WO2022131312A1 - Fibre composite et multifilament - Google Patents

Fibre composite et multifilament Download PDF

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Publication number
WO2022131312A1
WO2022131312A1 PCT/JP2021/046396 JP2021046396W WO2022131312A1 WO 2022131312 A1 WO2022131312 A1 WO 2022131312A1 JP 2021046396 W JP2021046396 W JP 2021046396W WO 2022131312 A1 WO2022131312 A1 WO 2022131312A1
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WIPO (PCT)
Prior art keywords
fiber
composite
cross
section
fibers
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PCT/JP2021/046396
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English (en)
Japanese (ja)
Inventor
達也 石川
知彦 松浦
正人 増田
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to KR1020237019975A priority Critical patent/KR20230119647A/ko
Priority to JP2021575507A priority patent/JPWO2022131312A1/ja
Priority to EP21906673.5A priority patent/EP4265828A1/fr
Priority to US18/267,798 priority patent/US20240110314A1/en
Priority to CN202180084298.7A priority patent/CN116583634A/zh
Publication of WO2022131312A1 publication Critical patent/WO2022131312A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—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
    • D01D5/32—Side-by-side structure; Spinnerette packs therefor
    • 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
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • 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
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties

Definitions

  • the present invention relates to a composite fiber and a multifilament composed of two or more kinds of components.
  • Synthetic fibers made of polyester, polyamide, etc. have excellent mechanical properties and dimensional stability, so they are used in a wide range of applications from clothing to industrial use. In recent years, the diversification of applications has further progressed, and the required properties have become more sophisticated and multifunctional, and there are cases where existing fibers made of a polymer cannot be used. Although it is possible to newly design a polymer to achieve the required properties, a composite spinning method that combines existing polymers is often selected from the viewpoint of reducing the cost and time required for its development.
  • Fibers produced by the composite spinning method so-called composite fibers, have an appearance that cannot be achieved by fibers made of a single polymer because the main polymer is coated with the other polymer in the fiber cross section (cross section with respect to the axial direction of the fiber). It can give an emotional effect such as texture.
  • the composite fiber is a functional polymer that has problems in chemical resistance and heat resistance by itself and cannot withstand practical use, if it is coated with another polymer, the chemical resistance and heat resistance are dramatically improved. It is also possible to make it practical.
  • Patent Document 1 proposes a fiber having a composite cross section in which a series of laminated structures in which two types of polymers are alternately laminated are joined in a plurality in a direction perpendicular to the laminating direction.
  • a large number of film-like elements constituting the fiber cross section are formed to increase the interface occupied by each film-like element, and a spine-like skeleton portion connecting the laminated structures supports each film-like element.
  • Patent Document 2 proposes a composite form fiber in which the outer periphery of a laminated structure in which two types of polymers are alternately laminated is coated with a protective layer. Similar to Patent Document 1, it is a technique aimed at suppressing interfacial peeling of a laminated structure, and aims at improving wear resistance by covering the outer periphery of the laminated structure with a high-strength polymer having a specific thickness. Is.
  • Patent Document 3 also proposes a composite form fiber in which the entire outer circumference of a laminated structure in which two types of polymers are alternately laminated is coated.
  • the same technical idea as in Patent Document 2 is that the coating is provided on the outermost periphery of the laminated structure to reduce peeling and splitting during the process and to improve the process passability.
  • the purpose is to produce ultrafine fibers by deteriorating the outermost coating by treatment under specific conditions and promoting peeling and splitting.
  • Patent Document 1 describes that the fiber cross section is composed of a large number of film-like elements, but the one actually manufactured in the examples has two structures laminated in at most 50 to 65 layers. Since they were joined side by side, the interface length was limited, and there were cases where it was insufficient to suppress peeling of each film-like element. Further, even if the manufacturing method is devised to increase the number of laminated layers, it is impossible to stably increase the number of laminated layers due to the principle of the manufacturing method.
  • Patent Document 2 and Patent Document 3 the presence of a protective layer responsible for wear resistance may have the effect of suppressing interfacial peeling against weak friction acting on the fiber surface.
  • the laminated structure inside the fiber has only the same number of laminated structures as in Patent Document 1, and interfacial peeling may occur when a large external force is applied or due to repeated rubbing.
  • interfacial peeling occurs, cracks generated by the peeling may propagate to the protective layer on the fiber surface, and the structure is relatively weak against repeated scratching, etc., and has a multi-layered laminated structure.
  • the characteristics of the fiber may be significantly impaired due to exposure to chemicals or heat, and the quality may be significantly deteriorated.
  • the flat ultrafine fiber has a flat fiber cross section, has a flatness of 15 or more, which is a value obtained by dividing the length of the major axis of the fiber cross section by the length of the minor axis, and has a flatness of 15 or more.
  • the multifilament according to (6) above, wherein the flat ultrafine fibers have an average thickness of 1000 nm or less.
  • the composite fiber of the present invention is evenly distributed at a plurality of interfaces existing in the cross section of the fiber even when an external force is applied to the fiber due to the increase in the interface length between the polymers, and the load is applied to a part of the cross section of the fiber. Since concentration is suppressed, even in a fiber composed of a composite of two or more types of polymers, peeling between components is greatly suppressed. Therefore, it is possible to provide a composite fiber and a multifilament having excellent durability such as abrasion resistance, chemical resistance and heat resistance.
  • FIG. 1 is a schematic cross-sectional view of a unidirectional laminated fiber according to an aspect of the present invention.
  • FIG. 2 is a partially enlarged view of FIG.
  • FIG. 3 is a schematic cross-sectional view of a radiated laminated fiber according to another aspect of the present invention.
  • FIG. 4 is a schematic cross-sectional view of a concentric laminated fiber according to another aspect of the present invention.
  • FIG. 5 is a schematic cross-sectional view of the flat ultrafine fibers constituting the multifilament of the present invention.
  • FIG. 6 is a schematic cross-sectional view of the multifilament of the present invention.
  • FIG. 7 is a schematic cross-sectional view of the multifilament when a functional substance is applied to the multifilament of the present invention.
  • FIG. 8 is a cross-sectional view of a composite base for explaining an example of the method for producing a composite fiber of the present invention.
  • FIG. 9 is a schematic cross-sectional view of a conventional coated unidirectional laminated fiber.
  • FIG. 10 is a schematic cross-sectional view of a conventional flat fiber.
  • FIG. 11 is a schematic cross-sectional view of a fiber bundle made of conventional flat fibers.
  • the composite fiber referred to in the present invention is a fiber composed of two or more kinds of polymers.
  • the composite fiber of the present invention is a composite having an extremely large total interface length (interface length) formed by two types of polymers in the cross section (fiber cross section) in the axial direction of the fiber, as compared with the conventional composite fiber. It is characterized by having a morphology.
  • the composite form formed by the two types of polymers and having an extremely large total interface length is defined by the total interface length and the area of the fiber cross section (hereinafter, also referred to as the fiber cross-sectional area).
  • the value obtained by dividing the total interface length referred to in the present invention by the fiber cross-sectional area is obtained as follows. That is, a multifilament made of the composite fiber is embedded with an embedding agent such as an epoxy resin, and an image is taken at a magnification at which the interface of each polymer can be discriminated by a transmission electron microscope (TEM). If the entire interface does not fit in one image, the position where the image was first taken is set as the shooting start position, and a series of images from the same interface to the fiber cross section and returning to the shooting start position are taken. Just take a picture. When the interface extends to the outer peripheral portion of the fiber cross section, a series of images are taken from the outer peripheral portion to the return to the shooting start position. At this time, if electron staining is applied only to a specific polymer, the contrast at the interface becomes clear and the measurement described later can be efficiently performed, which is preferable.
  • TEM transmission electron microscope
  • the fiber cross-sectional area is a magnification that allows the entire cross section of one fiber to be observed, and the cross section is photographed two-dimensionally with a stereomicroscope, and the cross section is extracted by binarization processing using image analysis software. , The area is calculated by rounding off the digits after the decimal point with an integer in nm 2 units.
  • the composite fiber of the present invention is characterized by having a composite form in which the total length (interface length) of the interfaces formed by two adjacent polymers is extremely large in the cross section of the fiber.
  • the value obtained by dividing the total interface length by the fiber cross-sectional area needs to be 0.0010 nm -1 or more, and the interface needs to be continuous in the fiber axis direction.
  • the interface length per unit area of the fiber cross section is extremely large, and it means that two or more kinds of polymers forming the composite cross section are finely divided into a large number of elements. is doing.
  • the element referred to here means a polymer that is surrounded and separated by different types of polymers in the cross section of the fiber.
  • the composite fiber of the present invention different types of polymers are finely divided into an extremely large number of elements in the cross section of the fiber, and the total interface length formed by the two types of polymers is larger than before. It is characterized by having an extremely large composite morphology, and the composite morphology can exhibit various excellent effects as described below.
  • the composite fiber of the present invention since the total of the interface lengths is extremely large, even when an external force is applied to the fiber, the force is distributed to the interfaces existing in a plurality of cross sections of the fiber, and the load is applied to the cross section of the fiber. Since concentration on a part of the fiber is suppressed, it is possible to greatly suppress peeling between the components even in a fiber composed of a composite of two or more types of polymers.
  • the value obtained by dividing the total interface length of the composite fiber of the present invention by the fiber cross-sectional area is 0.0010 nm -1 or more, even when the composite fiber is composed of two types of polymers having poor affinity, the composite fiber is formed. Interfacial peeling between components is less likely to occur, yarn breakage is less likely to be induced in yarn making and higher-order processing processes, good operability is maintained, and high-quality textiles can be processed.
  • the composite fiber is composed of two types of polymers with poor affinity, and this is used for relatively weak scratches such as general clothing. Even when it is subjected to the above, the effect of suppressing peeling between the components can be obtained, and it can be mentioned as a preferable form.
  • the composite fiber composed of two types of polymers having poor affinity can be used as an outdoor product. Even when it is used for applications that are subject to medium-strength scraping, such as, it is possible to effectively suppress peeling between components, and it can be mentioned as a more preferable form. Further, if the value obtained by dividing the total interface length by the cross-sectional area is 0.0500 nm -1 or more, peeling between the components is suppressed even when the product is used for repeated strong scraping such as workwear. Therefore, it can be mentioned as a particularly preferable form.
  • the value obtained by dividing the total interface length by the cross-sectional area is 0.0050 nm -1 or more, so that in addition to the above-mentioned improvement in mechanical properties, one type constituting the composite fiber Even if the component of is a polymer that is inferior in chemical resistance and heat resistance, it is possible to impart excellent chemical resistance and heat resistance by using a polymer with excellent properties as the other component. Become. This improvement in chemical and thermal properties is achieved by the fact that the layer that combines the properties of the two types of polymers formed near the interface becomes apparent due to the dramatic increase in interface length. be.
  • the molecular chains of different polymers may invade each other to form an interface layer having the characteristics of the two types of polymers.
  • the interface layer occupies a large ratio, and the characteristics of the interface layer become apparent, so that the polymer characteristics It exerts an excellent effect from the viewpoint of compounding.
  • the ratio of the interface layer in the fiber cross section is high, and for example, the easily soluble polymer. Even when the composite fiber composed of the poorly soluble polymer is melt-treated, the decrease in the fiber weight after the treatment is slight and excellent chemical resistance can be obtained, so that it can be mentioned as a preferable form. ..
  • the decrease in fiber weight can be extremely slightly stopped even when it is subjected to chemical treatment for a long time, and it can be mentioned as a more preferable form.
  • the value obtained by dividing the total interface length by the cross-sectional area is 0.050 nm -1 or more, the deterioration of fiber properties such as mechanical properties is greatly suppressed even after long-term chemical treatment. Therefore, it can be mentioned as a particularly preferable form.
  • the interface where different types of polymers come into contact tends to be hydrodynamically unstable, and when the interface length is extremely large as in the present invention, it is difficult to stably form a continuous interface. There is.
  • the value obtained by dividing the total interface length by the fiber cross-sectional area is less than 1.000 nm -1 , it is relatively easy to form a continuous interface in the fiber axis direction even when polymers having different rheological properties are composited. Therefore, it is possible to apply various combinations of polymers as the composite fiber of the present invention, and it can be mentioned as a preferable upper limit.
  • the composite fiber of the present invention is characterized by having a composite morphology having an extremely large interface length formed by the two kinds of polymers, and the composite morphology only brings about an excellent effect in mechanical properties.
  • excellent effects can be obtained in terms of chemical properties and thermal properties.
  • the cross sections of the composite fibers of the present invention are alternately composed of two types of polymers. It is preferable to have a laminated multi-layered structure.
  • the composite fiber of the present invention has such a structure, different types of polymers are finely divided into a large number of film-like elements (layers) in the cross section of the fiber, and a large number of layers constituting the cross section are formed. Even when cracks are generated in one layer due to interfacial peeling, the layers are finely composed, so that the cracks can be prevented from propagating. Therefore, it is possible to suppress the progress of fracture in the radial direction of the cross section of the fiber, and it is possible to effectively suppress fibrillation and split fiber even when repeated rubbing is applied.
  • the number of layers of the two types of polymers is 250 or more, fibrilization of the fiber surface can be effectively suppressed, and this is a preferable range. can.
  • the number of layers is 500 or more, the propagation of cracks can be stopped in an extremely minute range of the cross section of the fiber. , Can be mentioned as a more preferable range.
  • the number of laminates referred to here means the total number of film-like elements of the two types of polymers present in the cross section of the fiber.
  • the multilayer structure two types of polymers are alternately laminated in one direction (one-way lamination: one-way laminated fiber 1 shown in FIGS. 1 and 2) or radially laminated (radiation).
  • Lamination A wide variety of laminated forms such as the radiated laminated fiber 2) shown in FIG. 3 and the concentric laminated form (concentric laminated fiber 3 shown in FIG. 4) can be applied. From the viewpoint of minimizing the propagation of cracks, the multilayer structure is preferably unidirectionally laminated or concentric laminated.
  • the multi-layer laminated structure is one-way laminated or concentric laminated, the size of the film-like element (layer) does not become coarse at the outer peripheral portion of the fiber cross section, and a large load is likely to be applied due to bending deformation. However, the propagation of cracks can be stopped in a minute range, and it can be mentioned as a preferable laminated structure.
  • the composite fiber of the present invention has a multi-layered laminated structure in its cross section, so that the effect of improving mechanical properties can be enhanced. Furthermore, at least one type constituting the multi-layered laminated structure.
  • CV value variation of the layer thickness of the polymer relatively large, such as 10% or more, interfacial peeling between the components can be suppressed more effectively.
  • the variation in layer thickness referred to here is measured by measuring the thickness of the layer existing on the line that vertically bisects the long side of each layer with an integer in nm for 100 layers of one type of polymer constituting the fiber cross section. , The coefficient of variation obtained by dividing these standard deviations by the arithmetic mean is calculated by rounding off to the nearest whole number with an integer in%. In the case of radial stacking or concentric stacking where the layer thickness cannot be measured by the above method, the thickest part and the thinnest part of each layer are visually selected and the average value is taken as the layer thickness, and 100 layers are used. The variation in layer thickness can be calculated from the arithmetic mean and standard deviation of. If the number of layers is less than 100 in the cross section of one composite fiber, the total number of layers is 100 from the cross sections of a large number of composite fibers.
  • the variation in the layer thickness of one type of polymer constituting the multi-layer laminated structure becomes relatively large, there are thin and thick parts in the fiber cross section, and the above-mentioned interface layer is present in the thin layer.
  • the effect of is relatively strong and stress concentration is hard to occur, and in the thick layer, it deforms near the interface and disperses the stress. Due to these synergistic effects, the generation of stress in the cross section changes in a complicated manner, and the stress is relieved everywhere in the fiber, so that interfacial delamination between the components can be effectively suppressed.
  • the variation in the layer thickness of at least one type of polymer constituting the multi-layer laminated structure is 10% or more, the stress is complicatedly dispersed in the cross section even when compression deformation is applied in the twisting process or the like. Fluffing of the composite fiber is unlikely to occur, and it can be mentioned as a preferable range. Further, if the variation in the layer thickness of at least one type of polymer constituting the multi-layer laminated structure is 30% or more, even if strong compressive deformation is applied under heating such as in a false twisting process, interfacial peeling occurs. It is less likely to generate fluff and can be processed as a textile with high quality, which can be mentioned as a more preferable range.
  • the average layer thickness of at least one kind of polymer constituting the multilayer laminated structure is 1000 nm or less.
  • the average layer thickness of the polymer is more preferably 300 nm or less, further preferably 100 nm or less, particularly preferably 50 nm or less, and most preferably 30 nm or less.
  • the average layer thickness referred to here is calculated by rounding off the decimal point with an integer in nm unit to the arithmetic mean of the layer thickness of 100 layers of one type of polymer constituting the fiber cross section calculated above. .. If the number of layers is less than 100 in the cross section of one composite fiber, the total number of layers is 100 from the cross sections of a large number of composite fibers.
  • the layer thickness becomes relatively thin the ratio of the interface layer to one layer increases relatively, stress is easily transmitted between adjacent interface layers, and the stress is easily transmitted to the local section of the fiber cross section such as bending deformation. Even when subjected to deformation in which stress is concentrated, the stress is dispersed over the entire cross section, making it difficult for the interface to peel off.
  • the effect can be made more remarkable in terms of chemical properties and thermal properties. ..
  • the molecular chains of different polymers may invade each other to form an interface layer having the characteristics of the two types of polymers, and the interface layer may be formed.
  • the general thickness of is about several nm to 10 nm. That is, when the layer thickness of the polymer constituting the multilayer laminated structure approaches the thickness of the interface layer, most of one layer is composed of the interface layer, and the effect of the interface layer in each layer is extremely remarkable. Therefore, the effect of compounding the polymer properties becomes remarkable.
  • the average layer thickness of at least one kind of polymer constituting the multilayer laminated structure is 50 nm or less, most of the layer of the polymer is occupied by the interface layer.
  • the melting point of the low melting point polymer is obtained. Even when exposed to the above high temperature, it has the effect of suppressing fusion between fibers. The smaller the average layer thickness is, the more the interface layer becomes apparent in each layer constituting the fiber cross section. Therefore, if the average layer thickness of one type of polymer is 30 nm or less, the combination of the above polymers is used. Even when the composite fiber is subjected to a long-term melting treatment or heat treatment, the weight reduction of the fiber and the fusion between the fibers are suppressed, so that the composite fiber can be mentioned as the most preferable range.
  • the mechanical properties of the composite fiber of the present invention are further improved from the viewpoint of improving the dispersibility of the additive.
  • the polymer constituting the composite fiber generally contains additives such as titanium oxide, but these additives exist in an aggregated state, and peeling easily occurs at the interface between the coarse aggregate and the polymer.
  • Additives contained in the polymer are confined in a thin film having a multi-layered structure smaller than the aggregation size, so that the aggregation state is eliminated by the shearing force and the dispersibility is improved, and even when the polymer is repeatedly scraped.
  • the additive is confined in a layer sufficiently thinner than the aggregation diameter of a general additive, so that the dispersibility of the additive is improved. Since it has an excellent effect on wear resistance, it can be mentioned as a preferable range.
  • the solubility parameter (SP value) difference between the two types of polymers composited in the cross section of the fiber is set to 3.0 or less, so that the thinning immediately under the base is stabilized. , It is suitable because it has excellent thickness uniformity in the fiber axis direction.
  • the solubility parameter difference referred to here means a parameter that reflects the cohesive force of the substance defined by (evaporation energy / molar volume) 1/2 , for example, "Plastic Data Book", Asahi Kasei Amidas Co., Ltd.
  • the elongation deformation behavior of each polymer is different, so that the elongation deformation in the spinning process and the drawing process tends to be unstable.
  • the solubility parameter difference between the two types of polymers constituting the composite fiber is large, this instability is promoted, and the thickness unevenness in the fiber axial direction tends to increase.
  • the solubility parameter difference between the two polymers constituting the composite fiber is 3.0 or less, the elongation deformation in the spinning process and the drawing process becomes stable, and excessive thickness unevenness in the fiber axis direction occurs. Is suppressed.
  • the solubility parameter difference between the two types of polymers constituting the composite fiber is 3.0 or less.
  • the thickness spot in the fiber axis direction referred to here can be expressed by the value of Worcester (fineness spot) U%, which is an index of fineness spot, and U% is preferably 1.5% or less.
  • U% is 1.5% or less, even when an external force such as repeated tension is applied, it is possible to suppress the concentration of the load on a part in the fiber axial direction, so that the component constituting the fiber cross section. It is possible to prevent the gaps from peeling off and cracks from occurring.
  • U% can be controlled to 1.5% or less.
  • the composite fiber of the present invention not only exerts an excellent effect on improving mechanical properties by forming a composite morphology having an extremely large interface length, which has never existed in the past, but also by appropriately selecting a polymer to be combined. It can also exert excellent effects on chemical and thermal properties. From this, the composite fiber of the present invention is used for general clothing such as inner and outer, interior applications such as curtains and cloths, vehicle interior applications such as car seats, daily applications such as wiping cloths and health products, and harmful substances such as filters. It can be widely used for substance removal and industrial materials such as battery separators.
  • a multifilament composed of flat ultrafine fibers composed of the other type of polymer can be obtained.
  • the multifilament is derived from the characteristic of the composite fiber that the interface peeling is hard to occur, and since the generation of fluff and the like is small, the composite fiber has the characteristic that the interface length is extremely large in addition to being able to be processed into a high-quality textile product. Therefore, an extremely large specific surface area will be generated. Due to the effect of this specific surface area, when the multifilament is functionally processed, a large amount of functional substances are adsorbed, and excellent functionality can be exhibited.
  • the cross-sectional shape of the flat ultrafine fibers constituting the multifilament of the present invention is important, and the cross-sectional shape of the fiber is flat. It is important that the flatness is extremely high and the thickness is thin.
  • the flat shape referred to here means a shape such as a rectangle or an ellipse in which the length of the major axis and the length of the minor axis are different, and the degree of flatness of this shape is the length of the major axis to the length of the minor axis. It is defined as flatness, which is the value divided by. In the multifilament of the present invention, the flatness in the cross section of the fiber needs to be 15 or more.
  • the flatness referred to in the present invention is obtained as follows (see also FIG. 5).
  • the multifilament of the present invention is embedded with an embedding agent such as epoxy resin
  • the cross section of the fiber is cut with a microtome equipped with a diamond knife, and the cross section can be identified by a scanning electron microscope (SEM) or the like.
  • SEM scanning electron microscope
  • Shoot at magnification For the cross section of a single fiber (flat ultrafine fiber) existing in the captured image, measure the maximum length of the cross section using image analysis software, and use this value as the length of the long axis of the single fiber as an integer in nm. The following is rounded off.
  • the first requirement of the multifilament of the present invention is that the flat ultrafine fibers constituting the multifilament have a high flatness in the fiber cross section, and the flatness is 15 or more as an index of the cross-sectional shape. You will need it. Within this range, the specific surface area of the fiber is more than doubled as compared with the round cross-section fiber having the same fineness, and the adsorption efficiency of the functional substance, which is the object of the present invention, can be enhanced.
  • the multifilament 5 has a peculiar fiber bundle structure derived from the morphology of the flat ultrafine fibers 4, as shown in FIG. That is, due to the high shape anisotropy of the flat ultrafine fibers, restrictions are created in the arrangement direction of the fibers, and the flat ultrafine fibers are overlapped in the same direction. Due to such a fiber bundle structure, the number of fibers arranged per unit volume is greatly increased, and more excellent adsorption efficiency can be achieved in combination with the above-mentioned effect of increasing the specific surface area of one fiber.
  • the fiber bundle referred to here does not limit the aggregated form as long as a plurality of flat ultrafine fibers are aggregated, and the single fiber is clearly separated or the single fiber is used. Includes those that have aggregated into a single coarse fiber.
  • Shape That is, when the flatness is 30 or more, not only the specific surface area of the fiber is increased more than three times as compared with the round cross-section fiber having the same fineness, but also the more dense arrangement form makes the surface area increasing effect more remarkable. It is. In such a case, the flatness is preferably 30 or more because the adsorption efficiency of the functional substance is further increased and the function can be effectively exhibited.
  • the flatness is 40 or more
  • the remarkable shape anisotropy suppresses the direction of the fibers from being disturbed and overlapping in a part of the fiber bundle, and the fiber directions are uniformly aligned as a whole. It comes to take an array form. It is more preferable that the flatness is 40 or more because such an arrangement form enables a uniform function without spots as a whole.
  • the flatness is 50 or more, even when the fiber bundles of the flat ultrafine fibers are twisted, the fibers are arranged radially with respect to the center of the fiber bundles, and the arrangement form in which the fiber directions are aligned is maintained.
  • the arrangement direction can be changed arbitrarily.
  • Such a feature has an excellent effect in controlling the strength of the function derived from the functional substance, and when it is desired to change the arrangement direction of the fibers, the flatness should be 50 or more. Is particularly preferable.
  • the multifilament of the present invention has a specific surface area, which is the surface area per weight, as compared with ordinary fibers due to the extremely high flatness of the fiber cross section of the flat ultrafine fibers constituting the multifilament.
  • the specific surface area of this single fiber is greatly affected not only by the flatness of the cross section but also by the fiber diameter, and the fiber diameter is also an important requirement for the effect of increasing the surface area derived from the cross-sectional shape to be sufficient.
  • the second requirement is that the thickness of the flat ultrafine fiber, that is, the length of the minor axis of the cross section of the fiber is thin, and the average thickness needs to be 1000 nm or less. ..
  • the average thickness referred to here is obtained by rounding off the decimal point with an integer in nm unit to the arithmetic mean of the length of the minor axis of the 100 fibers measured above.
  • the average thickness of the flat ultrafine fibers is 1000 nm or less, a specific surface area equal to or greater than that of ordinary ultrafine fibers can be obtained, and high adsorption efficiency can be achieved. For this reason, in the multifilament of the present invention, the average thickness of the flat ultrafine fibers needs to be 1000 nm or less.
  • the thinner the average thickness of the flat ultrafine fibers the more the effect of increasing the specific surface area of the single fibers is promoted, and the thickness also affects the flexural rigidity of the fibers. It also brings an excellent effect. That is, the flexural rigidity in the minor axis direction decreases in proportion to the cube of the thickness of the fiber, and as the thickness becomes thinner, the fiber flexibly deforms with respect to irregularities and the like, and can follow the shape. , The fiber bundle structure tends to be densified.
  • the average thickness is 800 nm or less, not only the effect of increasing the specific surface area is further strengthened, but also the fibers are deformed according to the shape, so that it is possible to effectively suppress the formation of coarse voids between the fibers. It tends to have a dense structure. For this reason, the average thickness is preferably 800 nm or less.
  • the average thickness is 500 nm or less, the flexibility of the fiber becomes extreme, and an intermolecular force such as a van der Waals force acts to form a fiber bundle as if the single fibers were adhered to each other. Will come to do. In such a case, the voids between the fibers become extremely small from several nm to several hundred nm, and an excellent effect is obtained from the viewpoint of developing highly durable functions, which will be described later, so that the average thickness is 500 nm or less. Is more preferable.
  • the average thickness is 300 nm or less
  • the structure in which single fibers are aggregated as described above is uniformly formed in the entire fiber bundle, and when functionally processed, a uniform and uniform function is exhibited as a whole. Become. For this reason, it is particularly preferable that the average length of the minor axis is 300 nm or less.
  • the average thickness of the cross section of the fiber becomes thinner, it tends to break easily when an external force is applied in the processing process, but if the average thickness is 50 nm or more, there is a problem in actual use.
  • the object of the present invention can be achieved.
  • the specific surface area of the fiber is significantly increased due to the extremely high flatness of the cross-sectional shape of the flat ultrafine fiber constituting the multifilament, and the specific fiber is a dense fiber having the same direction.
  • the specific fiber is a dense fiber having the same direction.
  • a very large fiber surface is produced per unit volume.
  • the durability can be dramatically improved due to the unique fiber bundle structure. That is, when the multifilament of the present invention is functionally processed, not only a large amount of functional substances are adsorbed on the fiber surface, but also, as shown in FIG.
  • the flat ultrafine fibers 4 overlapping in the same direction The functional substance D will enter between them. For this reason, while a large amount of the functional substance is contained in the fiber bundle, the distribution state is such that the functional substance is hardly exposed on the surface of the fiber bundle, and the functional substance is hard to fall off due to scratching or the like, and the durability in terms of functionality is high. Is improved.
  • the variation in thickness referred to here is the variation obtained by calculating the arithmetic mean and standard deviation using the length of the minor axis of the 100 fibers measured above and dividing the standard deviation by the arithmetic mean.
  • the coefficient is calculated by rounding off the fractions with an integer in%.
  • each single fiber moves in a different manner and is well dispersed. In such a case, the fiber surface is exposed to the liquid without being hindered by other fibers, and the functional substance can be efficiently adsorbed.
  • the variation in thickness is 10% or more, the single fiber is easily dispersed in the liquid or the like, and the functional substance is easily impregnated. Therefore, the variation in thickness is preferably 10% or more.
  • the thickness variation is more preferably 20% or more.
  • the variation in thickness is 40% or more, the liquid easily permeates even between the single fibers even in the case of a high-density woven or knitted fabric in which the yarn is firmly restrained, and the high-density woven or knitted fabric is used.
  • the variation in thickness is 40% or more.
  • the fiber having a short thickness tends to break, but if the variation in thickness is less than 70%, there is no problem in actual use, and the present invention has no problem. Can achieve the purpose of.
  • the degree of unevenness on the fiber surface it may be possible to improve the dispersed state of the single fiber during functional processing, and the degree of unevenness on the cross section is also a noteworthy index. That is, due to the presence of appropriate irregularities on the fiber surface, minute voids of several nm to several hundred nm are formed between the fibers, and the fine voids are used as a starting point in a liquid containing a functional substance or the like. This makes it easier for the single fibers to be effectively dispersed.
  • the degree of unevenness referred to here is the length at which a line segment orthogonal to the maximum length line segment intersects the fiber cross section at a point where the maximum length of the cross section is divided into 10 equal parts by using an image of the fiber cross section taken. , The arithmetic average and standard deviation of the lengths of these 10 points are calculated, and the value obtained by dividing the standard deviation by the average value and rounding off the fractions in percent is used as the degree of unevenness of the single fiber. The same measurement is performed on the cross sections of 10 fibers, and the arithmetic mean of the calculated unevenness of the 10 fibers is taken as the unevenness referred to here.
  • the degree of unevenness is 20% or more, the single fibers are easily dispersed starting from the minute voids between the fibers, and the functional processing can be completed in a short time. Therefore, the degree of unevenness is preferably 20% or more.
  • the degree of unevenness increases, the load tends to concentrate on a part of the cross section and cracks tend to occur.
  • the degree of unevenness is less than 60%, there is no problem in actual use, and the object of the present invention is Can be achieved.
  • the multifilament of the present invention can significantly increase the specific surface area while maintaining the cross-sectional area of the fiber due to the unique cross-sectional shape of the cross section of the fiber, the strength of the single fiber is equivalent to that of a normal fiber. Therefore, there is no problem such as unnecessarily deteriorating the quality of textile products, and it is excellent in handleability. Further, the flat ultrafine fibers of the present invention have a continuous form in the fiber axis direction, and since the number of fiber ends in the fiber bundle is reduced, the quality of the fiber product is not easily impaired and the handleability is excellent.
  • a crystalline polymer is preferable in consideration of passability in a normal higher-order processing step and actual use
  • the polymer constituting the flat ultrafine fibers is polyester. It preferably contains at least one polymer selected from the group consisting of polyamides and polyolefins.
  • these polymers are thermoplastic, not only can the multifilament of the present invention be produced by a highly productive melt spinning method, but also the dynamics such as highly oriented crystallization in the drawing step. It is suitable from the viewpoint of adjusting the characteristics and the like.
  • the strength of the fiber is preferably 1 cN / dtex or more in consideration of actual use, and 2 cN when used as a woven fabric or a sheet used in a relatively harsh atmosphere. It is preferable that it is / dtex or more, and it can be mentioned as a more preferable range.
  • the multifilament of the present invention By utilizing the features of the multifilament of the present invention, not only can a large amount of functional substances be adsorbed by functional processing to effectively exhibit the functions, but also the functional substances are encapsulated in the fiber bundle due to the unique fiber bundle structure. As a result, it is possible to exhibit excellent durability in which the functional substance is hard to fall off. Further, by utilizing this, it is possible to obtain a sustained release effect such that the functional substance diffuses inside the fiber bundle or the fiber bundle is deformed by an external force so that the functional substance is gradually released. .. Therefore, when the multifilament of the present invention is used as a functional material in combination with a functional substance, it is preferable to process the multifilament into a state in which the functional substance is contained in a fiber bundle made of flat ultrafine fibers.
  • the functional substance referred to here refers to a substance that positively imparts functionality to the fiber, and is not particularly limited as long as it is a compound having a function. Further, the functional substance may be an organic compound or an inorganic compound. Examples of this functionality include UV protection, fragrance, deodorant, antibacterial, insect repellent, moisture absorption, antistatic, flame retardant, antifouling, beauty and healthcare, but are not limited to these functions. do not have.
  • various forms are conceivable as the state of existence of the functional substance in the fiber, and the forms include loading and exhaustion by chemical bonds, physical adsorption, and the like.
  • the multifilament of the present invention is an inner or an outer.
  • clothing applications such as curtains and cloths
  • vehicle interior applications such as car seats
  • daily applications such as wiping cloths and health products
  • harmful substance removal applications such as filters
  • industrial material applications such as battery separators.
  • the composite fiber and multifilament of the present invention can be produced by a silk reeling process using a composite base as described later, and it is preferable to use melt spinning from the viewpoint of high productivity.
  • the composite base used in the present invention for example, it is preferable to use the composite base 10 in which the three types of members of the measuring plate E, the composite plate F and the discharge plate G are laminated, as shown in FIG.
  • FIG. 8 shows an example in which two types of polymers such as the A component and the B component are used, and if necessary, three or more types of polymers may be used for spinning.
  • the composite base 10 the amount of polymer per hole of the composite plate F is measured by the measuring plate E, and the different types of polymer flows weighed are merged by the composite plate F to form a composite flow having an interface.
  • the interface in the cross section of the composite flow is increased by dividing and remerging the composite flow, and the discharge plate G plays a role of compressing and discharging the composite flow formed by the composite plate F.
  • the combined flow referred to here means a fluid having a cross section perpendicular to the flow direction composed of two or more kinds of polymers.
  • the composite plate F has a number of fine flow paths H having a confluence portion and a branch portion, which is equal to or larger than the number of discharge holes of the discharge plate G, and the confluence portion and the branch portion are appropriately formed so as to form a desired cross section.
  • the installation can be adjusted.
  • the merging portion referred to here means a portion where two or more flows merge
  • the branch portion means a portion where the flow is divided into two or more.
  • a composite cross section characterized in that the sum of the interface lengths of the two types of polymers required for the composite fiber of the present invention is extremely large with respect to the fiber cross section is formed.
  • the merging and splitting referred to here it is not necessary to repeat the merging and splitting, and the merging and splitting may be performed again after the merging or re-splitting after the merging.
  • the fluid supplied to the fine flow path of the composite plate F may be a blend of two kinds of polymers in advance, or a composite flow formed by another method or the like may be used.
  • the fine flow path used in the production of the present invention has a flow path configuration that minimizes the turbulence of the flow in the flow path, thereby enabling the production of the composite fiber of the present invention.
  • the above-mentioned fine flow path has the same characteristics as the conventional static mixer (static mixer) in that the fluid is merged or divided in the flow path.
  • a general stationary mixer has a flow path design for the purpose of mixing two types of polymers, and the inserted polymer flow is disturbed. Therefore, the composite of the present invention is used. It is difficult for even those skilled in the art to produce fibers.
  • the flow path configuration of the fine flow path of the present invention it is possible to control the form such as the thickness of each layer constituting the laminated composite flow formed in the flow path, and any composite form can be used. It is possible to form a fiber cross section of.
  • the members forming the flow path are provided according to the spinning machine and the spinning pack. You can use it.
  • the measuring plate E By designing the measuring plate E according to the existing flow path member, the existing spinning pack and the member can be utilized as it is. Therefore, it is not necessary to monopolize the spinning machine especially for the mouthpiece.
  • the composite polymer flow discharged from the discharge plate G is cooled and solidified, then oiled, and is taken up by a roller having a specified peripheral speed to become composite fibers.
  • the composite fiber of the present invention can be produced by using the composite base as described above.
  • the composite base is used, the composite fiber of the present invention can be produced even by a spinning method using a solvent such as solution spinning.
  • the polymer constituting the composite fiber of the present invention is as described above.
  • examples thereof include melt-moldable polymers such as polyethylene terephthalate or a copolymer thereof, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, polypropylene, polyolefin, polycarbonate, polyacrylate, polyamide, polylactic acid, and thermoplastic polyurethane. ..
  • melt-moldable polymers such as polyethylene terephthalate or a copolymer thereof, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, polypropylene, polyolefin, polycarbonate, polyacrylate, polyamide, polylactic acid, and thermoplastic polyurethane. ..
  • polycondensation polymers typified by polyester and polyamide have a high melting point and are more preferable.
  • the polymer contains various additives such as titanium oxide, silica, inorganic substances such as barium oxide, carbon black, colorants such as dyes and pigments, flame retardants, fluorescent whitening agents, antioxidants, and ultraviolet absorbers. You may be. Further, when a polymer containing these additives is selected, unevenness is generated in each layer of the multilayer laminated fiber corresponding to the particle size of the fine particles as the additive, and the flat ultrafine fibers generated based on the unevenness are generated. Any unevenness can be added.
  • the polymers are polyesters
  • the interface at one interface. It is preferable because the layer is formed more widely.
  • the fiber contains the easily soluble polyester. Is also suitable because it can impart excellent chemical resistance.
  • polyester copolymerized with a metal sulfonic acid base when a polyester obtained by copolymerizing sodium sulfoisophthalic acid or polyethylene glycol alone or in combination is used, in addition to excellent chemical resistance, after dyeing.
  • the color development property is also good, which is preferable.
  • the spinning temperature at the time of spinning the composite fiber of the present invention is a temperature at which the high melting point or high viscosity polymer mainly exhibits fluidity among two or more kinds of polymers.
  • the temperature indicating this fluidity may be set at a melting point of + 60 ° C. or lower from the melting point of the polymer, although it varies depending on the molecular weight. If it is less than this, the polymer is not thermally decomposed in the spinning head or the spinning pack, and the decrease in molecular weight is suppressed, which is preferable.
  • Stable production can be achieved by setting the discharge amount when spinning the composite fiber of the present invention to 0.1 g / min ⁇ hole to 20.0 g / min ⁇ hole. In particular, it is preferable to set the discharge amount to a single hole so that the fineness of the single fiber after stretching is less than 4 dtex, because a flexible texture can be obtained when the woven fabric is formed due to its fineness.
  • the ratio of the A component and the B component when spinning the composite fiber of the present invention can be selected in the range of 5/95 to 95/5 in the A component / B component ratio based on the discharge amount. Even when a polymer with inferior chemical resistance and heat resistance is used, if it is desired to impart excellent chemical resistance and heat resistance by increasing the interface between the components, the chemical resistance and heat resistance can be increased. It is preferable to combine an excellent polymer with the other to increase the ratio thereof. For example, when the component A is a highly chemical resistant polymer and the component B is a low chemical resistant polymer, the component A / component B is used. When the ratio is 99/1 to 70/30, the weight loss of the fiber is slight even if the dissolution treatment is performed for a long time, which is preferable.
  • the polymer flow discharged in this way is cooled and solidified, oiled, and taken up by a roller whose peripheral speed is regulated to become composite fibers.
  • the take-up speed may be determined from the discharge amount and the target fiber diameter, but in order to stably produce the composite fiber used in the present invention, it is preferably in the range of 100 to 7000 m / min.
  • the composite fiber may be stretched from the viewpoint of high orientation and improvement of mechanical properties. This stretching may be performed after being wound once in the spinning step, or may be continued without being wound once.
  • the first setting is set to a temperature equal to or higher than the glass transition temperature and lower than the melting point. It is possible to obtain a composite fiber having a composite cross section as shown in FIG. 1 by being stretched reasonably in the fiber axis direction and thermally set and wound by the peripheral speed ratio of the roller and the second roller corresponding to the crystallization temperature. can.
  • the upper limit of the temperature of the first roller is preferably a temperature at which the yarn path disorder of the fiber does not occur in the preheating process. For example, in the case of polyethylene terephthalate having a glass transition temperature of around 70 ° C., this preheating is usually performed. The temperature is set at about 80 to 95 ° C.
  • the method for producing a composite fiber of the present invention has been described based on a general melt spinning method, but it goes without saying that it can also be produced by a melt blow method and a spunbond method, and further, wet and dry wet methods and the like. It is also possible to manufacture by the solution spinning method of.
  • the multi-layer laminated fiber is immersed in a solvent or the like in which the easily soluble polymer can be dissolved to remove the easily soluble polymer.
  • the easily soluble polymer is a copolymerized polyethylene terephthalate in which 5-sodium sulfoisophthalic acid or the like is copolymerized
  • an alkaline aqueous solution such as an aqueous sodium hydroxide solution can be used.
  • the polymer may be made of fiber or a textile made of the fiber, and then immersed in an alkaline aqueous solution. At this time, it is preferable to heat the alkaline aqueous solution to 50 ° C. or higher because the progress of hydrolysis can be accelerated.
  • the method for generating multifilaments from the multi-layer laminated fiber is not limited to the above-mentioned dissolution treatment, but by dissolving and removing the easily soluble polymer, it becomes a single fiber of a flat ultrafine fiber made of a poorly soluble polymer. The damage of the fiber can be minimized while the separation is surely made, and the multifilament of the present invention can be satisfactorily generated.
  • A. Melt Viscosity The chip-shaped polymer was dried by a vacuum dryer to a moisture content of 200 ppm or less, and the strain rate was changed stepwise by a capillograph manufactured by Toyo Seiki Seisakusho Co., Ltd. to measure the melt viscosity.
  • the measured temperature is the same as the spinning temperature, and the melt viscosity at a shear rate of 1216s -1 is described in Examples or Comparative Examples. It took 5 minutes from the time the sample was put into the heating furnace to the start of the measurement, and the measurement was performed in a nitrogen atmosphere.
  • Solubility parameter difference is a parameter that reflects the cohesive force of a substance defined by the square root of (evaporation energy / molar volume), and the polymer is immersed in various solvents to maximize the swelling pressure.
  • the value of the solvent (evaporation energy / molar volume) was determined as the (evaporation energy / molar volume) of the polymer.
  • the SP value thus obtained is described in, for example, "Plastic Data Book", Asahi Kasei Amidas Co., Ltd./Plastic Editorial Department co-edited, page 189, and this value can be used.
  • the solubility parameter difference of the polymer to be combined was calculated as an absolute value of (SP value of component A-SP value of component B).
  • Fineness The weight of the composite fiber of 100 m was measured, and the value was multiplied by 100 to calculate the value. This measurement was repeated 10 times, and the average value was taken as the fineness (dtex). Further, the value obtained by dividing the above fineness by the number of filaments was defined as the single fiber fineness (dtex).
  • the Uster U% (H) of the composite fiber was measured using a fineness spot measuring device Zellweger (UT-4) under the conditions of a yarn feeding speed of 100 m / min, a twister rotation speed of 6000 rpm, and a measurement length of 100 m.
  • UT-4 fineness spot measuring device Zellweger
  • the composite fiber is cut at an arbitrary position in the fiber axis direction perpendicular to the fiber axis direction, and the cut surface is observed with an optical microscope manufactured by OLYMPUS to observe the entire cross section of one single yarn.
  • Two-dimensional images are taken at a magnification that can be obtained, one single yarn cross section is extracted using image analysis software (WINROOF), and then the fiber cross section is measured in nm units from the cross section parameters obtained through the binarization process. Calculated by rounding off the digits after the decimal point with an integer.
  • the layer thickness The length of the layer existing on the straight line that vertically divides the long side of one layer (film-like element) constituting the fiber cross section into two equal parts is defined as the layer thickness, and the total of the above-mentioned interface lengths is measured. From the cross-sectional image of the composite fiber taken by the same method as above, 100 elements of the B component were randomly extracted, and the layer thickness was measured by rounding off the fractions with an integer in nm units. When the number of layers in the cross section of one composite fiber is less than 100, the total number of layers is 100 from the cross sections of a large number of composite fibers.
  • the arithmetic mean and standard deviation of the obtained values were calculated, and the coefficient of variation obtained by dividing the standard deviation by the arithmetic mean was rounded off to the nearest whole number in% to calculate the variation in layer thickness.
  • the coefficient of variation obtained by dividing the standard deviation by the arithmetic mean was calculated as the variation in layer thickness.
  • H Average layer thickness (composite fiber)
  • the length of the layer existing on the straight line that vertically divides the long side of one layer constituting the fiber cross section into two equal parts is defined as the layer thickness, and the sum of the interface lengths described above is measured by the same method. From the cross-sectional image of the composite fiber taken, 100 elements of the B component were randomly extracted, and the layer thickness was measured by rounding off the fractions with an integer in nm units. When the number of layers in the cross section of one composite fiber is less than 100, the total number of layers is 100 from the cross sections of a large number of composite fibers. The arithmetic mean of the obtained values was rounded off to the nearest whole number with an integer in nm to calculate the average layer thickness.
  • the thickest part and the thinnest part of each layer are visually selected, and the average value is taken as the thickness of each layer. Similarly, this arithmetic mean was calculated as the average layer thickness.
  • Abrasion resistance The number of fibers of the composite fiber was adjusted so that the weaving density was 180 fibers / 2.54 cm, and a plain weave fabric was prepared.
  • a plain woven fabric cut to a diameter of 10 cm is set in the sample holder of an appearance retention tester (ART type tester) manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd., and the pressing load is 3.9 N, and a friction plate made of silicon carbide (3K). ), The friction plate stopped every one rotation, and the number of frictions at which the occurrence of fibrils was confirmed on the fiber surface was measured and calculated as the average value of the five measurements.
  • Friction frequency is 100 or more and B (good): Friction is 50 or more and less than 100.
  • the dry heat shrinkage rate was obtained from 5 measurements, and the arithmetic mean was calculated by rounding off the second digit after the decimal point.
  • the surface of the treated skein fibers was observed with an optical microscope manufactured by Olympus Corporation to confirm whether fusion occurred between the fibers, and the heat resistance was evaluated by the following three-step evaluation.
  • R. Deodorant acetaldehyde concentration
  • 1 g of the functionally processed fabric processed in Q above is placed in a 5 L tetra bag, and 3 L of acetaldehyde having a concentration of 30 ppm is injected into the tetra bag.
  • the gas concentration (ppm) in the tetrabag after 10 minutes was measured using a gas detector tube (manufactured by Gastec).
  • Example 1 As component A, polyethylene terephthalate (PET, melt viscosity: 120 Pa ⁇ s, melting point: 254 ° C, SP value: 21.4 MPa 1/2 ), and as component B, 5-sodium sulfoisophthalic acid 8.0 mol%, polyethylene.
  • PET polyethylene terephthalate
  • SSIA-PEG copolymerized PET melt viscosity: 95 Pa ⁇ s, melting point: 233 ° C., SP value: 22.9 MPa 1/2
  • the composite ratio of the A / B component is set to 90/10, and the composite polymer is poured into the spinning pack incorporating the composite base 10 illustrated in FIG.
  • the flow was discharged.
  • the composite plate F is provided with a microchannel H capable of alternately laminating both components in 1024 layers, and is in a composite form in which two types of polymers as shown in FIG. 1 are alternately laminated in one direction. Discharged like this. After the discharged composite polymer stream was cooled and solidified, an oil agent was applied, the yarn was wound at a spinning speed of 1000 m / min, and undrawn yarn having a 200 dtex-24 filament (total discharge amount 20 g / min) was collected.
  • the wound unstretched fiber was stretched 3.6 times between rollers heated to 90 ° C. and 130 ° C. to obtain a drawn fiber of 56dtex-24 filament.
  • the U% (H) which is an index of fineness spots, was 0.6%, and the thickness uniformity in the fiber axis direction was excellent.
  • the total interface length / fiber cross-sectional area was 0.0557 nm -1 , and the total interface length with respect to the fiber cross-sectional area was extremely large, and the same interface was the fiber. It was continuous in the axial direction. Further, the average layer thickness of the B component was 4 nm, the layer thickness variation was relatively large at 32%, and it was divided into extremely thin film-like elements.
  • Examples 2, 3, 4, 5, 6 In the method described in Example 1, the total number of layers of the A component and the B component is 512 layers (Example 2), 256 layers (Example 3), 128 (Example 4), 64 (Example 5), 32 (Example 5). All were carried out in the same manner as in Example 1 except that the composite plate provided with the fine flow path to be laminated was changed to Example 6). The evaluation results of these composite fibers are as shown in Table 1.
  • the composite fibers of Examples 2 to 6 had a composite structure as shown in FIG. 1 in which two types of polymers were alternately laminated in one direction, and the same interface was continuous in the fiber axial direction.
  • Example 2 no fibril was observed even when the number of frictions was 100 or more, but in Examples 3 to 6, the number of laminated layers of the two types of polymers in the fiber cross section was higher than that in Example 2.
  • the value of the total interface length / fiber cross-sectional area decreases as the number of frictions decreases, fibrils were observed with several single yarns when the number of frictions was 50 or more.
  • Example 1 In the method described in Example 1, all the same steps as in Example 1 were carried out except that the total number of layers of the components A and B was changed to a composite plate provided with a microchannel having fine flow paths laminated in 8 layers (Comparative Example 1). .. The evaluation results of these composite fibers are as shown in Table 1.
  • the composite fiber of Comparative Example 1 has a composite structure in which two types of polymers are alternately laminated in one direction as shown in FIG. 1, the number of divisions (number of stacks) thereof is compared with that of the composite fiber of the present invention. Since the value of the total interface length / fiber cross-sectional area is small, fibrils were observed in a large number of single fibers when the number of frictions was 20 or more, and the wear resistance was inferior. .. Moreover, when the chemical resistance of the obtained tubular knitted fabric of the composite fiber was evaluated, the weight loss rate was 10.0% or more, which was inferior in chemical resistance.
  • Example 7 In the method described in Example 1, polyethylene terephthalate (SPG-CHDC copolymerized PET, melt viscosity 75 Pa ⁇ s, melting point: none [glass transition] obtained by copolymerizing 21 mol% of spiroglycol and 29 mol% of cyclohexanedicarboxylic acid as component B. Temperature: 76 ° C.], SP value: 23.0 MPa 1/2 )), and melted at 285 ° C., all of which were carried out in the same manner as in Example 1 except that the composite ratio of A / B components was 50/50. The evaluation results of this composite fiber are as shown in Table 2.
  • the composite fiber of Example 7 had a composite structure as shown in FIG. 1 in which two types of polymers were alternately laminated in one direction, and the same interface was continuous in the fiber axis direction.
  • the peeling resistance of the obtained composite fiber woven fabric no fibril was observed even when the number of frictions was 100 or more.
  • the obtained composite fiber skein was treated with a hot air dryer at 160 ° C. for 15 minutes, the dry heat shrinkage rate was less than 15.0%, which was excellent in thermal dimensional stability, and the glass transition temperature was amorphous and the glass transition temperature was hot air. No fusion between fibers was observed despite the use of SPG-CHDC copolymerized PET below the treatment temperature of the dryer.
  • Example 8 and 9 All except that in the method described in Example 7, the total number of layers of the components A and B was changed to a composite plate having a microchannel for laminating the 512 layers (Example 8) and the 256 layers (Example 9). It was carried out in the same manner as in Example 7. The evaluation results of these composite fibers are as shown in Table 2.
  • Example 8 the generation of fibril was not observed even when the number of frictions was 100 or more, but in Example 9, the number of layers of the two types of polymers in the fiber cross section was reduced as compared with Example 8. As a result, the value of the total interface length / fiber cross-sectional area decreases, so fibril was observed in several single fibers when the number of frictions was 50 or more. Further, as the composite ratio of the SPG-CHDC copolymerized PET, which is inferior in heat resistance, is increased, the dry heat shrinkage rate is increased, and the heat resistance is lowered although it is at a level that is not a problem in Example 9. Further, in Example 9, since two kinds of polymers having different characteristics were alternately laminated with a layer thickness such that thin film interference of visible light occurred, the obtained composite fiber had a structural color of blue.
  • Example 2 In the method described in Example 7, all were carried out in the same manner as in Example 7 except that a composite plate provided with a microchannel for laminating the total number of layers of A component and B component in 8 layers was used. The evaluation results of these composite fibers are as shown in Table 2.
  • the composite fiber of Comparative Example 2 has a composite structure in which two types of polymers are alternately laminated in one direction as shown in FIG. 1, the number of divisions (number of stacks) is compared with that of the composite fiber of the present invention. Since the value of the total interface length / fiber cross-sectional area is small, fibrils were observed in a large number of single fibers when the number of frictions was 20 or more, and the wear resistance was inferior. .. Moreover, when the heat resistance of the obtained tubular knitted fabric of the composite fiber was evaluated, the dry heat shrinkage rate was 20.0% or more, the fusion between the fibers was remarkable, and the texture of the skein was very hard. Met.
  • Examples 10, 11, 12 In the method described in Example 7, the component B was melted as polyamide-6 (N6, melt viscosity 100 Pa ⁇ s, melting point: 225 ° C.], SP value: 23.7 MPa 1/2 ) at 280 ° C., and both components were melted. All were carried out in the same manner as in Example 7 except that the composite plate provided with the microchannels laminated on the 1024 layer (Example 10), the 512 layer (Example 11) and the 256 layer (Example 12) was used. The evaluation results of these composite fibers are as shown in Table 3.
  • Example 13 and 14 In the method according to the tenth embodiment, the total number of layers of the A component and the B component is changed to a composite plate provided with a microchannel for laminating 256 layers, and a concentric laminated structure (Example 13) and a radial laminated structure are provided. Everything was carried out in the same manner as in Example 10 except that the flow path arrangement was changed so as to be in Example 14. The evaluation results of these composite fibers are as shown in Table 3.
  • Example 13 a composite structure as shown in FIG. 4 in which two types of polymers are alternately laminated in a concentric manner is formed, and in Example 14, two types of polymers are alternately laminated in multiple layers in a radial pattern.
  • a composite structure as shown in 3 was formed, and the same interface was continuous in the fiber axis direction. Since the composite fiber is composed of a composite of polymers with a large difference in solubility parameter, fibrils were observed in several single fibers when the number of frictions was 50 or more, but the wear resistance was generally good. Met.
  • Example 3 In the method described in Example 10, all were carried out in the same manner as in Example 10 except that a composite plate provided with a microchannel for laminating the total number of layers of A component and B component in 8 layers was used. The evaluation results of this composite fiber are as shown in Table 3.
  • the composite fiber of Comparative Example 3 has a composite structure in which two types of polymers are alternately laminated in one direction as shown in FIG. 1, the number of divisions (number of stacks) is compared with that of the composite fiber of the present invention. Since the value of the total interface length / fiber cross-sectional area is small, fibrils are generated in a large number of single fibers even if the number of frictions is 20 or less, and the wear resistance is inferior. Further, also in the weaving process, fibrilization occurs, yarn breakage occurs frequently, and there is a problem in high-order processing passability.
  • Comparative Example 4 In the method described in Comparative Example 3, all were carried out in the same manner as in Comparative Example 3 except that a composite plate provided with a flow path for discharging only the component A was used around the fine flow path in which both components were laminated in eight layers. ..
  • the evaluation results of this composite fiber are as shown in Table 3.
  • the multi-layer laminated structure as shown in FIG. 9 is a composite structure (coated type unidirectional laminated fiber 6) in which the A component is coated, the laminated structure thereof.
  • the number is significantly smaller than that of the composite fiber of the present invention, and the value of the total interface length / fiber cross-sectional area is small. Therefore, even when a coating is provided on the fiber surface, the number of frictions is 20 or less. Many single fibers were fibrillated and had poor wear resistance.
  • Example 15 As component A, polyethylene terephthalate (PET, melt viscosity: 120 Pa ⁇ s, melting point: 254 ° C, SP value: 21.4 MPa 1/2 ), and as component B, 5-sodium sulfoisophthalic acid 8.0 mol%, polyethylene.
  • PET polyethylene terephthalate
  • SSIA-PEG copolymerized PET melt viscosity: 95 Pa ⁇ s, melting point: 233 ° C., SP value: 22.9 MPa 1/2
  • the solubility parameter difference between these polymers is 1.5 MPa 1/2 .
  • the composite ratio of the A / B component is set to 80/20, and the composite polymer is poured into the spinning pack incorporating the composite base 10 illustrated in FIG.
  • the flow was discharged.
  • the composite plate F is provided with a microchannel H capable of alternately laminating both components in 128 layers, and is in a composite form in which two types of polymers as shown in FIG. 1 are alternately laminated in one direction. Discharged like this.
  • the yarn was wound at a spinning speed of 1000 m / min, and undrawn yarn having a 300 dtex-24 filament (total discharge amount: 30 g / min) was collected.
  • the wound unstretched fiber was stretched 3.6 times between rollers heated to 90 ° C. and 130 ° C. to obtain a stretched fiber of 84dtex-24 filament.
  • the U% (H) which is an index of fineness spots, was 0.6%, and the thickness uniformity in the fiber axis direction was excellent.
  • the composite fiber had a plate-like laminated structure in which the stacking directions were aligned as shown in FIG. 1 and was a multilayer laminated fiber.
  • the cross section of the obtained flat ultrafine fibers was observed, it was a ribbon-shaped cross section in which the lengths of the major axis and the minor axis were remarkably different, the flatness was 80, and the average thickness was 225 nm. Further, the variation in the thickness of the cross section was 36%, the degree of unevenness was 30%, the thickness had an appropriate variation, and the surface had an appropriate unevenness.
  • a woven fabric composed of flat ultrafine fibers is dipped in a dyeing solution prepared by adjusting an imtainable dye (acidic black dye) to 10% owf, and treated with a bath ratio of 1:50, a treatment temperature of 30 ° C., and a treatment time of 30 minutes.
  • a dyeing solution prepared by adjusting an imtainable dye (acidic black dye) to 10% owf, and treated with a bath ratio of 1:50, a treatment temperature of 30 ° C., and a treatment time of 30 minutes.
  • a woven fabric composed of flat ultrafine fibers is treated with a 10% aqueous solution of dodecane diacid dihydrazide as a solid content at 20% off, a bath ratio of 1:20, a treatment temperature of 130 ° C., and a treatment time of 1 hour. Odor function processing was performed.
  • the concentration decreased from the initial concentration of 30 ppm to 2 ppm in 10 minutes, and it had a high deodorizing property.
  • the content of the functional substance is 5.0%, the content after washing does not decrease significantly to 4.2%, a large amount of the functional substance is adsorbed, and it is hard to fall off and has high durability. It was a thing.
  • Example 16 and 17 In the method described in Example 15, all except that the total number of layers of the components A and B was changed to a composite plate having a microchannel for laminating 64 layers (Example 16) and 32 layers (Example 17). It was carried out in the same manner as in Example 15. These composite fibers were subjected to the same dissolution treatment as described above to generate flat ultrafine fibers. The evaluation results of these composite fibers and flat ultrafine fibers are as shown in Table 4.
  • Examples 16 and 17 had an ultrathin cross-sectional shape with a high flatness, although the degree was different, and had an appropriate variation in the length of the minor axis and a degree of unevenness.
  • the flat ultrafine fibers had a dense fiber bundle structure in which the directions were aligned and overlapped, but the flatness decreased and the average layer thickness increased as compared with Example 15. Therefore, the interfiber voids of the fiber bundle were coarse, and the aggregated portions of the single fibers were small. When immersed in the non-dyeable dye, the dye was distributed so as to be contained in the fiber bundle.
  • Example 15 since the specific surface area is reduced as compared with Example 15, the content of the functional substance is slightly reduced, but the high content is maintained, and sufficient deodorant property is exhibited. rice field. In addition, even after washing, the high content of functional substances was maintained, and it was difficult for the functional substances to fall off.
  • Example 18 In the method described in Example 15, all except that the total number of layers of the A component and the B component was changed to a composite plate having a microchannel for laminating 256 layers (Example 18) and 512 layers (Example 19). It was carried out in the same manner as in Example 15. These composite fibers were subjected to the same dissolution treatment as described above to generate flat ultrafine fibers. The evaluation results of these composite fibers and flat ultrafine fibers are as shown in Table 4.
  • an ultrathin ribbon-shaped cross section having an extremely high flatness had an appropriate variation in the length of the minor axis and a degree of unevenness.
  • the flat ultrafine fibers had a dense fiber bundle structure in which the directions were aligned and overlapped, but the flatness was increased and the average of the minor axis was increased as compared with Example 15. Since the length is reduced, the interfiber voids of the fiber bundles are extremely small, ranging from several nm to several tens of nm, and the single fibers are aggregated as if they were adhered to each other in the entire fiber bundle. When immersed in the non-dyeable dye, the dye was distributed so as to be contained in the fiber bundle.
  • the average length of the short axis was extremely short, so that the woven fabric was excessively flexible and inferior in handleability. Since the specific surface area was increased as compared with Example 15, the content of the functional substance was increased and the deodorant property was excellent. In addition, since the fiber bundle has a strong aggregated structure containing the functional substance, the content of the functional substance does not easily decrease even after washing, and the functional substance can be retained with high durability.
  • Comparative Example 5 is a round cross-section fiber having a general fiber diameter, has a small specific surface area, and has a sparse structure in which the distance between single fibers is large even as a fiber bundle. No dye adhesion was observed when immersed in the non-staining dye.
  • the specific surface area is small, the content of the functional substance is small, and the deodorant property is inferior.
  • the content of the functional substance was reduced to nearly 0 by washing, and the functional substance adhering to the fiber surface was easily removed.
  • Example 6 All were carried out in the same manner as in Example 15 except that a spinning pack incorporating an 8-island type sea-island composite mouthpiece in which the A component was an island component and the B component was a sea component was used.
  • the sea-island composite fiber was subjected to the same dissolution treatment as described above to generate ultrafine fibers.
  • the evaluation results of these ultrafine fibers are as shown in Table 4.
  • Comparative Example 6 was an ultrafine fiber having a significantly reduced fiber diameter and a large specific surface area. Moreover, in the fiber bundle, the distance between the single fibers was short. When immersed in the non-staining dye, the woven fabric was not colored, and no dye adhesion was observed between the fibers. When functionally processed, the specific surface area increased due to the ultra-thinning, so the functional substance adhered to a moderate degree, but it did not exhibit high deodorant properties, and the amount of the functional substance adsorbed by washing increased. It was a significant decrease.
  • Example 7 In the method described in Example 15, all the steps were carried out in the same manner as in Example 15 except that the total number of layers of the A component and the B component was changed to a composite plate provided with a microchannel for laminating eight layers. The composite fiber was subjected to the same dissolution treatment as described above to generate flat fiber. The evaluation results of the composite fiber and the flat fiber are as shown in Table 4.
  • the flat fiber 7 of Comparative Example 7 had a cross-sectional shape with a low flatness. Further, since the flatness is low, in the multifilament, the directions of the flat fibers 7 as shown in FIG. 11 are not aligned, and the fibers have a fiber bundle structure in which the distances between the single fibers are separated. No dye adhesion was observed when immersed in the non-staining dye. In addition, since the specific surface area is small, the content of the functional substance is small, and the deodorant property is inferior. In addition, the content of the functional substance was reduced to nearly 0 by washing, and the functional substance adhering to the fiber surface was easily removed.
  • Example 20 In the method described in Example 15, all were carried out in the same manner as in Example 15 except that a composite plate having a flow path diameter different from that of the fine flow path having a merging portion and a branching portion was used.
  • the composite fiber was subjected to the same dissolution treatment as described above to generate flat ultrafine fibers.
  • the evaluation results of the composite fiber and the flat ultrafine fiber are as shown in Table 5.
  • Example 20 had an ultrathin cross-sectional shape with a high flatness similar to that of Example 15, but due to a change in the flow path design of the composite plate, the variation in the length of the minor axis and the degree of unevenness were small and homogeneous. It was a thing. Further, it had a dense fiber bundle structure in which the directions of the flat ultrafine fibers were aligned and overlapped as in Example 15, but since the degree of unevenness was small, the interfibers of the fiber bundles were compared with those of Example 15. There was a large proportion of fine voids of several nm to several hundred nm.
  • the dye When immersed in the non-dyeable dye, the dye was contained in the fiber bundle but not uniformly distributed as a whole, and a part where the dye was not contained was observed. Further, as compared with Example 15, since the dispersibility of the single fiber was low, the content of the functional substance was slightly inferior, but it was difficult for the functional substance to fall off by washing.
  • Example 21 In the method described in Example 15, the component A is polyamide-6 (N6, melt viscosity: 100 Pa ⁇ s, melting point: 225 ° C., SP value: 23.7 MPa 1/2 ), and the component B is 5-sodium sulfoisophthalic acid. 280 ° C. as polyethylene terephthalate (SSIA-PEG copolymerized PET, melt viscosity: 95 Pa ⁇ s, melting point: 233 ° C., SP value: 22.9 MPa 1/2 ) obtained by copolymerizing 8.0 mol% and 9 wt% polyethylene glycol. Everything was carried out in the same manner as in Example 1 except that the yarn was spun in. The solubility parameter difference of the combined polymer is 0.8MP 1/2 .
  • the composite fiber was subjected to the same dissolution treatment as described above to generate flat ultrafine fibers. The evaluation results of the composite fiber and the flat ultrafine fiber are as shown in Table 5.
  • Example 21 had an ultrathin cross-sectional shape with a high flatness similar to that of Example 15, but because hydrogen bonds acted between the fibers, the fiber bundles aggregated more densely than in Example 15. It was a structure.
  • the fibers showed the same content of functional substances as in Example 15, and since the fibers were connected by hydrogen bonds, they swelled during washing and were easily redispersed into single fibers, which was higher than in Example 15. Functional substances were easily removed by washing.
  • Example 22 In the method according to Example 15, the component A is polypropylene (PP, melt viscosity: 70 Pa ⁇ s, melting point: 165 ° C., SP value: 16.8 MPa 1/2 ), and the component B is 5-sodium sulfoisophthalic acid 8. Spinned at 280 ° C as polyethylene terephthalate (SSIA-PEG copolymerized PET, melt viscosity: 95 Pa ⁇ s, melting point: 233 ° C, SP value: 22.9 MPa 1/2 ) obtained by copolymerizing 0 mol% and 9 wt% polyethylene glycol. Everything except that was carried out in the same manner as in Example 15.
  • the solubility parameter difference of the combined polymer is 6.1 MPa 1/2 .
  • the cross-sectional morphology of this composite fiber was observed, the cross-sectional formability became unstable due to the large difference in solubility parameter, and an irregular laminated structure in which the laminating direction was changed locally in the cross section, which was different from Example 15, was obtained. Had had.
  • the composite fiber was subjected to the same dissolution treatment as described above to generate flat ultrafine fibers.
  • the evaluation results of the composite fiber and the flat ultrafine fiber are as shown in Table 5.
  • Example 22 since the flatness is lower and the specific surface area is reduced as compared with Example 15, the content of the functional substance is reduced, but the content is high, and the functional substance is released by washing. It was hard to fall off.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Multicomponent Fibers (AREA)

Abstract

La présente invention concerne une fibre composite dans laquelle la somme des longueurs des interfaces qui sont formées par deux types ou plus de polymères qui constituent une section transversale de fibre est extrêmement élevée. Une fibre composite selon la présente invention a une section transversale de fibre qui est composée d'au moins deux types de polymères qui forment une pluralité d'interfaces ; la valeur obtenue en divisant la somme des longueurs d'interface entre deux types de polymères par l'aire de la section transversale de fibre est égale ou supérieure à 0,0010 nm-1 ; et les interfaces sont continues dans la direction de l'axe des fibres.
PCT/JP2021/046396 2020-12-18 2021-12-15 Fibre composite et multifilament WO2022131312A1 (fr)

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JP2021575507A JPWO2022131312A1 (fr) 2020-12-18 2021-12-15
EP21906673.5A EP4265828A1 (fr) 2020-12-18 2021-12-15 Fibre composite et multifilament
US18/267,798 US20240110314A1 (en) 2020-12-18 2021-12-15 Conjugate fiber and multifilament
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Citations (9)

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JPS60246725A (ja) * 1985-03-05 1985-12-06 カネボウ株式会社 清掃用織・編物
JPH01132812A (ja) 1987-11-16 1989-05-25 Toray Ind Inc 多葉型繊維
JPH0726433A (ja) * 1993-07-07 1995-01-27 Toyobo Co Ltd 複合マルチフィラメント
JPH07195603A (ja) * 1993-12-29 1995-08-01 Nissan Motor Co Ltd 近紫外線と近赤外線の一方あるいは両方を反射する構造体
JPH08246337A (ja) * 1995-03-07 1996-09-24 Kanebo Ltd フィブリル化繊維又は布帛
JPH11181630A (ja) 1997-05-02 1999-07-06 Teijin Ltd 複合繊維
JPH11189911A (ja) * 1997-12-24 1999-07-13 Nissan Motor Co Ltd 複合繊維構造体の製造方法及び製造用紡糸口金
JP2000282333A (ja) 1999-03-31 2000-10-10 Kuraray Co Ltd 接合型複合ステープル繊維及びその製造方法
JP2017115254A (ja) * 2015-12-22 2017-06-29 東レ株式会社 多層積層繊維

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60246725A (ja) * 1985-03-05 1985-12-06 カネボウ株式会社 清掃用織・編物
JPH01132812A (ja) 1987-11-16 1989-05-25 Toray Ind Inc 多葉型繊維
JPH0726433A (ja) * 1993-07-07 1995-01-27 Toyobo Co Ltd 複合マルチフィラメント
JPH07195603A (ja) * 1993-12-29 1995-08-01 Nissan Motor Co Ltd 近紫外線と近赤外線の一方あるいは両方を反射する構造体
JPH08246337A (ja) * 1995-03-07 1996-09-24 Kanebo Ltd フィブリル化繊維又は布帛
JPH11181630A (ja) 1997-05-02 1999-07-06 Teijin Ltd 複合繊維
JPH11189911A (ja) * 1997-12-24 1999-07-13 Nissan Motor Co Ltd 複合繊維構造体の製造方法及び製造用紡糸口金
JP2000282333A (ja) 1999-03-31 2000-10-10 Kuraray Co Ltd 接合型複合ステープル繊維及びその製造方法
JP2017115254A (ja) * 2015-12-22 2017-06-29 東レ株式会社 多層積層繊維

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US20240110314A1 (en) 2024-04-04
EP4265828A1 (fr) 2023-10-25

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