plate 3, from top to bottom, to constitute a layered structure which is built into a spinning pack to be used for spinning.
  • Fig. 12 shows an example in which three polymers, that is, polymer A, polymer B, and polymer C, are used. It is difficult for conventional composite spinnerets to form a composite flow containing three or more polymers, and therefore, it is preferable to use a composite spinneret having fine flow channels as illustrated in Fig. 12 .
  • the measuring plate 1 feeds polymers while measuring the polymer feeding rate for each discharge hole and distribution hole, and the distribution plate 2 controls the composite cross section and the cross-sectional shape of each single fiber. Then, the discharge plate 3 compresses and discharges the composite polymer flow formed by the distribution plate 2.
  • the members located above the measuring plate 1 are not shown in the figure to avoid complexity in explaining the composite spinneret, but any appropriate ones may be used if they have flow channels that are suitable for use with the spinning machine and spinning pack.
  • a conventional spinning pack and its members may serve effectively without any modifications if the measuring plate 1 is tailored to the existing flow channel members. It is not necessary, therefore, to prepare a specially designed spinning machine for use with this spinneret. In actual cases, furthermore, it may be desirable to provide a plurality of flow channel plates between the flow channels and the measuring plate or between the measuring plate 1 and the distribution plate 2.
  • the composite polymer flow discharged through the discharge plate 3 is then processed by the aforementioned production method in which it is cooled for solidification, supplied with a lubricant, and taken up on a roller with a prescribed circumferential speed. Subsequently, it is stretched by heated rollers to form an intended core-sheath composite fiber.
  • aqueous alkali solution such as aqueous solution of sodium hydroxide can be used when the easily dissolvable component is, for example, polylactic acid, copolymer polyethylene terephthalate copolymerized with 5-sodium sulfoisophthalic acid, polyethylene glycol, etc.
  • aqueous alkali solution it is preferable to heat the aqueous alkali solution at 50°C or more because its hydrolysis can be accelerated. Furthermore, the use of a fluid dyeing machine etc. is preferable from an industrial viewpoint because a large batch can be processed at a time.
  • the core-sheath composite fiber and the multifilament according to the present invention will now be illustrated in detail below with reference to examples.
  • Chips of a polymer were dried in a vacuum dryer to a moisture content of 200 ppm or less and subjected to melt viscosity measurement using a Capilograph, manufactured by Toyo Seiki Co., Ltd., in which the strain rate was changed stepwise.
  • the measuring temperature used was the same as the spinning temperature, and measurement was started in 5 minutes after putting a sample into a nitrogen atmosphere in a heating furnace.
  • a melt viscosity measurement taken at a shear rate of 1,216 s -1 was adopted for evaluation of the polymer.
  • Chips of a polymer were dried in a vacuum dryer to a moisture content of 200 ppm or less and a sample of about 5 mg was weighed and heated from 0°C to 300°C in a differential scanning calorimeter (DSC) (Q2000, manufactured by TA Instruments) at a heating rate of 16°C/min. It was maintained at 300°C for 5 minutes and then subjected to DSC measurement. The melting point was calculated from the melting peak observed during the heating step. Three measurements were taken from a sample, and their average was adopted as its melting point. Here, in the case where two or more melting peaks were observed, the melting peak appearing at the highest temperature was adopted to determine the melting point.
  • DSC differential scanning calorimeter
  • the weight of a multifilament sample with a length of 100 m was measured and the measured value was multiplied by 100. This procedure was repeated 10 times, and the average was rounded off to the first decimal place to give value to represent the fineness (dtex) of the multifilament.
  • a core-sheath composite fiber was embedded in an embedding material such as epoxy resin, and its cross section perpendicular to the fiber axis was photographed using a HITACHI scanning electron microscope (SEM) at a magnification where 10 or more fibers could be observed.
  • the image obtained was analyzed using WinROOF (computer software supplied by Mitani Shoji Co., Ltd.) to determine the value of R B /R A , i.e., the ratio between the diameter R B of the circumscribed circle of the fiber (for example, the diameter of B in Fig. 4A(a)) and the diameter R A of the inscribed circle of the fiber (for example, the diameter of A in Fig. 4(a) ).
  • WinROOF computer software supplied by Mitani Shoji Co., Ltd.
  • three measurements were taken from each filament and the arithmetic number average of the measurements taken from 10 filaments were calculated and rounded off to the second decimal place to give a value to represent R B /R A .
  • a core-sheath composite fiber was embedded in an embedding material such as epoxy resin, and its cross section perpendicular to the fiber axis was photographed by transmission electron microscopy (TEM) at a magnification where 10 or more fibers could be observed.
  • TEM transmission electron microscopy
  • metal dyeing can serve to dye different polymers to different degrees, thereby enhancing contrast at the boundaries between the composite components. From the photographed image, the ratio of S min /D between the minimum thickness S min of the sheath component and the fiber diameter D and the ratio of S max /S min between the maximum thickness Smax of the sheath component and the minimum thickness S min of the sheath component were calculated.
  • fibers were selected at random in each image of the photographed images, and their diameters were measured in ⁇ m to the first decimal place. This procedure was repeated to measure the diameters of 10 randomly selected fibers, and the arithmetic number average of the measurements was calculated and rounded off to a whole number to give a value to represent the fiber diameter D ( ⁇ m).
  • D the fiber diameter
  • the fiber's cross section perpendicular to the fiber axis was not a perfect circle, its area was measured, and the diameter calculated therefrom assuming a circle was adopted.
  • fibers are selected at random in each image of the photographed images, and a straight line is drawn from the center of gravity G1 of the core component 1, which exists in a fiber cross section, to an arbitrary fiber surface as described in, for example, Fig. 2(a) and Fig. 5(a) . Then, the distance S1-F from the intersection S1 between the perimeter of the core component 1 and the straight line to the intersection F between the fiber surface and the straight line is measured to the first decimal place, and the smallest one of the measurements taken is determined.
  • the arithmetic number average of the ratio of S min /D was calculated and rounded off to the second decimal place to give a value to represent the ratio of S min /D.
  • fibers are selected at random in each image of the photographed images, and a straight line is drawn from the center of gravity G1 of the core component 1, which exists in the fiber cross section, toward an arbitrary fiber surface as described in, for example, Fig. 2(a) and Fig. 5(a) . Then, the distance S1-F from the intersection S1 between the perimeter of the core component 1 and the straight line to the intersection F between the fiber surface and the straight line is measured to the first decimal place, and the largest one of the measurements taken is determined.
  • the distance GM referred to for the present invention which is measured from the center of gravity G of the core component to the bottom M of the groove, is determined by calculating the distance from the center of gravity G1 of the core component, which is the intersection between two arbitrary straight lines each dividing the area of the core component into halves, to the bottom M1 of the groove, which is the point on the groove surface located nearest to the center of gravity G1 of the core component. In this instance, if there were two or more core component regions, the largest value among these core component regions was adopted.
  • This procedure was repeated to take measurements from 10 randomly selected fibers, and the arithmetic number average of the measurements was calculated and rounded off to a whole number to give a value to represent the distance GM ( ⁇ m) from the center of gravity G of the core component to the bottom M of the groove.
  • the distance GN referred to for the present invention which is measured from the center of gravity G of the core component to the apex N of the convex portion, is determined by calculating the distance from the center of gravity G1 of the core component to the apex N1 of the convex portion, which is the point on the groove surface located farthest from the center of gravity G1 of the core component. In this instance, if there were two or more core component regions, the largest value among these core component regions was adopted.
  • the arithmetic number average of the ratio of GN/GM was calculated and rounded off to the second decimal place to give a value to represent the ratio of GN/GM.
  • a multifilament cloth is examined by a HITACHI scanning electron microscope (SEM) to photograph the cloth's cross section perpendicular to the length direction of the cloth and also perpendicular to the fiber axis direction of the multifilament at a magnification where 10 or more fibers can be observed.
  • the photographed image was analyzed using WinROOF (computer software supplied by Mitani Shoji Co., Ltd.). For an arbitrary fiber X in the multifilament as illustrated in Fig.
  • a multifilament cloth was prepared and a multifilament was pulled out of the cloth in such a manner that it did not suffer plastic deformation.
  • One end of the multifilament was fixed and a weight of 1 mg/dtex was attached to the other end.
  • marks were made on the multifilament in such a manner that the distance between them measured in the fiber axis direction was 1 cm.
  • a fiber was separated from the multifilament in such a manner that it did not suffer plastic deformation and fixed on a slide glass in such a manner that the distance between the marks made above was adjusted to the original length of 1 cm.
  • a multifilament cloth was prepared and a multifilament was pulled out of the cloth in such a manner that it did not suffer plastic deformation.
  • One end of the multifilament was fixed and a weight of 1 mg/dtex was attached to the other end.
  • marks were made on the multifilament in such a manner that the distance between them measured in the fiber axis direction was 1 cm.
  • a fiber was separated from the multifilament in such a manner that it did not suffer plastic deformation and fixed on a slide glass in such a manner that the distance between the marks made above was adjusted to the original length of 1 cm.
  • a multifilament cloth is examined by a HITACHI scanning electron microscope (SEM) to photograph the cloth's cross section perpendicular to the length direction of the cloth and also perpendicular to the fiber axis direction of the multifilament at a magnification where 10 or more fibers can be observed.
  • the image obtained was analyzed using WinROOF (computer software supplied by Mitani Shoji Co., Ltd.).
  • WinROOF computer software supplied by Mitani Shoji Co., Ltd.
  • a perfect circle that contains 10 fibers was drawn as illustrated in Fig. 8(b) , and a fiber was selected arbitrarily from the 10 fibers existing in the perfect circle.
  • a multifilament cloth is examined by a HITACHI scanning electron microscope (SEM) to photograph the cloth's cross section perpendicular to the length direction of the cloth and also perpendicular to the fiber axis direction of the multifilament at a magnification where 10 or more fibers can be observed.
  • the image obtained was analyzed using WinROOF (computer software supplied by Mitani Shoji Co., Ltd.).
  • WinROOF computer software supplied by Mitani Shoji Co., Ltd.
  • a perfect circle that contains 10 fibers was drawn as illustrated in Fig. 8(b) , and the total cross-sectional area of the 10 fibers existing in the perfect circle was subtracted from the cross-sectional area of the perfect circle.
  • a fiber was included in the calculation if 1/2 or more of its area existed inside the perfect circle, and the area of a cross section was measured in ⁇ m 2 to the first decimal place. Subsequently, the calculated value was divided by the cross section of the perfect circle, multiplied by 100, and rounded off to a whole number to give a value to represent the space proportion (%).
  • Fibers were selected at random in each of the images photographed in the section K, and their diameters were measured in ⁇ m to the first decimal place. This procedure was repeated for 10 randomly selected fibers, and the largest one of the fiber diameter measurements was rounded off to a whole number to give a value to represent the fiber diameter D ( ⁇ m).
  • D the fiber diameter
  • the fiber's cross section perpendicular to the fiber axis was not a perfect circle, its area was measured, and the diameter calculated therefrom assuming a circle was adopted.
  • the image photographed in the section K was analyzed using WinROOF (computer software supplied by Mitani Shoji Co., Ltd.) to determine the value of R D /R C , i.e., the ratio between the diameter R D of the circumscribed circle of the fiber (for example, the diameter of C in Fig. 9(a) ) and the diameter Rc of the inscribed circle of the fiber (for example, the diameter of C in Fig. 9(a) ).
  • WinROOF computer software supplied by Mitani Shoji Co., Ltd.
  • the multifilament is embedded in an embedding material such as epoxy resin, and its cross section perpendicular to the fiber axis is photographed using a HITACHI scanning electron microscope (SEM) at a magnification where 10 or more fibers can be observed. Fibers were randomly selected from each of the photographed images and analyzed using WinROOF (computer software supplied by Mitani Shoji Co., Ltd.). As illustrated in Fig.
  • the diameter D of the fiber was also determined in ⁇ m to the first decimal place. In this instance, if the fiber cross section perpendicular to the fiber axis was not a perfect circle, its area was measured, and the diameter calculated therefrom assuming a circle was adopted to represent the fiber diameter D.
  • the ratio of MN/D was calculated to the fourth decimal place. This procedure was performed for 10 randomly selected fibers and the arithmetic number average of the results was calculated and rounded off to the second decimal place to give a value to represent the ratio of MN/D.
  • an automatic goniophotometer (GP-200, manufactured by Murakami Color Research Laboratory Co., Ltd.) was used to apply a light beam to a sample at an incident angle 60° and perform two-dimensional reflected light distribution measurement to measure the light intensity over the light receiving angle range of 0° to 90° in 0.1° steps, and the maximum light intensity (specular reflection) at a light receiving angle of about 60° was divided by the minimum light intensity (diffuse reflection) at a light receiving angle of about 0°.
  • This procedure was repeated to take measurements at 10 positions, three measurements at each position, and their arithmetic number average was calculated and rounded off to the first decimal place to give a value to represent the contrast gloss. Based on the contrast gloss values obtained above, a gloss evaluation was performed according to the three stage criterion specified below.
  • the thickness (cm) of a 20 cm ⁇ 20 cm fabric sample was measured using a constant pressure thickness gauge (PG-14J, manufactured by TeloTech) and used to calculate the volume of the fabric sample, and then the weight of the fabric sample (g) was divided by the volume obtained above to calculate the apparent density of the fabric (g/cm 3 ). Based on the apparent density measured above, a lightness evaluation was performed according to the three stage criterion specified below.
  • PG-14J constant pressure thickness gauge
  • a 20 cm ⁇ 20 cm fabric sample was fixed with an effective specimen length of 20 cm ⁇ 1 cm on a pure bending test machine (KES-FB2, manufactured by Kato Tech Co., Ltd.) and bent in the weft direction up to maximum curvatures of ⁇ 2.5 cm -1 .
  • KS-FB2 pure bending test machine
  • the difference in bending moment per unit width (gf•cm/cm) between the curvatures of 0.5 cm -1 and 1.5 cm -1 was divided by the difference in curvature of 1 cm -1
  • the difference in bending moment per unit width (gf•cm/cm) between the curvatures of -0.5 cm -1 and -1.5 cm -1 was divided by the difference in curvature of 1 cm -1 , followed by calculating the average of the quotients.
  • a 20 cm ⁇ 20 cm fabric sample was fixed with an effective specimen length of 20 cm ⁇ 1 cm on a pure bending test machine (KES-FB2, manufactured by Kato Tech Co., Ltd.) and bent in the weft direction, and the hysteresis width (gf•cm/cm) at the curvature of ⁇ 1.0 cm -1 was calculated.
  • This procedure was repeated to take measurements at 10 positions, three measurements at each position, and their arithmetic number average was calculated, rounded off to the third decimal place, and divided by 100 to give a value to represent the bending recovery 2HB ⁇ 10 -2 (gf•cm/cm).
  • a resilience evaluation was performed according to the three stage criterion specified below.
  • a dry touch evaluation was made by using an automated surface testing machine (KES-FB4 Kato Tech Co., Ltd.), in which a 1 cm ⁇ 1 cm arm wound with piano wire was slid at a speed of 1.0 mm/sec under a load of 50 g over a 10 cm ⁇ 10 cm area of a 20 cm ⁇ 20 cm fabric sample to determine the average friction coefficient MIU. This procedure was repeated to take measurements at 10 positions, three measurements at each position, and their arithmetic number average was calculated and rounded off to the first decimal place to give a value to represent the friction coefficient. Based on the friction coefficient obtained above, a dry touch evaluation was performed according to the three stage criterion specified below.
  • a plain weave fabric was produced with the numbers of fibers adjusted so that the warp-directional cover factor (CFA) was 1,100 and the weft-directional cover factor (CFB) was 1,100.
  • the resulting fabric was dyed in black using a disperse dye (Sumikaron Black S-3B, 10% owf).
  • a circular sample with a diameter of 10 cm was cut out of the dyed fabric, wetted with distilled water, and fixed on a disk.
  • a 30 cm ⁇ 30 cm portion was cut out of the fabric and, while kept in a dry state, fixed on a horizontal plate.
  • the disk carrying a fabric sample wetted with distilled water was maintained horizontally as it was brought into contact with the fabric fixed on the horizontal plate, and then the disk was moved in a circular motion in such a manner that the center of the disk drew a circle with a diameter of 10 cm at a speed of 50 rpm for 10 minutes while applying a load of 420 g to cause the two pieces of fabric to rub each other. After the end of the rubbing step, they were left to stand for 4 hours and the degree of discoloration of the fabric sample fixed on the disk was determined according to a gray scale for discoloration test. It was rated in five grades, from 1 to 5 in 0.5 steps. Based on the rating made above, a wear resistance evaluation was performed according to the three stage criterion specified below.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1 and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, 254°C) was prepared as polymer 2.
  • polymers were melted separately at 290°C, weighed to adjust the weight ratio of polymer 1/polymer 2 to 30/70, and fed to a spinning pack containing a composite spinneret as illustrated in Fig. 12 , and then the polymers fed were discharged through a discharge hole to form a perfect circular core-sheath composite fiber having a composite structure in which a core component having a trifoliate cross section with a groove at the apex of each convex portion was completely surrounded by a sheath component as illustrated in Fig. 5(a) .
  • the polymer 1 and the polymer 2 were arranged in such a manner that they formed the sheath component and the core component, respectively.
  • the composite polymer flow discharged above was cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 36 filament core-sheath composite fiber.
  • the ratio of S min /D between the minimum thickness of the resulting sheath component and the fiber diameter was 0.03 and the ratio of S max /S min between the maximum thickness and the minimum thickness of the sheath component was 16.
  • the ratio of GN/GM between the distance GM from the center of gravity G of the core component to the bottom M of a groove and the distance GN from the center of gravity G of the core component to the apex N of the convex portion was 1.42, proving that this core-sheath composite fiber was one according to the present invention.
  • the ratio between the diameter R A of the inscribed circle and the diameter R B of the circumscribed circle of the core-sheath composite fiber was 1.0, indicating that if it exists in the form of a multifilament, closest packing can be achieved easily and interfiber spaces can be formed uniformly without unevenness by the dissolution of the sheath component.
  • a fabric was produced by weaving the resulting core-sheath composite fiber and treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component to provide a fabric containing multifilaments (fiber diameter 10 ⁇ m) formed of the core component of the core-sheath composite fiber.
  • the fabric containing multifilaments had a space structure in which fine interfiber spaces with fiber-to-fiber distances of less than 5 ⁇ m and coarse interfiber spaces with fiber-to-fiber distances of 10 ⁇ m or more coexist uniformly as in natural silk to realize a natural silk-like texture having a good gloss independent on view angle (contrast gloss: 1.7), dry touch (friction coefficient: 0.7) with resilience (bending recovery 2HB: 0.6 ⁇ 10 -2 gf•cm/cm), high lightness (apparent density: 0.40 g/cm 3 ), and high flexibility (flexural rigidity B: 0.7 ⁇ 10 -2 gf•cm 2 /cm).
  • Example 2 Except that the weight ratio of polymer 1 to polymer 2 was 20/80 (Example 2) or 10/90 (Example 3), the same procedure as in Example 1 was carried out.
  • Example 1 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 2(a) , the same procedure as in Example 1 was carried out.
  • Example 4 no groove existed at the apex of each convex portion of the fibers in the multifilament and consequently, diffused reflection of light decreased, leading to an increased reflection intensity and an increased gloss visibility. A higher wear resistance was also achieved. Results are shown in Tables 1-1.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1 and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, 254°C) was prepared as polymer 2.
  • polymers were melted separately at 290°C, weighed to adjust the weight ratio of polymer 1/polymer 2 to 30/70, and fed to a spinning pack containing a composite spinneret as illustrated in Fig. 12 , and then the polymers fed were discharged through a discharge hole to form a perfect circular core-sheath composite fiber having a simple composite structure in which a core component having a circular cross section was surrounded by a sheath component as illustrated in Fig. 3(a) .
  • the polymer 1 and the polymer 2 were arranged in such a manner that they formed the sheath component and the core component, respectively.
  • the composite polymer flow discharged above was cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 36 filament core-sheath composite fiber.
  • a fabric was produced by weaving the resulting core-sheath composite fiber and treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component to provide a fabric containing multifilaments (fiber diameter 10 ⁇ m) formed of the core component of the core-sheath composite fiber.
  • Comparative example 2 although the core component had a trifoliate cross section to achieve a slight improvement in dry touch, there were no fine interfiber spaces of less than 5 ⁇ m between individual fibers after dissolution of the sheath component, resulting in poor lightness and resilience. Results are shown in Tables 1-1.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1 and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, 254°C) was prepared as polymer 2.
  • polymers were melted separately at 290°C, weighed to adjust the weight ratio of polymer 1/polymer 2 to 5/95, and fed to a spinning pack containing a composite spinneret as illustrated in Fig. 12 , and then the polymers fed were discharged through a discharge hole to form a composite structure that contained an hardly dissolvable component of a trifoliate shape in combination with an easily dissolvable component that was located at the apex of each convex portion and tapered toward the interior of the fiber as described in Japanese Unexamined Patent Publication (Kokai) No. SHO 57-5912 and illustrated in Fig. 6(a) .
  • the polymer 1 and the polymer 2 were arranged so as to work as the easily dissolvable component and the hardly dissolvable component, respectively.
  • the composite polymer flow discharged above was cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 36 filament composite fiber.
  • a fabric was produced by weaving the composite fiber and treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component to provide a fabric containing multifilaments (fiber diameter 12 ⁇ m) formed of the hardly dissolvable component of the composite fiber.
  • Example 5 Except for controlling the discharge rate in such a manner that the irregular cross-sectional fiber containing only the core component of the core-sheath composite fiber had a fiber diameter of 14 ⁇ m (Example 5) or 17 ⁇ m (Example 6), the same procedure as in Example 4 was carried out.
  • the fiber in the multifilament formed by the dissolution of the sheath component had a trifoliate cross section to enhance the degree of shape irregularity, leading to an increased reflection intensity to allow the resulting fabric to have a further increased gloss visibility.
  • its flexural rigidity also increased to realize characteristic elastic touch while maintaining a natural silk-like texture. Results are shown in Tables 1-2.
  • Example 4 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 2(b) , the same procedure as in Example 4 was carried out.
  • Example 7 the fiber in the multifilament had a tetrafoliate cross section, instead of a trifoliate cross section, to increase the diffused reflection of light in the convex portions.
  • a fabric that not only had a further improved luxurious gloss but also had a texture with an improved friction coefficient and improved dry touch. Results are shown in Tables 1-2.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1 and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, 254°C) was prepared as polymer 2.
  • polymers were melted separately at 290°C, weighed to adjust the weight ratio of polymer 1/polymer 2 to 20/80, and fed to a spinning pack containing a composite spinneret as illustrated in Fig. 12 , and then the polymers fed were discharged through a discharge hole to form a composite structure in which the hardly dissolvable component was divided by the easily dissolvable component into a plurality of parts as illustrated in Fig. 3(C) and as described in Japanese Unexamined Patent Publication (Kokai) No. 2010-222771 .
  • the polymer 1 and the polymer 2 were arranged so as to work as the easily dissolvable component and the hardly dissolvable component, respectively.
  • the composite polymer flow discharged above was cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 18 filament composite fiber.
  • a fabric was produced by weaving the composite fiber and treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component to provide a fabric containing multifilaments (fiber diameter 6 ⁇ m) formed of the hardly dissolvable component of the composite fiber.
  • the fibers in the multifilaments had small fiber diameters to give a good gloss and high flexibility, but they failed to have fine interfiber spaces of less than 5 ⁇ m and coarse interfiber spaces of 10 ⁇ m or more failed to coexist uniformly between individual fibers, resulting in poor lightness and resilience. In addition, being small in fiber diameter, they were difficult to color with a dye and had poor color development property. Results are shown in Tables 1-2.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1; a polyethylene terephthalate copolymerized with 7 mol% of isophthalic acid (IPA copolymerized PET, melt viscosity 140 Pa•s, melting point 232°C) was prepared as polymer 2; and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, melting point 254°C) was prepared as polymer 3.
  • SSIA-PEG copolymerized PET melt viscosity 100 Pa•s, melting point 233°C
  • polymers were melted separately at 290°C, weighed to adjust the weight ratio of polymer 1/polymer 2/polymer 3 to 30/35/35, and fed to a spinning pack containing a composite spinneret as illustrated in Fig. 12 , and then the polymers fed were discharged through a discharge hole to form an elliptic core-sheath composite fiber having a composite structure in which the core components were completely surrounded by the sheath component and divided by the sheath component in two regions, that is, the core component 1 and the core component 2, each having a trifoliate cross section with a groove at the apex of each convex portion, as illustrated in Fig. 5(b) .
  • the polymer 1, the polymer 2, and the polymer 3 were arranged in such a manner that they formed the sheath component, the core component 1, and the core component 2, respectively.
  • the composite polymer flow discharged above was cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 18 filament core-sheath composite fiber.
  • the ratio of S min /D between the minimum thickness of the resulting sheath component and the fiber diameter was 0.03 and the ratio of S max /S min between the maximum thickness and the minimum thickness of the sheath component was 12.
  • the ratio of GN/GM between the distance GM from the center of gravity G of the core component to the bottom M of a groove and the distance GN from the center of gravity G of the core component to the apex N of the convex portion was 1.38, proving that this core-sheath composite fiber was one according to the present invention.
  • the ratio between the diameter R A of the inscribed circle and the diameter R B of the circumscribed circle of the core-sheath composite fiber was 1.8, indicating that if it exists in the form of a multifilament, closest packing can be achieved easily and interfiber spaces can be formed uniformly without unevenness by the dissolution of the sheath component.
  • a fabric was produced by weaving the resulting core-sheath composite fiber, treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component, and heat-treated with moist heat at 130°C to provide a fabric containing multifilaments (fiber diameter 10 ⁇ m) formed of the core components of the core-sheath composite fiber.
  • a fabric was produced by weaving the resulting core-sheath composite fiber, treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component, and heat-treated with moist heat at 130°C to provide a fabric containing multifilaments (fiber diameter 10 ⁇ m) formed of the core components of the core-sheath composite fiber.
  • the fabric containing multifilaments had a space structure in which fine interfiber spaces of less than 5 ⁇ m and coarse interfiber spaces of 10 ⁇ m or more coexisted uniformly between individual fibers as in natural silk, and the core component 1 and the core component 2, which differed in shrinkage rate, developed a difference in fiber length as they were heat-treated after dissolving out the sheath component. Consequently, the interfiber spaces of 10 ⁇ m or more were coarser than those formed in Example 1, leading to a space structure more closely resembling that of interfiber spaces in natural silk.
  • the texture had a luxurious gloss independent on view angle (contrast gloss: 1.4), dry touch (friction coefficient: 0.8) with high resilience (bending recovery 2HB: 0.8 ⁇ 10 -2 gf•cm/cm), very high lightness (apparent density: 0.32 g/cm 3 ), and high flexibility (flexural rigidity B: 0.9 ⁇ 10 -2 gf•cm 2 /cm).
  • Example 9 Except for using polypropylene terephthalate (PPT) (Example 9) and polyethylene terephthalate (PET) (Example 10) as the polymer 2, the same procedure as in Example 8 was carried out.
  • PPT polypropylene terephthalate
  • PET polyethylene terephthalate
  • Example 9 rubber elasticity of the PPT was added to allow the fabric to have not only a texture with a higher flexibility, but also a unique stretchable feature that cannot be realized in natural silk. Furthermore, PPT is lower in refractive index than PET and served to produce a fabric having good color development property.
  • Example 10 Although a difference in fiber length was not developed, a natural silk-like texture was formed to a sufficiently high degree, and in addition, the two separated core components worked to allow the fine interfiber spaces of less than 5 ⁇ m and coarse interfiber spaces of 10 ⁇ m or more to exist more uniformly, resulting in a fabric having a texture with improved lightness, flexibility, and resilience. Results are shown in Tables 2-1.
  • Example 8 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 4(a) , the same procedure as in Example 8 was carried out.
  • Example 11 no groove existed at the apex of each convex portion of the fibers having irregular cross-sectional shapes, and consequently, diffused reflection of light decreased, leading to an increased reflection intensity and an increased gloss visibility. A higher wear resistance was also achieved. Results are shown in Tables 2-1.
  • Example 8 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 4(a) and that the weight ratio of the polymer 2 to the polymer 3 was 50/20 (Example 12) and 20/50 (Example 13), respectively, the same procedure as in Example 8 was carried out.
  • Example 8 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 4(a) and that the shape irregularity ratio R B /R A was 3.0, the same procedure as in Example 8 was carried out.
  • Example 8 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 4(b) and the shape irregularity ratio R B /R A was 1.0, the same procedure as in Example 8 was carried out.
  • Example 8 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 4(c) and the shape irregularity ratio R B /R A was 1.0, the same procedure as in Example 8 was carried out.
  • Example 16 since six core component regions are divided by the sheath component, the fibers having irregular shaped cross sections formed by removing the sheath component had smaller fiber diameters, leading to a fabric not only having a milder and more luxurious gloss but also having a texture with higher flexibility. Results are shown in Tables 2-2.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1; a polyethylene terephthalate copolymerized with 7 mol% of isophthalic acid (IPA copolymerized PET, melt viscosity 140 Pa•s, melting point 232°C) was prepared as polymer 2; and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, melting point 254°C) was prepared as polymer 3.
  • SSIA-PEG copolymerized PET melt viscosity 100 Pa•s, melting point 233°C
  • HEI-2-145825 wherein the hardly dissolvable components were of two different polymer species, that is, a higher shrinkage component and a lower shrinkage component, as illustrated in Fig. 6(b) .
  • the polymer 1, the polymer 2, and the polymer 3 were arranged so as to work as the easily dissolvable component, the higher shrinkage hardly dissolvable component, and the lower shrinkage hardly dissolvable component, respectively.
  • the composite polymer flow discharged above was cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 36 filament composite fiber (higher shrinkage: 28 dtex - 18 filament, lower shrinkage: 28 dtex - 18 filament).
  • a fabric was produced by weaving the resulting composite fiber, treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component, and heat-treated with moist heat at 130°C to provide a fabric containing multifilaments (fiber diameter 12 ⁇ m) formed of the hardly dissolvable components of the composite fiber.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1; a polyethylene terephthalate copolymerized with 7 mol% of isophthalic acid (IPA copolymerized PET, melt viscosity 140 Pa•s, melting point 232°C) was prepared as polymer 2; and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, melting point 254°C) was prepared as polymer 3.
  • SSIA-PEG copolymerized PET melt viscosity 100 Pa•s, melting point 233°C
  • polymers were melted separately at 290°C, weighed to adjust the weight ratio of polymer 1/polymer 2/polymer 3 to 30/35/35, and fed to a spinning pack containing a composite spinneret as illustrated in Fig. 12 , and then the polymers fed were discharged through a discharge hole to form a core-sheath composite fiber having a composite structure in which the core components were completely surrounded by the sheath component and divided by the sheath component in two regions, that is, the core component 1 and the core component 2, each having a trifoliate cross section with a groove at the apex of each convex portion, as illustrated in Fig. 10(b) .
  • the polymer 1, the polymer 2, and the polymer 3 were arranged in such a manner that they formed the sheath component, the core component 1, and the core component 2, respectively.
  • the composite polymer flow discharged above was cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 18 filament core-sheath composite fiber.
  • the ratio of S min /D between the minimum thickness of the resulting sheath component and the fiber diameter was 0.03 and the ratio of S max /S min between the maximum thickness and the minimum thickness of the sheath component was 12.
  • the ratio of GN/GM between the distance GM from the center of gravity G of the core component to the bottom M of a groove and the distance GN from the center of gravity G of the core component to the apex N of the convex portion was 1.38, proving that this core-sheath composite fiber was one according to the present invention.
  • the ratio between the diameter R A of the inscribed circle and the diameter R B of the circumscribed circle of the core-sheath composite fiber was 1.8, indicating that if it exists in the form of a multifilament, closest packing can be achieved easily and interfiber spaces can be formed uniformly without unevenness by the dissolution of the sheath component.
  • a fabric was produced by weaving the core-sheath composite fiber, heat-treated with moist heat at 130°C, and treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component to provide a fabric containing multifilaments in which crimped fibers of different polymers coexisted uniformly.
  • the resulting crimped fibers had a composite structure (shape irregularity ratio: 1.6) having a trifoliate cross section with a groove at the apex of each convex portion (MN/D: 0.13).
  • the crimped fibers had a fiber diameter of 10 ⁇ m and the number of crimp peaks was 14 peaks/cm. They were formed of polymers with different melting points with a fiber length difference of 7%.
  • the multifilament fabric In the multifilament fabric, crimps were formed during moist heat treatment due to a difference in thermal shrinkage rate between polymers with different melting points and excluded volume effect occurred between fibers. As a result, not only coarse interfiber spaces of 10 ⁇ m or more were formed between individual fibers, but also interfiber spaces of less than 5 ⁇ m were formed between mutually adjacent crimped fibers made of polymers with different melting points. In this way, the multifilament contained fine interfiber spaces of less than 5 ⁇ m and coarse interfiber spaces of 10 ⁇ m or more coexisting uniformly to form a space structure closely resembling that of interfiber spaces existing in natural silk. An examination of the space structure showed that the average interfiber space distance was 10.5 ⁇ m, and the proportion of spaces with an interfiber space distance of less than 5 ⁇ m was 25%. The space proportion was 65%.
  • the fabric had a luxurious gloss independent on view angle (contrast gloss: 1.4), very high lightness (apparent density: 0.32 g/cm 3 ), and good dry touch (friction coefficient: 0.8), and at the same time, interfiber spaces of less than 5 ⁇ m were formed more stably than in Example 8, leading to a better resilience (bending recovery 2HB: 0.7 ⁇ 10 -2 gf•cm/cm) and flexibility (flexural rigidity B: 0.8 ⁇ 10 -2 gf•cm 2 /cm).
  • bending recovery 2HB 0.7 ⁇ 10 -2 gf•cm/cm
  • flexibility flexibility
  • Example 18 Except that the weight ratio of polymer 1/polymer 2/polymer 3 was 20/40/40 (Example 18) or 10/45/45 (Example 19), the same procedure as in Example 17 was carried out.
  • Example 17 Except for using polypropylene terephthalate (PPT, melt viscosity: 150 Pa•s, melting point: 233°C) as the polymer 2, the same procedure as in Example 17 was carried out.
  • PPT polypropylene terephthalate
  • Example 20 rubber elasticity of the PPT was added to allow the fabric to have not only a texture with a higher flexibility, but also a unique stretchable feature that cannot be realized in natural silk. Furthermore, PPT is lower in refractive index than PET and served to produce a fabric having good color development property. Results are given in Table 3.
  • Example 17 Except for using a polyethylene terephthalate with a high melt viscosity (high viscosity PET, melt viscosity 250 Pa•s, melting point 254°C) as the polymer 2, the same procedure as in Example 17 was carried out.
  • Example 5 since crimps were formed by making use of a difference in viscosity, instead of a difference in melting point, between the polymer 3 and the polymer 2, the crimp number of the crimped fibers in the multifilament decreased and the diffused reflection of light by the space structure in the multifilament was suppressed, leading to an enhanced gloss visibility. Furthermore, the crimps formed by moist heat treatment were small and accordingly, the proportion of interfiber spaces with distances of less than 5 ⁇ m increased, leading to better resilience. Results are given in Table 3.
  • a polyethylene terephthalate copolymerized with 8 mol% of 5-sodium sulfoisophthalic acid and 9 wt% of polyethylene glycol (SSIA-PEG copolymerized PET, melt viscosity 100 Pa•s, melting point 233°C) was prepared as polymer 1; a polyethylene terephthalate copolymerized with 7 mol% of isophthalic acid (IPA copolymerized PET, melt viscosity 140 Pa•s, melting point 232°C) was prepared as polymer 2; and a polyethylene terephthalate (PET, melt viscosity 130 Pa•s, melting point 254°C) was prepared as polymer 3.
  • SSIA-PEG copolymerized PET melt viscosity 100 Pa•s, melting point 233°C
  • the polymer 1, the polymer 2, and the polymer 3 were arranged so as to work as the easily dissolvable component, the higher shrinkage component, and the lower shrinkage component, respectively.
  • the composite polymer flows discharged above were cooled for solidification, then supplied with a lubricant, wound up at a spinning speed of 1,500 m/min, and stretched between rollers heated at 90°C and 130°C to produce a 56 dtex - 36 filament composite fiber (higher shrinkage: 28 dtex - 18 filament, lower shrinkage: 28 dtex - 18 filament).
  • a fabric was produced by weaving the composite fiber, heat-treated with moist heat at 130°C, and treated in a 1 wt% aqueous solution of sodium hydroxide (bath ratio 1:50) heated at 90°C to remove 99% or more of the sheath component to provide a fabric containing multifilaments (fiber diameter 12 ⁇ m) formed of the hardly dissolvable components of the composite fiber.
  • Example 17 Except that the core-sheath composite fiber had a composite structure as illustrated in Fig. 10(a) , the same procedure as in Example 17 was carried out.
  • Example 22 no groove existed at the apex of each convex portion of the crimped fibers in the multifilament and consequently, diffused reflection of light decreased, leading to an increased reflection intensity and an increased gloss visibility. A higher wear resistance was also achieved. Results are given in Table 4.
  • Example 23 Except that the weight ratio of polymer 2/polymer 3 was 50/20 (Example 23) or 20/50 (Example 24), the same procedure as in Example 17 was carried out.
  • Example 25 Except for controlling the discharge rate in such a manner that the fiber diameter of the crimped fibers in the multifilament was 14 ⁇ m (Example 25) or 17 ⁇ m (Example 26), the same procedure as in Example 17 was carried out.
  • the multifilament according to the present invention contains two or more types of crimped fibers that are formed of different polymers and coexist uniformly in the multifilament, and accordingly, they can form a unique space structure in which fine interfiber spaces of less than 5 ⁇ m and coarse interfiber spaces of 10 ⁇ m or more coexist uniformly between the individual fibers in the multifilament as in natural silk. Therefore, fiber materials formed of the multifilament according to the present invention can develop various natural silk-like textural features.
  • Example 12 polymer polymer 1 SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET polymer 2 IPA copolymerized PET PPT PET IPA copolymerized PET IPA copolymerized PET polymer 3 PET PET PET PET PET (melting point of polymer 3) - (melting point of polymer 2) 22°C 21°C 0°C 22°C 22°C weight ratio (polymer 1/2/3) 30/35/35 30/35/35 30/35/35 30/35/35 30/35/35 30/50/20 cross section of fiber cross-sectional shape elliptic elliptic elliptic elliptic composite structure Fig.
  • Example 14 Example 15
  • Example 16 Comparative example 5 polymer polymer 1 SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET polymer 2 IPA copolymerized PET IPA copolymerized PET IPA copolymerized PET IPA copolymerized PET polymer 3 PET PET PET PET PET (melting point of polymer 3) - (melting point of polymer 2) 22°C 22°C 22°C 22°C 22°C weight ratio (polymer 1/2/3) 30/20/50 30/35/35 30/35/35 30/35/35 5/42.5/42.5 cross section of fiber cross-sectional shape elliptic elliptic perfect circle perfect circle elliptic composite structure Fig.
  • Example 17 Example 18 Example 19 Example 20
  • Example 21 Comparative example 6 composite fiber polymer 1 SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET polymer 2 IPA copolymerized PET IPA copolymerized PET IPA copolymerized PET PPT high-viscosity PET IPA copolymerized PET polymer 3 PET PET PET PET PET PET PET PET PET PET PET PET PET (melting point of polymer 3) - (melting point of polymer 2) 22°C 22°C 22°C 21°C 0°C 22°C weight ratio (polymer 1/2/3) 30/35/35 20/40/40 10/45/45 30/35/35 30/35/35 5/47.5/47.5 composite cross-sectional structure Fig.
  • Example 22 Example 23 Example 24 Example 25 Example 26 composite fiber polymer 1 SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET SSIA-PEG copolymerized PET polymer 2 IPA copolymerized PET IPA copolymerized PET IPA copolymerized PET IPA copolymerized PET polymer 3 PET PET PET PET PET (melting point of polymer 3) - (melting point of polymer 2) 22°C 22°C 22°C 22°C 22°C weight ratio (polymer 1/2/3) 30/35/35 30/50/20 30/20/50 30/35/35 30/35/35 composite cross-sectional structure Fig.

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US20220341060A1 (en) 2022-10-27

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