CN116583634A - Composite fiber and multifilament - Google Patents
Composite fiber and multifilament Download PDFInfo
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- CN116583634A CN116583634A CN202180084298.7A CN202180084298A CN116583634A CN 116583634 A CN116583634 A CN 116583634A CN 202180084298 A CN202180084298 A CN 202180084298A CN 116583634 A CN116583634 A CN 116583634A
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- KMGARVOVYXNAOF-UHFFFAOYSA-N benzpiperylone Chemical compound C1CN(C)CCC1N1C(=O)C(CC=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 KMGARVOVYXNAOF-UHFFFAOYSA-N 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/253—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
- 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
- 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
- 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
Landscapes
- 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
The present invention provides a composite fiber in which the sum of the lengths of the interfaces formed by 2 or more polymers constituting the fiber cross section is extremely large. The composite fiber of the present invention is made of more than 2 kinds of polymers, has a fiber cross section formed with a plurality of interfaces, and has a value of 0.0010nm obtained by dividing the sum of interface lengths formed by the 2 kinds of polymers by the area of the fiber cross section ‑1 The interface is continuous in the fiber axis direction as described above.
Description
Technical Field
The present invention relates to a composite fiber and a multifilament each composed of 2 or more components.
Background
Synthetic fibers made of polyester, polyamide, or the like are used in a wide range of applications from clothing to industrial applications because of their excellent mechanical properties and dimensional stability. In recent years, the diversity of applications has further progressed, and there are cases where the required characteristics are higher and more functional, and fibers made of conventional polymers cannot cope with them. In addition, a composite spinning method in which conventional polymers are combined is often selected from the viewpoints of cost and reduction in the period required for development of the polymer, although redesigning the polymer to achieve the desired characteristics is also considered.
In the fiber obtained by the composite spinning method, the so-called composite fiber, the other polymer is coated with the main polymer or the like in the fiber cross section (cross section in the axial direction of the fiber), and a feeling effect such as appearance and feel which cannot be achieved by a fiber composed of a single polymer can be imparted. In addition, even if a functional polymer which is problematic in terms of chemical resistance, heat resistance, and the like and is not practically usable is used as a composite fiber, if it is coated with another polymer, the chemical resistance, heat resistance, and the like can be drastically improved and put to practical use.
Various composite forms and target effects exist among composite forms and target effects of composite fibers, but as a common problem, there is a problem that when affinity of a polymer to be combined is poor, interfaces where 2 polymers come into contact are peeled off when an external force such as an impact is applied to the fibers. This interfacial delamination not only impairs the effect that is the original object, but also propagates cracks generated by the delamination to the fiber surface, which makes the wire-making and the wire-breaking in advanced processing steps frequent, and makes stable production itself difficult.
Such problems may be solved by working out the composite form of the composite fiber, and for example, patent document 1, patent document 2, and patent document 3 propose the composite form of the fiber.
Patent document 1 proposes a fiber having a composite cross section in which a series of laminated structures of 2 kinds of polymers are alternately laminated and a plurality of bonded in a direction perpendicular to the lamination direction. In this technique, a plurality of film-like elements constituting a fiber cross section are formed, the interface occupied by each film-like element is increased, and a backbone-like skeleton portion bonded between the laminated structures is used as a core for supporting each film-like element, so that the improvement of the process-passability is aimed at by suppressing the interface separation.
Patent document 2 proposes a composite fiber in which the outer periphery of a laminated structure in which 2 kinds of polymers are alternately laminated is covered with a protective layer. As in patent document 1, the technique aims at suppressing interfacial delamination of a laminated structure, and aims at improving abrasion resistance by coating the outer periphery of the laminated structure with a high-strength polymer having a specific thickness.
Patent document 3 also proposes a composite fiber in which the outer periphery of a laminated structure in which 2 kinds of polymers are alternately laminated is entirely coated. The technique of providing a coating film on the outermost periphery of the laminated structure reduces peeling and fiber cutting in the process, and aims at improving the process-passing performance as in patent document 2, but this technique aims at producing ultrafine fibers by degrading the outermost periphery of the coating film by treatment under specific conditions and promoting peeling and fiber cutting.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 1-132812 (pages 1-2)
Patent document 2: japanese patent laid-open No. 11-181630 (claims)
Patent document 3: japanese patent laid-open No. 2000-282333 (pages 1-3)
Disclosure of Invention
Problems to be solved by the invention
Although patent document 1 describes that the fiber cross section is composed of a plurality of film-like elements, in the examples, the material actually produced is a material in which at most 2 adjacent structural bodies having 50 to 65 layers are bonded, and there is a limit in the interface length, which may be insufficient for suppressing peeling of each film-like element. In addition, even if the number of layers is increased by taking the manufacturing method into consideration, it is theoretically impossible to stably increase the number of layers.
In patent documents 2 and 3, the presence of the protective layer having abrasion resistance may provide an effect of suppressing interfacial peeling with respect to weak friction acting on the fiber surface. However, the laminate structure in the fiber is similar to the laminate structure of patent document 1 in the number of layers, and there are cases where a large external force is applied and interfacial separation occurs due to repeated rubbing. In addition, when interfacial peeling occurs, the cracks generated by peeling may propagate to the protective layer on the fiber surface, and particularly, the protective layer may have a weak structure against repeated rubbing or the like, and when the multilayer laminated structure is exposed to the surface, the protective layer may be exposed to chemicals or heat, and thus the properties of the fiber may be greatly impaired, and the quality may be greatly reduced.
As described above, with the conventional composite spinning method, it is difficult to suppress interfacial separation in the fiber interior of the obtained fiber. Further, even if apparent fiber cutting or the like is suppressed by coating the outer periphery of the laminated structure, the possibility of occurrence of interfacial peeling is high for the laminated structure inside thereof, and use is sometimes limited from the viewpoint of durability.
Accordingly, there is a strong demand for a conjugate fiber having improved durability such as abrasion resistance, chemical resistance and heat resistance.
Means for solving the problems
The above object is achieved by the following means.
(1) A composite fiber comprising 2 or more polymers having a fiber cross section in which a plurality of interfaces are formed, wherein the sum of the lengths of the interfaces formed by the 2 polymers divided by the area of the fiber cross section has a value of 0.0010nm -1 The above interface is continuous in the fiber axis direction.
(2) The conjugate fiber according to the above (1), wherein the sum of the interfacial lengths of the 2 polymers is divided by the aboveThe value of the cross-sectional area of the fiber was 0.0050nm -1 The above.
(3) The conjugate fiber according to the above (1) or (2), wherein the fiber cross section has a multilayer structure in which 2 kinds of polymers are alternately laminated.
(4) The conjugate fiber according to any one of the above (1) to (3), wherein the variation (CV value) in the layer thickness of at least 1 polymer is 10% or more.
(5) The conjugate fiber according to any one of the above (1) to (4), wherein the average layer thickness of at least 1 polymer is 1000nm or less.
(6) A multifilament yarn comprising flat ultrafine fibers, wherein the flat ultrafine fibers are composed of 1 polymer remaining after 1 polymer among 2 polymers constituting the multilayer laminate structure is removed from the composite fiber of (3).
(7) The multifilament according to the item (6), wherein the flat ultrafine fiber has a flat fiber cross section, the flat degree of 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 is 15 or more, and the average thickness of the flat ultrafine fiber is 1000nm or less.
(8) The multifilament according to the item (6) or (7), wherein the variation in thickness (CV value) of the flat ultrafine fiber is 10% or more.
(9) The multifilament yarn according to any one of (6) to (8), wherein the polymer constituting the flat ultrafine fiber comprises at least 1 polymer selected from the group consisting of polyesters, polyamides and polyolefins.
(10) The multifilament according to any one of the above (6) to (9), wherein a functional substance is enclosed in a fiber bundle composed of the flat ultrafine fibers.
(11) A fiber product comprising the conjugate fiber according to any one of (1) to (5) or the multifilament according to any one of (6) to (10) in at least a part thereof.
ADVANTAGEOUS EFFECTS OF INVENTION
The composite fiber of the present invention is uniformly dispersed in a plurality of interfaces existing in the cross section of the fiber even when an external force is applied to the fiber due to an increase in the length of the interface between the polymers, and thus the load is suppressed from concentrating on a part of the cross section of the fiber, and even in a fiber formed by compositing 2 or more polymers, the separation between the components is greatly suppressed. Accordingly, a composite fiber and a multifilament excellent in durability such as abrasion resistance, chemical resistance and heat resistance can be provided.
Drawings
Fig. 1 is a schematic view of a cross section of unidirectional ply fiber as an aspect of the present invention.
Fig. 2 is an enlarged view of a portion of fig. 1.
Fig. 3 is a schematic cross-section of a radial ply fiber as an alternative aspect of the invention.
Fig. 4 is a schematic view of a cross section of concentric circular laminate fiber as another aspect of the present invention.
FIG. 5 is a schematic drawing of a cross section of flat microfine fibers constituting the multifilament yarn of the present invention.
Fig. 6 is a schematic drawing of a cross section of a multifilament yarn of the invention.
Fig. 7 is a schematic view of a cross section of a multifilament in the case where a functional substance is added to the multifilament of the present invention.
Fig. 8 is a cross-sectional view of a composite die for explaining an example of a method for producing a composite fiber according to the present invention.
Fig. 9 is a schematic cross-sectional view of a conventional film-coated unidirectional laminated fiber.
Fig. 10 is a schematic view of a cross section of a conventional flat fiber.
Fig. 11 is a schematic view of a cross section of a fiber bundle composed of conventional flat fibers.
Detailed Description
The present invention will be described in detail with reference to preferred embodiments.
The conjugate fiber in the present invention is a fiber composed of 2 or more polymers. The composite fiber of the present invention is characterized by having a composite form in which the sum of the lengths of the interfaces (interface lengths) formed from 2 kinds of polymers is extremely large in comparison with conventional composite fibers in a cross section (fiber cross section) in the axial direction of the fiber.
The composite form in which the sum of the interfacial lengths of the 2 polymers is extremely large is defined by the sum of the interfacial lengths and the area of the fiber cross section (hereinafter, also referred to as the fiber cross section area.) and means that the value obtained by dividing the sum of the interfacial lengths by the fiber cross section area is 0.0010nm, where the length of the fiber cross section of the interfacial surface formed of the 2 polymers, which is continuous in the fiber axis direction, is defined as the interfacial length -1 The above composite forms.
In the present invention, the value obtained by dividing the sum of the interfacial lengths by the fiber cross-sectional area is obtained as follows.
That is, the multifilament yarn composed of the composite fiber is embedded with an embedding agent such as an epoxy resin, and an image is taken with a Transmission Electron Microscope (TEM) at a magnification at which the interface between the polymers can be recognized. When the entire 1 interface among the 1 images does not completely enter, a series of images may be captured by tracing the same interface in the fiber section until the image is returned to the imaging start position again, with the imaging start position being the position at which the image was first captured. When the interface reaches the outer periphery of the fiber cross section, a series of images is captured, which follow the outer periphery until the image is returned again to the imaging start position. In this case, if only a specific polymer is subjected to electron dyeing, the contrast of the interface becomes clear, and the measurement to be described later can be efficiently performed, which is preferable.
The measurement start point is arbitrarily determined for 1 interface of the image located at the imaging start position by using image analysis software, and the length from the measurement start point to the point where the same interface is returned again after being traced by a series of cross-sectional images is measured. At this time, when the fiber cross section reaches the outer peripheral portion until the measurement start point is returned, the length of the portion passing through the outer peripheral portion is not included and the measurement is performed. The value is expressed as an integer in nm (decimal point is rounded off) by setting the value to 1 interface length. The same measurement was performed on all interfaces of the fiber cross section, and the sum of the interface lengths obtained by adding them was divided by The calculated value is expressed in nm by the fiber cross-section -1 The unit count is calculated by rounding the 5 th bit after the decimal point. The cross-sectional area of the fiber was taken 2-dimensionally with a stereo microscope at a magnification at which the entire cross-section of 1 fiber could be observed, and the cross-section was extracted by 2-valued processing using image analysis software, and the area was measured in nm 2 The integer count of the unit is obtained by rounding off the decimal point. In the case where the fiber cross section of the composite fiber of the present invention is composed of 3 or more polymers, the total of the interface lengths of the interfaces formed by the combination of all the polymers is not only the interface of the specific 2 polymers.
The composite fiber of the present invention is characterized by having a composite form in which the sum of the lengths (interface lengths) of the interfaces formed by the adjacent 2 polymers is extremely large in the cross section of the fiber, and the value obtained by dividing the sum of the interface lengths by the cross section of the fiber is required to be 0.0010nm as an index of the composite form -1 Above, and the interface is required to be continuous in the fiber axis direction. If the ratio is within this range, the interfacial length per unit area of the fiber cross section is extremely large, which means that 2 or more polymers forming a composite cross section are finely divided into a plurality of elements. Here, the term "element" refers to a polymer that is separated by surrounding the fiber cross section with a different kind of polymer.
As described above, the composite fiber of the present invention is characterized by having a composite form in which the different types of polymers are finely divided into a plurality of elements in the fiber cross section, and the sum of the interfacial lengths of the 2 types of polymers is extremely large compared with the conventional one, and by this composite form, various excellent effects as described below can be exhibited.
That is, the composite fiber of the present invention has an extremely large sum of the interface lengths, and even when an external force is applied to the fiber, the force is dispersed in the interfaces existing in the fiber cross section, and the concentration of the load in a part of the fiber cross section is suppressed, so that even in the fiber formed by compounding 2 or more polymers, the separation between the components can be greatly suppressed.
If the sum of the interfacial lengths of the composite fibers of the present invention is divided by the fiber cross-sectional area, the value is 0.0010nm -1 In the above-mentioned manner, even when the composite fiber is composed of 2 kinds of polymers having poor affinity, interfacial separation between components is less likely to occur, breakage in the filament making and advanced processing steps is less likely to be induced, and the composite fiber can be processed into a textile product with high quality while maintaining good handleability.
The larger the value obtained by dividing the sum of the interface lengths by the fiber cross-sectional area, the more preferable is from the viewpoint of equally dispersing the forces to a plurality of interfaces existing in the fiber cross-section. If the sum of the interface lengths is divided by the cross-sectional area to obtain a value of 0.0050nm -1 As described above, even when a conjugate fiber is formed of 2 kinds of polymers having poor affinity and is used for applications in which general clothing and the like are subjected to weak abrasion, an effect of suppressing separation between components is obtained, and this is cited as a preferable form. If the above-mentioned points are advanced, if the value obtained by dividing the sum of the interface lengths by the cross-sectional area is 0.0200nm -1 As described above, even when the composite fiber composed of 2 kinds of polymers having poor affinity is used for application to a medium-strength scratch represented by an outdoor-oriented product, separation between components can be effectively suppressed, and a more preferable form is exemplified. Furthermore, if the sum of the interface lengths is divided by the cross-sectional area, the value is 0.0500nm -1 As described above, even when the film is used in applications such as work clothes where strong rubbing is repeatedly applied, separation between components is suppressed, and a particularly preferable embodiment is exemplified.
Further, for the composite fiber of the present invention, the value obtained by dividing the sum of the interface lengths by the cross-sectional area was 0.0050nm -1 In addition to the improvement of the mechanical properties, even when the 1 component constituting the composite fiber is a polymer having poor chemical resistance and heat resistance, the use of a polymer having excellent properties as the other component can impart excellent chemical resistance and heat resistance. Improvements in and relating to such chemical and thermal propertiesThe layer having the characteristics of the 2 polymers formed near the interface exhibits its effect by a drastic increase in the interface length. That is, in the layer near the interface formed of different polymers, the molecular chains of the different polymers may intrude into each other to form an interface layer having characteristics of 2 kinds of polymers. When the interface length in the fiber cross section is dramatically increased as in the composite fiber of the present invention, the interface layer occupies a large ratio, and the characteristics of the interface layer are exhibited, so that excellent effects are exhibited from the viewpoint of compositing of polymer characteristics.
In the composite fiber of the present invention, if the value obtained by dividing the sum of the interface lengths by the fiber cross-sectional area is 0.0050nm -1 As described above, the ratio of the interfacial layer in the fiber cross section is high, and for example, even when the composite fiber composed of the easily soluble polymer and the poorly soluble polymer is subjected to the dissolution treatment, the reduction in the fiber weight after the treatment is slight, and excellent chemical resistance is obtained, and thus, this is preferable. The larger the value obtained by dividing the sum of the interface lengths by the cross-sectional area of the fiber is, the more suitable from the viewpoint of increasing the ratio of the interface layers in the cross-section of the fiber, if the value obtained by dividing the sum of the interface lengths by the cross-sectional area is 0.0200nm -1 In the above, even when the chemical treatment is performed for a long period of time, the decrease in the weight of the fiber can be made extremely slight, and a more preferable form is exemplified. If the above-mentioned points are advanced, if the value obtained by dividing the sum of the interface lengths by the cross-sectional area is 0.050nm -1 As described above, even after a long-term chemical treatment, the decrease in the fiber properties such as mechanical properties is greatly suppressed, and thus a particularly preferable form is exemplified.
Thus, in the composite fiber of the present invention, the larger the value obtained by dividing the sum of the interfacial lengths by the fiber cross-sectional area is, the more remarkable the effect of the characteristic cross-sectional morphology is exhibited, and a preferable upper limit of the value is less than 1.000nm -1 . In general, interfaces where different kinds of polymers come into contact are hydrodynamically prone to becoming unstableIn some cases, it is difficult to stably form a continuous interface when the interface length is extremely large as in the present invention. If the sum of the interface lengths divided by the fiber cross-sectional area is less than 1.000nm -1 Since the interface continuous in the fiber axis direction can be formed relatively easily even when polymers having different rheological properties are compounded, various combinations of polymers can be applied as the composite fiber of the present invention, and a preferable upper limit is given.
As described above, the composite fiber of the present invention is characterized by having a composite form in which the interface length formed by 2 kinds of polymers is extremely large, and by this composite form, not only an excellent effect is brought about in mechanical properties, but also excellent effects can be brought about in chemical properties and thermal properties by further increasing the interface length. While there are various composite forms among the composite forms having extremely large interfacial lengths, from the viewpoint of promoting the effect exerted by the composite fiber of the present invention, the composite fiber of the present invention is preferably a multilayer laminated structure in which 2 kinds of polymers are alternately laminated in cross section.
If the composite fiber of the present invention has such a structure, the polymer of different types is finely divided into a plurality of film-like elements (layers) in the fiber cross section, and even when 1 layer of the plurality of layers constituting the cross section is peeled off by the interface and cracks occur, the layers are finely structured, so that propagation of the cracks can be prevented. Therefore, the breaking can be suppressed from proceeding in the radial direction of the fiber cross section, and even when repeated rubbing is applied, fibrillation and fiber cutting can be effectively suppressed.
From the viewpoint of preventing propagation of the crack, the more the number of layers of the multi-layer laminated structure of the fiber cross section is, the finer the crack can be made. In the case of application to industrial products or the like in which strong rubbing is repeatedly applied, if the number of layers of 2 polymers is 250 or more, fibrillation on the fiber surface can be effectively suppressed, and a preferable range is given. In addition, in the case of use for applications where cracks are particularly likely to occur, such as repeated bending, if the number of stacked layers is 500 or more, crack propagation can be stopped in an extremely small range of the fiber cross section, and thus a more preferable range is given. The number of layers referred to herein refers to the total number of film elements of 2 polymers present in the fiber cross section.
In the multilayer laminated structure, various laminated forms such as a form in which 2 kinds of polymers are alternately laminated in one direction (unidirectional laminated fibers 1 shown in fig. 1 and 2), a form in which the polymers are radially laminated (radial laminated fibers 2 shown in fig. 3), and a form in which the polymers are concentrically laminated (concentric laminated fibers 3 shown in fig. 4) can be used. The multilayer laminated structure is preferably a unidirectional laminate or a concentric laminate from the viewpoint of minimizing propagation of cracks. If the multilayer laminated structure is a unidirectional laminated structure or a concentric laminated structure, the size of the film-like element (layer) does not become large in the outer peripheral portion of the fiber cross section, and even in the outer peripheral portion which is susceptible to a large load due to bending deformation, the propagation of cracks can be suppressed to a minute range, and a preferable laminated structure is exemplified.
As described above, the composite fiber of the present invention has a multilayer laminated structure in its cross section, whereby the effect of improving mechanical properties can be enhanced, and further, the variation (CV value) in the layer thickness of at least 1 polymer constituting the multilayer laminated structure is made to be 10% or more, whereby interfacial delamination between components can be more effectively suppressed.
The variation in layer thickness is calculated by measuring the thicknesses of 100 layers of 1 polymer constituting the fiber cross section in terms of an integer in nm, which is present on a line bisecting the long sides of each layer perpendicularly, dividing the standard deviation by an arithmetic mean, and rounding off the coefficient of variation in% units in an integer in decimal. In the case of a radial stack, a concentric stack, or the like in which the layer thickness cannot be measured by the above method, the average value of the positions at which the thicknesses of the respective layers are maximum and the positions at which the thicknesses of the respective layers are minimum may be visually selected to be the layer thickness, and the deviation of the layer thickness is calculated from the arithmetic average and standard deviation of 100 layers. When the number of layers is less than 100 in the cross section of 1 composite fiber, the total of the cross sections of the composite fibers is 100 layers.
The thickness variation of the layer of the 1 polymer constituting the multilayer laminated structure is relatively large, and thus, there are thin and thick positions of the layer in the fiber cross section, and the influence of the interface layer is relatively strong in the thin position of the layer, so that stress concentration is less likely to occur, and the thick position of the layer is deformed in the vicinity of the interface, thereby dispersing the stress. By the synergistic effect of these, the generation of stress in the cross section changes in a complex manner, and the stress is relaxed everywhere in the fiber, so that interfacial separation between components can be effectively suppressed. If the variation in layer thickness of at least 1 polymer constituting the multilayer laminated structure is 10% or more, the internal stress is dispersed in a complicated manner in a cross section and fuzzing of the composite fiber is less likely to occur even when compression deformation is applied in a twisting step or the like, and a preferable range is exemplified. Further, if the thickness of at least 1 polymer layer constituting the multilayer laminated structure varies by 30% or more, hairiness due to interfacial peeling is less likely to occur even when strong compression deformation is applied under heating in a false twisting step or the like, and the multilayer laminated structure can be processed into a textile with high quality, and a more preferable range is exemplified.
In addition, from the viewpoint of further improving the effect of improving the mechanical properties of the composite fiber of the present invention, it is preferable that the average layer thickness of at least 1 polymer constituting the multilayer laminated structure is 1000nm or less. The average layer thickness of the polymer is more preferably 300nm or less, still more preferably 100nm or less, particularly preferably 50nm or less, and most preferably 30nm or less. The average layer thickness is calculated by rounding off the arithmetic average of the calculated layer thicknesses of the 1 polymer 100 layers constituting the fiber cross section to the decimal point in an integer of nm. When the number of layers is less than 100 in the cross section of 1 composite fiber, the total of the cross sections of the composite fibers is 100 layers.
The thickness of the layer becomes relatively thin, so that the proportion of the interface layer occupied by each 1 layer is relatively increased, and stress is easily transmitted between adjacent interface layers, and even when stress such as bending deformation is applied to the local deformation of the fiber cross section, the stress is dispersed throughout the cross section, and the interface is not easily peeled off.
Further, by setting the average layer thickness of at least 1 polymer constituting the multilayer laminated structure to 50nm or less, the effect can be made more remarkable in terms of chemical properties and thermal properties.
As described above, in the layer near the interface formed of different types of polymers, there is a case where the molecular chains of different polymers intrude into each other to form an interface layer having characteristics of 2 types of polymers, and the general thickness of the interface layer is generally considered to be about several nm to ten nm. That is, since the thickness of the layer of the polymer constituting the multilayer laminated structure is close to the thickness of the interface layer, most of 1 layer is constituted by the interface layer, and the effect of the interface layer in each layer becomes extremely remarkable, the effect of compositing the polymer characteristics is remarkable. In the cross section of the composite fiber of the present invention, if the average layer thickness of at least 1 polymer constituting the multilayer laminated structure is 50nm or less, most of the layers of the polymer are occupied by the interface layer. Thus, even when a soluble polymer is used as the polymer, if the other polymer is a poorly soluble polymer, the soluble polymer is hardly dissolved even when the dissolution treatment is performed, and excellent chemical resistance is exhibited, and a preferable range is exemplified. In addition, when a low-melting polymer and a high-melting polymer are selected and each polymer is alternately laminated so that the average layer thickness of the low-melting polymer becomes 50nm or less to form a multilayer laminated structure, an effect of suppressing fusion between fibers is exhibited even when the laminated structure is exposed to a high temperature equal to or higher than the melting point of the low-melting polymer. The average layer thickness is preferably such that the interfacial layer appears in each layer constituting the fiber cross section, and if the average layer thickness of 1 polymer is 30nm or less, even when the composite fiber formed by the combination of the above polymers is subjected to a long-time dissolution treatment or a heat treatment, the weight of the fiber is reduced and fusion between the fibers is suppressed, and thus the most preferable range is exemplified.
In addition, the average layer thickness of at least 1 polymer constituting the multilayer laminated structure is 50nm or less, so that the mechanical properties of the composite fiber of the present invention may be further improved from the viewpoint of improving the dispersibility of the additive. That is, the polymer constituting the composite fiber generally contains an additive such as titanium oxide, but these additives exist in an agglomerated state, and peeling is likely to occur at the interface between the coarse agglomerates and the polymer. The additive contained in the polymer is contained in the film having a multilayer laminated structure having a size equal to or smaller than the aggregation size, whereby the aggregation state is eliminated by the shearing force, and the dispersibility is improved, and even when repeatedly rubbed, the effect of suppressing the occurrence of cracks is obtained. If the average layer thickness of at least 1 polymer is 50nm or less, the additive is limited to a layer sufficiently thinner than the aggregation diameter of a general additive, so that the dispersibility of the additive is improved and excellent effects are exhibited in terms of abrasion resistance, and thus, a preferable range is included.
Further, the conjugate fiber of the present invention is suitable because the difference in solubility parameter (SP value) between 2 polymers compounded in the fiber cross section is 3.0 or less, thereby stabilizing the refinement immediately below the die, and the uniformity of the thickness in the fiber axis direction is excellent. Here, the difference in solubility parameter means a difference between the values of the components (evaporation energy/molar volume) 1/2 The defined parameter reflecting the cohesive force of the substance may be defined by, for example, "tap-tap", the Xudi chemical industry corporation/cartridge is edited together with the hub, the absolute value of the value obtained by subtracting the solubility parameter of one component from the solubility parameter of the other component, calculated from the value described in page 189 or the like, is the so-called solubility parameter difference in the present invention.
In general, in a composite fiber composed of 2 or more polymers, elongation and deformation behaviors of the respective polymers are different, and thus elongation and deformation in a spinning process and a drawing process tend to become unstable. In particular, when the solubility parameter difference of 2 polymers constituting the composite fiber is large, the instability is promoted, and the thickness unevenness in the fiber axis direction tends to become large. By making the difference in solubility parameter of 2 kinds of polymers among the constituent composite fibers 3.0 or less, elongation deformation in the spinning step and the drawing step is stabilized, and occurrence of excessive thickness unevenness in the fiber axis direction is suppressed. As a result, even when an external force such as stretching is applied, the stress can be equally applied in the fiber axis direction, and the concentration of the load on a part of the fiber axis direction can be suppressed, so that the occurrence of cracks at the interface between the components can be more effectively suppressed. Based on the above, in order to further improve the effect of improving the mechanical properties of the composite fiber of the present invention, the solubility parameter difference of 2 polymers constituting the composite fiber is preferably 3.0 or less.
The thickness unevenness in the fiber axis direction may be represented by a value of Uster (fineness unevenness) U% which is an index of fineness unevenness, and U% is preferably 1.5% or less. If the U% is 1.5% or less, even when an external force such as repeated stretching is applied, the load concentration in a part of the fiber axis direction can be suppressed, and thus the occurrence of cracks due to peeling between components constituting the fiber cross section can be suppressed. In addition, from the viewpoints of chemical properties and thermal properties, when the fineness unevenness is small, the chemical resistance and heat resistance in the fiber axis direction are also uniform, and defects due to extremely thin portions are also reduced, so that it is preferable to control U% to 1.5% or less.
The composite fiber of the present invention can exhibit excellent effects not only in terms of improvement of mechanical properties but also in terms of chemical properties and thermal properties by appropriately selecting the polymer to be combined by forming a composite form having an extremely large interfacial length, which has not been conventionally achieved. Accordingly, the composite fiber of the present invention can be widely used for general clothing applications such as underwear and outerwear, interior applications such as curtains and cloths, vehicle interior applications such as car seats, living applications such as rags and health products, applications for removing harmful substances such as filters, and applications for industrial materials such as battery separators.
Further, in the composite fiber of the present invention, 1 polymer out of 2 polymers constituting a multilayer laminated section is removed, whereby a multifilament yarn composed of flat ultrafine fibers composed of another 1 polymer can be obtained. That is, in the case of a composite fiber having a multilayer laminated cross section in which 2 kinds of polymers are alternately bonded as film-like elements (layers), when 1 kind of polymer is removed, a plurality of layers of another 1 kind of polymer are separated. These layers were each formed of flat ultrafine fibers, and multifilament 5 composed of flat ultrafine fibers 4 having a thin cross-section as shown in fig. 5 and 6 was obtained.
The multifilament is less likely to cause the occurrence of hairiness due to the characteristics of the composite fiber such as interfacial peeling, and therefore can be processed into a fiber product with high quality, and has extremely large specific surface area due to the characteristics of the composite fiber such as extremely large interfacial length. By virtue of the effect of the specific surface area, when the multifilament is subjected to functional processing, a large amount of functional substances are adsorbed, and excellent functionality can be exhibited.
In view of the above-described functionality and quality of the fiber material, the cross-sectional shape of the flat ultrafine fiber constituting the multifilament of the present invention is important from the viewpoint of securing long-term durability, and the fiber cross-section is flat, the flatness is extremely high, and the thickness thereof is important to be thin.
The flat shape herein refers to a shape in which the length of the major axis is different from the length of the minor axis, such as a rectangle or an ellipse, and the degree of flatness of the shape is defined as the flatness of a value obtained by dividing the length of the major axis by the length of the minor axis. For the multifilament yarn of the present invention, it is required that the flatness in the fiber cross section is 15 or more.
The flatness in the present invention is obtained by the following procedure (see also fig. 5).
The multifilament yarn of the present invention is embedded with an embedding agent such as an epoxy resin, a cross section of the fiber is cut by a microtome equipped with a diamond blade, and the cross section is photographed by a Scanning Electron Microscope (SEM) or the like at a magnification at which the cross section can be recognized. The maximum length of the cross section of the single fiber (flat ultrafine fiber) existing in the captured image was measured by using image analysis software, and this value was expressed by rounding off the decimal point and the like in an integer of nm, with the length of the long axis of the single fiber. Next, the length of the intersection of the fiber cross section with the line segment orthogonal to the line segment of the maximum length at the midpoint of the maximum length was measured, and this value was expressed as the length of the short axis of the single fiber by rounding the decimal point and thereafter in an integer of nm units. Using the length of the major axis and the length of the minor axis, the flatness of the filaments was calculated by the following formula.
Flatness = length in the long axis direction (nm)/length in the short axis direction (nm)
The flatness of each fiber was calculated by performing the above measurement on 100 fibers, and the arithmetic average of the calculated flatness was defined as the flatness of the present invention.
The multifilament of the present invention requires a flatness of 15 or more as an index of the cross-sectional shape, which is the 1 st element that the flatness of the fiber cross-section of the flat ultrafine fibers constituting the multifilament is high. When the specific surface area of the fiber is 2 times or more larger than that of a fiber having a circular cross section of the same fineness, the adsorption efficiency of the functional substance to be targeted can be improved.
If the flatness of the flat ultra-fine fibers is 15 or more, the multifilament 5 has a specific fiber bundle structure originating from the form of the flat ultra-fine fibers 4 as shown in fig. 6. That is, the flat ultrafine fibers are aligned in the direction of the alignment of the fibers due to the high shape anisotropy of the flat ultrafine fibers, and the directions of the flat ultrafine fibers are aligned and superposed. The fiber bundle structure greatly increases the number of fibers arranged per unit volume, and the fiber bundle structure interacts with the effect of increasing the specific surface area of 1 fiber, thereby achieving more excellent adsorption efficiency.
The fiber bundle herein is not limited to the form of a collection of a plurality of flat ultrafine fibers, and includes a form in which single fibers are clearly separated and a form in which single fibers are aggregated to become exactly 1 coarse fiber.
Based on the above technical idea, the higher the flatness, the more the specific surface area of the fibers is increased, and the more the fiber direction is aligned, the densely packed arrangement is made, and the shape is advantageous for producing a larger fiber area. That is, if the flatness is 30 or more, the specific surface area of the fiber is increased by 3 times or more compared with the round-section fiber having the same fineness, and the fiber is arranged more densely, so that the effect of increasing the surface area is more remarkable. In such a case, the adsorption efficiency of the functional substance is further improved, and the function thereof can be effectively found, so that the flatness is preferably 30 or more.
Further, if the flatness is 40 or more, the significant shape anisotropy suppresses the disturbance of the fiber direction in a part of the fiber bundle, and a dense arrangement pattern in which the fiber direction is uniform throughout is obtained. With such an arrangement, a uniform function is obtained without unevenness as a whole, and thus the flatness is more preferably 40 or more.
Further, if the flatness is 50 or more, even when the fiber bundle of the flat ultrafine fibers is twisted, the fibers are radially arranged without being disturbed with respect to the center of the fiber bundle, and the arrangement direction thereof can be arbitrarily changed while maintaining the arrangement form in which the fiber directions are uniform. Such a feature exerts an excellent effect of controlling the strength of the function derived from the functional substance, and when a change is desired to be imparted to the arrangement direction of the fibers, the flatness is particularly preferably 50 or more.
Further, as the flatness of the cross section increases, when an external force is applied in the processing step, bending and cracking tend to occur easily in the longitudinal direction of the cross section, but if the flatness is less than 500, there is no problem in practical use, and the object of the present invention can be achieved.
As described above, the multifilament of the present invention has a very high degree of flatness of the fiber cross section of the flat ultrafine fibers constituting the multifilament, and thus the specific surface area as the surface area per unit weight is increased as compared with a normal fiber, and further the fibers are densely arranged, whereby a very large fiber surface is generated when a fiber assembly is produced.
The specific surface area of the 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 in order to sufficiently increase the surface area due to the cross-sectional shape. As an index of fiber diameter, the multifilament of the present invention is required to have an average thickness of 1000nm or less, taking the thickness of flat ultrafine fibers, that is, the length of the short axis of the fiber cross section as the 2 nd element.
The average thickness is obtained by rounding off the decimal point and the whole number of the length of the minor axis of 100 fibers measured as described above.
When the average thickness of the flat ultrafine fibers is 1000nm or less, at least a specific surface area of the usual ultrafine fibers or more is obtained, and a high adsorption efficiency is achieved. For this reason, the multifilament of the present invention is required to have an average thickness of 1000nm or less of the flat ultrafine fibers.
As described above, the smaller the average thickness of the flat ultrafine fibers is, the more the effect of increasing the specific surface area of the individual fibers is promoted, and the further thickness affects the bending rigidity of the fibers, so that the effect of densification of the fiber bundles is excellent. That is, the bending rigidity in the short axis direction decreases in proportion to the cube of the thickness of the fiber, and the fiber becomes thinner, so that the fiber deforms flexibly against irregularities and the like, and can follow the shape, and the fiber bundle structure is easily densified. When the average thickness is 800nm or less, not only the effect of increasing the specific surface area is more enhanced, but also the fibers are deformed to follow the shape, so that the formation of coarse voids between the fibers can be effectively suppressed and a dense structure is easily obtained. For this reason, the average thickness is preferably 800nm or less.
Further, when the average thickness is 500nm or less, the softness of the fibers becomes limited, and the fibers are formed into bundles in which the filaments are exactly bonded to each other by intermolecular forces such as van der Waals forces. In such a case, the voids between fibers are extremely minute voids ranging from several nm to several hundred nm, and the average thickness is more preferably 500nm or less because they exert excellent effects in terms of the highly durable functional performance described later.
Further, if the average thickness is 300nm or less, the structure in which the single fibers are aggregated as described above is obtained uniformly throughout the fiber bundle, and the function is uniformly exhibited without unevenness throughout the fiber bundle when the function processing is performed. For this reason, it is particularly preferable that the average length of the minor axis is 300nm or less.
The multifilament of the present invention tends to be easily broken when an external force is applied during the processing step as the average thickness of the fiber cross section becomes smaller, but the multifilament of the present invention is practically usable without any problem if the average thickness is 50nm or more.
As described above, the multifilament yarn of the present invention has a cross-sectional shape extremely high in flatness of the flat ultrafine fibers constituting the multifilament yarn, and thus the specific surface area of the fibers is greatly increased, and further, the multifilament yarn becomes a dense fiber bundle having aligned directions, thereby producing a very large fiber surface per unit volume. If the large fiber surface is effectively utilized, not only the adsorption efficiency of the functional substance but also the durability can be dramatically improved by the specific fiber bundle structure. That is, when the multifilament yarn of the present invention is subjected to the functional processing, not only a large amount of the functional substance is adsorbed on the fiber surface, but also as shown in fig. 7, the functional substance D is incorporated between the flat ultrafine fibers 4 which are overlapped in the same direction. Therefore, the functional substance is contained in the fiber bundle in a large amount, while the functional substance is hardly released by rubbing or the like in a distributed state in which the surface of the fiber bundle is hardly exposed, and the durability in terms of the functionality is improved.
From the viewpoint of effectively exhibiting functions by functional processing by taking advantage of the characteristics of the multifilament of the present invention, the ease of impregnation with a functional substance is also important, and variations in the thickness of flat ultrafine fibers become an indicator to be paid attention.
The variation in thickness is obtained by calculating an arithmetic mean and a standard deviation using the measured lengths of the short axes of 100 fibers, dividing the standard deviation by the arithmetic mean, and rounding off the coefficient of variation obtained by dividing the standard deviation by the arithmetic mean to decimal points in the whole number of% units.
As described above, since the bending rigidity of the fiber greatly varies depending on the thickness, when there is a moderate variation in the thickness, each single fiber does not perform homogenization, for example, each single fiber is well dispersed with different behavior in a liquid containing a functional substance. In this case, the fiber surface is not hindered by other fibers and is exposed to the liquid, and the functional substance can be efficiently adsorbed.
If the variation in thickness is 10% or more, the single fibers tend to be well dispersed in a liquid, and the functional substance tends to be impregnated, so that the variation in thickness is preferably 10% or more.
If this consideration is advanced, the larger the variation in the thickness of the fibers, the more the behavior of each single fiber becomes uneven and the single fibers are easily dispersed, and when the functional processing is completed in a short time in order to effectively expose the surface of the single fiber, the variation in the thickness is more preferably 20% or more.
If the variation in thickness is 40% or more, even in the case of a high-density fabric or the like in which filaments are strongly bound, liquid tends to penetrate between filaments, and if efficient functional processing is desired in the high-density fabric or the like, the variation in thickness is preferably 40% or more in particular.
In addition, as the thickness variation becomes larger, when an external force is applied in the processing step, fiber breakage easily occurs in a short thickness, but if the thickness variation is less than 70%, there is no problem in practical use, and the object of the present invention can be achieved.
Further, the degree of irregularities on the fiber surface may increase the dispersion state of the single fibers during the functional processing, and the degree of irregularities on the cross section may be an indicator of attention. That is, by providing appropriate irregularities on the surface of the fibers, minute voids of several nm to several hundred nm are formed between the fibers, and the single fibers are easily and effectively dispersed in a liquid containing a functional substance with the minute voids as a starting point.
The "unevenness" here is a single-fiber unevenness obtained by measuring lengths at which a line segment orthogonal to a line segment of the maximum length and a point at which the maximum length of the cross section is divided by 10 intersect with each other, using captured images of the cross section of the fiber, calculating an arithmetic average and standard deviation of the lengths at these 10 points, dividing the standard deviation by the average, and rounding the points in% units. The same measurement was performed on 10 fiber sections, and the calculated arithmetic average of the concavities and convexities of 10 fibers was referred to herein as the concavities and convexities.
If the degree of the unevenness is 20% or more, the single fibers are easily dispersed with the minute gaps between the fibers as the starting points, and the functional processing can be completed in a short time, so that the degree of the unevenness is preferably 20% or more.
On the other hand, as the degree of concavity and convexity becomes higher, there is a tendency that a load is concentrated on a part of a cross section and cracking is liable to occur, but if the degree of concavity and convexity is less than 60%, there is no problem in practical use, and the object of the present invention can be achieved.
The multifilament of the present invention has a specific cross-sectional shape of the cross-section of the fiber, and thus the specific surface area can be greatly increased while maintaining the cross-sectional area of the fiber, and therefore the monofilament has a strength equivalent to that of a normal fiber, and is excellent in handleability without problems such as unnecessarily lowering the quality of a fiber product. Further, the flat ultrafine fibers of the present invention have a continuous form along the fiber axis direction, and since the fiber ends in the fiber bundles are reduced, the quality of the fiber product is not easily damaged, and the operability is excellent. Among the polymers constituting the flat ultrafine fibers, crystalline polymers are suitable in consideration of the passability in general advanced processing steps and practical use, and it is preferable that the polymer constituting the flat ultrafine fibers contains at least 1 polymer selected from the group consisting of polyesters, polyamides and polyolefins. In addition to the above advantages, among these polymers, thermoplastic is preferable from the viewpoint of adjustment of mechanical properties and the like, since the multifilament of the present invention can be produced by a melt spinning method with high productivity, and also can be highly oriented and crystallized in a drawing step.
In the multifilament of the present invention, the strength of the fiber is preferably 1cN/dtex or more in consideration of practical use, and in the case of using the fiber as a woven fabric or sheet to be used under a relatively severe atmosphere, 2cN/dtex or more is preferable, and a more preferable range is exemplified.
By effectively utilizing the characteristics of the multifilament yarn of the present invention, not only a large amount of functional substances can be adsorbed by functional processing to effectively exhibit functions, but also the functional substances are contained in the fiber bundle by a specific fiber bundle structure, so that the functional substances are less likely to fall off and excellent durability can be exhibited. Further, if the functional substance is effectively used, the functional substance is spread inside the fiber bundle or the fiber bundle is deformed by an external force, and thus a slow-release effect such that the functional substance is gradually released can be obtained. Therefore, when the multifilament yarn of the present invention is used as a functional material in combination with a functional substance, it is preferable to process the multifilament yarn in such a state that the functional substance is contained in a fiber bundle composed of flat ultrafine fibers.
The functional substance is not particularly limited as long as it is a compound having a function, and refers to a substance that positively imparts a function to a fiber. The functional substance may be an organic compound or an inorganic compound. Examples of the functions include ultraviolet light blocking, fragrance, deodorization, antibacterial, insect control, moisture absorption, antistatic, flame retardant, antifouling, beauty, health care, and the like, but are not limited to these functions.
As the state of the functional substance existing in the fiber, various forms are considered, and examples of the form include loading by chemical bond, exhaustion, physical adsorption, and the like. In order to dramatically improve the functionality, durability and touch, it is preferable to process the functional substance by utilizing the characteristics of the flat ultrafine fiber of the present invention. For example, after a specific functional substance is contained in a fiber bundle by functional processing in a general solution, other functional substances are formed into a film on the surface of the fiber bundle by a pad drying method or the like, whereby 2 or more functions may be combined or the limit pursuit of functions due to the mutual effects of different functional substances may be sought.
As described above, the multifilament of the present invention can be used widely in general clothing applications such as underwear and outerwear, interior applications such as curtains and cloths, vehicle interior applications such as car seats, living applications such as wiping cloths and health products, applications for removing harmful substances such as filters, industrial material applications such as battery separators, and the like, because functional materials having excellent durability can be obtained by effectively utilizing the characteristics of the multifilament of the present invention.
An example of the method for producing the composite fiber and multifilament of the present invention is described in detail below.
The composite fiber and multifilament of the present invention can be produced by a filament-making process using a composite die as described below, and is preferably melt-spun from the viewpoint of high productivity.
The composite die 10 in which 3 members, for example, the metering plate E, the composite plate F, and the discharge plate G are laminated as shown in fig. 8 is preferably used as the composite die used in the present invention. Incidentally, fig. 8 is an example in which 2 kinds of polymers such as the a component and the B component are used, and if necessary, 3 or more kinds of polymers may be used for the shredding. In the composite die 10, the amount of polymer in each hole of the composite plate F is measured by the measuring plate E, the measured different types of polymer flows are joined by the composite plate F to form a composite flow having an interface, the composite flow is divided and recombined to increase the interface in the cross section of the composite flow, and the composite flow formed by the composite plate F is compressed by the discharge plate G to be discharged. The composite flow is a fluid having a cross section perpendicular to the flow direction and composed of 2 or more polymers.
In the composite plate F, the number of the minute flow paths H having the merging portions and the branching portions is equal to or greater than the number of the discharge holes of the discharge plate G, and the arrangement of the merging portions and the branching portions can be appropriately adjusted so as to form a desired cross section. Here, the merging portion refers to a portion where 2 or more streams merge, and the branching portion refers to a portion where the streams are divided into 2 or more streams. With such a configuration, when different types of polymers pass through the composite sheet F, the polymers flowing out of the respective flow path holes merge at the merging portion to form a composite flow, and the composite flow is divided at the branching portion and is repeatedly performed to form a composite cross section, which is a characteristic that the sum of the interface lengths of 2 types of polymers necessary for the composite fiber of the present invention is extremely large with respect to the fiber cross section. Here, the joining and dividing are not repeated, and may be performed again after the joining or may be performed again after the dividing. In addition, 2 kinds of polymers may be blended in advance in the fluid supplied to the minute flow path of the composite plate F, 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 is constituted by a flow path in which turbulence of the flow in the flow path is minimized, whereby the composite fiber of the present invention can be produced. Incidentally, the above-described minute flow path has the same characteristics as those of a conventional static mixer (static mixer) in that the minute flow path merges and splits the fluid in the flow path. However, since a general static mixer is designed to have a flow path for mixing 2 kinds of polymers, turbulence is generated in the polymer flow to be inserted, and thus it is difficult for those skilled in the art to manufacture the composite fiber of the present invention. Incidentally, by densely designing the flow path structure of the fine flow path of the present invention, the form such as the thickness of each layer constituting the laminated composite flow formed in the flow path can be controlled, and the fiber cross section of an arbitrary composite form can be formed.
In order to avoid the complexity of the description of the composite die, a member that is stacked above the metering plate E may be used as a member that forms a flow path according to the spinning machine and the spinning assembly, although not shown. By designing the metering plate E according to the existing flow path member, the existing spin pack assembly and its components can be directly and effectively utilized. Therefore, it is not necessary to specialize the spinning machine for the die in particular. In practice, it is preferable to stack a plurality of flow path plates between the flow path and the measuring plate E or between the measuring plate E and the composite plate F. The purpose is to provide a flow path for efficiently transferring the polymer in the die cross-section direction and the filament cross-section direction, and to introduce the polymer into the composite sheet F. The composite polymer stream discharged from the discharge plate G is cooled and solidified, and then applied with an oil solution, and pulled by a roll having a predetermined circumferential velocity to form composite fibers.
The composite fiber of the present invention can be produced using the composite die described above. Incidentally, if this composite die is used, it is needless to say that the composite fiber of the present invention can be produced even by a spinning method using a solvent such as solution spinning.
In the case of selecting melt spinning, the polymer constituting the composite fiber of the present invention is as described above. Examples thereof include polymers that can be melt molded, such as polyethylene terephthalate or copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, polypropylene, polyolefin, polycarbonate, polyacrylate, polyamide, polylactic acid, and thermoplastic polyurethane. In particular, polycondensation polymers such as polyesters and polyamides are more preferable because they have a high melting point. The polymer may contain various additives such as inorganic substances such as titanium oxide, silica, and barium oxide, colorants such as carbon black, dyes, and pigments, flame retardants, fluorescent brighteners, antioxidants, and ultraviolet absorbers. When the polymer containing these additives is selected, irregularities are formed in each layer of the multilayer laminated fiber according to the particle diameter of the fine particles as the additive, and any irregularities can be imparted to the flat ultrafine fiber thus formed.
These polymers are combined in 2 or more types to form a multilayer laminated fiber, and the combination of polymers is also important from the viewpoint of making the laminated structure good.
That is, as the solubility parameter (SP value) difference of the polymers to be combined becomes smaller, a good laminated structure without interflow or the like between layers is formed, and it is preferable to select the polymers so that the solubility parameter difference of 2 kinds of polymers forming the interface becomes 3.0 or less. The so-called solubility parameter is described herein above.
In addition, from the viewpoint of making the interface layer having characteristics of 2 polymers formed in the vicinity of the interface, which is a characteristic of the composite fiber of the present invention, appear, if the polymers are polyesters, the interface layer is formed more widely in 1 interface, which is preferable. In particular, when a readily soluble polyester in which a metal sulfonate base is copolymerized is used as one polymer, if the other polymer is made to be a hardly soluble polyester, excellent chemical resistance can be imparted even to a fiber containing the readily soluble polyester, and thus it is preferable. In particular, when a polyester obtained by copolymerizing sodium isophthalate sulfonate and polyethylene glycol is used alone or in combination as the polyester obtained by copolymerizing a metal sulfonate base, the color development after dyeing is excellent in addition to excellent chemical resistance, and it is preferable. As an example of the combination of the polymers, there can be mentioned a polymer comprising 5 to 15mol% of polyethylene terephthalate copolymerized with 5 to 15mol% of sodium isophthalic acid-5-sulfonate and polyethylene glycol 5 to 15wt% of polyethylene glycol having a weight average molecular weight of 500 to 3000 copolymerized in addition to the above sodium isophthalic acid-5-sulfonate, based on the relation of the melting points, and a polymer comprising polyethylene terephthalate.
The spinning temperature at the time of spinning the composite fiber of the present invention is a temperature at which a polymer having a high melting point and a high viscosity among 2 or more polymers mainly exhibits fluidity. The temperature at which fluidity is exhibited varies depending on the molecular weight, but is preferably set from the melting point of the polymer to a temperature of +60℃. If it is less than this, the polymer is not thermally decomposed in the spinneret or spin pack, and the decrease in molecular weight is suppressed, which is preferable. The discharge amount of the composite fiber of the present invention at the time of spinning was 0.1 g/min Kong 20.0.20.0 g/min pore, and thus the composite fiber was stably produced. In particular, if the single fiber fineness after stretching is set to a single hole discharge amount of less than 4dtex, the fineness is preferably because it is thin, and a soft hand is obtained when a woven fabric is produced.
The ratio of the A component to the B component in spinning the composite fiber of the present invention can be selected in the range of 5/95 to 95/5 in terms of the ratio of the A component to the B component based on the discharged amount. Even in the case of using a polymer having poor chemical resistance and heat resistance, if the interface between the components is increased, it is preferable to compound the polymer having excellent chemical resistance and heat resistance as the other polymer, and the ratio of the polymer is increased, for example, if the component A is a polymer having high chemical resistance and the component B is a polymer having low chemical resistance, the weight of the fiber is reduced to a minimum even if the dissolution treatment is performed for a long period of time, and it is preferable to increase the ratio of the component A to the component B to 99/1 to 70/30.
The polymer stream thus discharged is cooled and solidified, and the oiling agent is applied, and the resultant is drawn by a roll having a predetermined circumferential velocity to form a composite fiber. The drawing speed is determined by the discharge amount and the target fiber diameter, but is preferably in the range of 100 to 7000 m/min for stably producing the conjugate fiber used in the present invention. From the viewpoint of improving mechanical properties for high orientation, the composite fiber is preferably drawn. The stretching may be performed after being temporarily wound in the spinning step, or may be performed after the stretching without being temporarily wound.
As this stretching condition, for example, in a stretching machine composed of a pair or more of rolls, if a fiber composed of a polymer exhibiting thermoplasticity which is generally melt-spinnable, a composite fiber having a composite cross section as shown in fig. 1 can be obtained by setting the circumferential speed ratio of the 1 st roll at a temperature of not less than the glass transition temperature and not more than the melting point to the 2 nd roll at the crystallization temperature, thereby being naturally stretched in the fiber axis direction and being heat-set and wound. The upper limit of the temperature of the 1 st roll is preferably a temperature at which disturbance of the fiber channel does not occur during preheating, and for example, when the glass transition temperature is about 70 ℃ in the case of polyethylene terephthalate, the preheating temperature is usually set to about 80 to 95 ℃.
As described above, although the method for producing a composite fiber according to the present invention is described based on a general melt spinning method, it is needless to say that the composite fiber can be produced by a melt blowing method or a spunbonding method, and further, can be produced by a solution spinning method such as wet or dry-wet method.
In order to obtain the multifilament of the present invention from the composite fiber having the multilayer laminated structure obtained in the above-described manner, the multilayer laminated fiber is immersed in a solvent or the like in which the readily soluble polymer is soluble, and the readily soluble polymer is removed, whereby a flat ultrafine fiber composed of a poorly soluble polymer and a fiber bundle thereof can be obtained. In the case where the easily soluble polymer is a copolymer polyethylene terephthalate in which sodium isophthalic acid-5-sulfonate or the like is copolymerized, an aqueous alkali solution such as an aqueous sodium hydroxide solution may be used as the method, and for example, after a multilayer laminated fiber or a textile formed therefrom is produced, the multilayer laminated fiber may be immersed in the aqueous alkali solution. In this case, if the aqueous alkali solution is heated to 50℃or higher, the progress of hydrolysis can be accelerated, and thus it is preferable. The method for producing the multifilament from the multilayered fiber is not limited to the above-described dissolution treatment, but the multifilament of the present invention can be produced favorably by surely separating the multifilament into individual fibers of flat ultrafine fibers made of a poorly soluble polymer by dissolution and removal of the readily soluble polymer, while minimizing fiber damage.
Examples
The composite fiber of the present invention will be specifically described below with reference to examples.
The following evaluations were performed for examples and comparative examples.
A. Melt viscosity
The polymer sheet was dried by a vacuum dryer so that the water content was 200ppm or less, and the prepared kobufin was manufactured by the Toyo refiner of Kagaku Co., ltdThe strain rate was changed stepwise, and the melt viscosity was measured. In the examples and comparative examples, the shear rate 1216s was described by making the measurement temperature the same as the spinning temperature -1 Is a melt viscosity of (a) a (b). After a sample was put into the heating furnace, the measurement was performed under a nitrogen atmosphere for 5 minutes until the start of the measurement.
B. Melting point
About 5mg of the flake-like polymer dried by a vacuum dryer so as to have a water content of 200ppm or less was weighed, and a Differential Scanning Calorimeter (DSC) model Q2000 manufactured by Takara Shuzo Co., ltd., was used, and after the temperature was raised from 25℃to 300℃at a temperature-raising rate of 16℃per minute, the polymer was kept at 300℃for 5 minutes, and DSC measurement was performed. The melting point was calculated from the melting peak observed during the temperature rise. The measurement was performed 3 times on sample 1, and the average value was set as the melting point. When a plurality of melting peaks are observed, the melting peak top on the highest temperature side is set to the melting point.
C. Solubility parameter difference
The solubility parameter (SP value) is a parameter defined by the square root of (evaporation energy/molar volume) and reflecting the cohesive force of a substance, and is obtained by immersing a polymer in various solvents, and setting the value of (evaporation energy/molar volume) of a solvent in which the swelling pressure becomes extremely large as the value of (evaporation energy/molar volume) of the polymer. The SP value obtained in this way is described in, for example, "tap-tap", this value can be used in the joint editing of the uro chemical and acoustic library, page 189, and the like. The solubility parameter difference of the polymer to be combined is calculated as the absolute value of (SP value of component A-SP value of component B).
D. Denier of denier
The weight of the composite fiber was measured at 100m, and the value was multiplied by 100 times. This measurement was repeated 10 times, and the average value thereof was set as fineness (dtex). The value obtained by dividing the fineness by the number of filaments is referred to as a single fiber fineness (dtex).
E. Uster U%
The Uster U% (H) of the conjugate fiber was measured using a fineness unevenness measuring apparatus (UT-4) manufactured by Zellweger under conditions of a yarn feeding speed of 100 m/min, a twisting machine rotation speed of 6000rpm, and a measurement length of 100 m.
F. Sum of interfacial lengths/fiber cross-sectional area (nm -1 )
The composite fiber was embedded with an embedding medium such as epoxy resin, frozen by a FC.4E type frozen section system manufactured by Reichert corporation, and cut by a Reichert-Nissei ultracut N (microtome) equipped with a diamond knife. Then, the cut surface was imaged with a Transmission Electron Microscope (TEM) of H-7100FA manufactured by hitachi corporation at a magnification at which an interface formed of 2 polymers could be recognized. The length from the measurement start point arbitrarily determined for 1 interface to the measurement start point returned again was measured using image analysis software (winrook), and the length of 1 interface (interface length) was obtained by rounding off the decimal points and the like in an integer of nm. When the fiber cross section reaches the outer peripheral portion until the fiber is returned to the measurement start position, the fiber cross section is measured without including the length of the portion passing through the outer peripheral portion, which is the length from the measurement start point to the time when the interface/outer peripheral portion is searched for until the fiber is returned to the measurement start position again. The same measurement was performed for all interfaces existing in the fiber cross section, and the total interface length was added up to calculate the sum of the interface lengths. Dividing the sum of the interface lengths by the fiber cross-sectional area to obtain a value of the sum of the interface lengths/the fiber cross-sectional area in nm -1 The unit is calculated by rounding the 5 th bit after the decimal point. In the calculation of the fiber cross-sectional area, the composite fiber was cut at an arbitrary position in the fiber axis direction perpendicularly to the fiber axis direction, the cut surface was photographed with an OLYMPUS optical microscope at a magnification of 2 dimensions so that the entire 1-filament cross-section could be observed, and the fiber cross-section was calculated by taking 1-filament cross-section using image analysis software (winrook), performing 2-valued processing, and rounding the fiber cross-section to a decimal point or later in an integer of nm from the obtained cross-section parameter.
G. Deviation of layer thickness (composite fiber)
The length of a layer present on a straight line that vertically bisects the long sides of 1 layer (film-like element) constituting the fiber cross section is defined as the layer thickness, and the layer thickness is measured by optionally extracting 100 elements of the B component from a cross-sectional image of the composite fiber taken by the same method as the measurement of the sum of the interface lengths, and rounding off the decimal point and thereafter in an integer of nm. When the number of layers is less than 100 in the cross section of 1 composite fiber, the total of the cross sections of the composite fibers is 100 layers. 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 by decimal points in an integer of% units, to calculate the deviation of the layer thickness. In the case of a radial stack or a concentric stack in which the thickness of each layer cannot be measured by the above method, the position where the thickness of each layer is largest and the position where the thickness is smallest are visually selected, the average value is set as the thickness of each layer, and the coefficient of variation obtained by dividing the standard deviation by the arithmetic average is calculated as the deviation of the layer thickness, similarly to the above.
H. Average layer thickness (composite fiber)
The length of the layer present on a straight line which vertically bisects the long sides of 1 layer constituting the fiber cross section is defined as the layer thickness, and the layer thickness is measured by optionally taking 100 elements of the B component from the cross-sectional image of the composite fiber taken by the same method as the measurement of the sum of the interface lengths, and rounding off the decimal point in an integer of nm. When the number of layers is less than 100 in the cross section of 1 composite fiber, the total of the cross sections of the composite fibers is 100 layers. The arithmetic average of the obtained values was rounded off after decimal points in an integer of nm to calculate the average layer thickness. In the case of a radial stack or a concentric stack in which the thickness of each layer cannot be measured by the above method, the position where the thickness of each layer is largest and the position where the thickness is smallest are visually selected, and the average value is calculated as the thickness of each layer, and the arithmetic average is calculated as the average layer thickness in the same manner as described above.
I. Wear resistance
The number of the composite fibers was adjusted so that the weave density became 180 fibers/2.54 cm, and a plain weave was produced. The plain weave fabric cut to have a diameter of 10cm was placed on a sample holder of an appearance retention tester (ART tester) manufactured by Kagaku Kogyo Co., ltd.) to have a pressing load of 3.9N, and was rubbed with a silicon carbide friction plate (3K), and the number of rubs in which the occurrence of fibrils was confirmed on the surface of the fiber was measured every 1 rotation of the friction plate, and the average value of 5 measurements was obtained. The number of rubs was obtained by rounding off the decimal point, and the abrasion resistance of the fiber was evaluated by the following 4-level evaluation.
[ evaluation criterion ]
A (good): the number of friction times is more than 100
B (good): the number of friction times is more than 50 and less than 100
C (pass): the number of friction times is 20 times or more and less than 50 times
D (reject): the number of friction times is less than 20
J. Chemical resistance
A tubular knitted fabric of composite fibers was produced, which was treated with a 1% aqueous sodium hydroxide solution at 90℃for 30 minutes, washed with water, and dried sufficiently at 60℃to calculate the weight loss from the weight before and after the treatment. The value of the decrement ratio is obtained by rounding the 2 nd bit of the decimal point, and the chemical resistance is evaluated by the following 4-level evaluation.
[ evaluation criterion ]
A (good): the decrement rate is more than 0.0% and less than 2.0%
B (good): the decrement rate is more than 2.0% and less than 5.0%
C (pass): the decrement rate is more than 5.0% and less than 10.0%
D (reject): the decrement rate is more than 10.0 percent
K. Heat resistance
The composite fiber was wound 10 times with a length measuring machine having a frame circumference of 1.0m, and the twisted yarn length before treatment was measured by applying a load of 0.0294 cN/dtex. The skein was placed in a hot air dryer at 160℃for 15 minutes in a state of no load, and the skein length after the treatment was measured by applying a load of 0.0294cN/dtex to the skein taken out again. The dry heat shrinkage was calculated from the equation of [ dry heat shrinkage (%) = (length of twisted wire before treatment-length of twisted wire after treatment)/length of twisted wire before treatment×100 ]. The dry heat shrinkage was obtained from 5 measurements, and the arithmetic average was calculated by rounding the 2 nd position after the decimal point. The fiber surface of the treated skein was observed with an optical microscope made by feun corporation to confirm whether fusion occurred between fibers, and the heat resistance was evaluated by the following 3-level evaluation.
[ evaluation criterion ]
A (good): the dry heat shrinkage is less than 15.0% and there is no interfiber fusion
B (pass): the dry heat shrinkage is 15.0% or more, and no interfiber fusion is caused
C (reject): with interfiber fusion
L. flatness
The multifilament yarn composed of flat ultrafine fibers was embedded with an embedding agent such as an epoxy resin, frozen by a frozen section system of FC.4E manufactured by Reichert, and cut with a Reichert-Nissei ultracut N (microtome) equipped with a diamond knife, and then the cut surface was imaged with a Transmission Electron Microscope (TEM) of H-7100FA type manufactured by Hitachi, inc. at a magnification allowing the cross section to be recognized. The maximum length of the cross section of the filament was measured using image analysis software (winrook), and this value was defined as the length of the long axis of the filament, and the filament was obtained by rounding off the decimal point with an integer in nm. Next, the length of the intersection of the fiber cross section with a line segment orthogonal to the line segment of the maximum length at the midpoint of the maximum length was measured, and the value was obtained by rounding off the decimal point with an integer of nm as the length of the short axis of the single fiber. Using the length of the major axis and the length of the minor axis, the flatness of the filaments was calculated by the following formula.
Flatness = length in the long axis direction (nm)/length in the short axis direction (nm)
The measurement was performed on 100 fibers to calculate the flatness of each fiber, and the arithmetic average decimal point was rounded off to calculate the flatness of the flat ultrafine fiber.
M. average thickness of fiber (Flat ultrafine fiber)
The arithmetic average of the lengths of the short axes of the 100 fibers measured above was rounded off after decimal points in an integer of nm, and the average thickness of the flat ultrafine fibers was calculated.
N. variation in thickness of fibers (Flat ultrafine fibers)
The arithmetic mean and standard deviation were calculated using the measured lengths of the short axes of 100 fibers, and the variation coefficient obtained by dividing the standard deviation by the arithmetic mean was rounded off after the decimal point in an integer of% unit to calculate the variation in the thickness of the flat ultrafine fiber.
O, relief degree
Using the captured images of the fiber cross sections, the lengths at which the line segments orthogonal to the line segments of the maximum length at the points where the maximum length of the cross sections was 10 equal were each measured and the fiber cross sections were intersected were calculated, the arithmetic mean and standard deviation of the lengths at these 10 points were calculated, and the values obtained by dividing the standard deviation by the mean and rounding the decimal points in% units were calculated as the irregularities of the single fibers. The same measurement was performed on 10 fiber sections, and the arithmetic average of the calculated concavities and convexities of 10 individual fibers was calculated as the concavities and convexities of flat ultrafine fibers.
P. distribution state of functional substances
In order to evaluate the distribution state model of the functional material when the fiber bundle was treated with the functional material, a dye solution in which the dye solution was adjusted to 10% owf with respect to the dye, telon Black LD02 manufactured by Dystar corporation, which is non-dyeable with respect to polyester, was used at a bath ratio of 1: after the woven fabric was treated at a treatment temperature of 30℃for 30 minutes, the surface and cross section of the woven fabric were observed by a VHX-6000 digital microscope available from Kyowa Kabushiki Kaisha. The distribution state at this time is determined based on the following criteria.
[ evaluation criterion ]
The inside of the fiber bundle: there is dye (coloring matter) between the fibers of the fiber bundle section.
The method is free of: there is no dye (coloring matter) between the fibers of the fiber bundle cross section.
Q. functional processing (deodorization processing)
A 10% aqueous solution of dodecanedioic acid dihydrazide having an adsorption ability for acetaldehyde was used, and the solution was prepared at a solid content of 20% owf: 20. the woven fabric was treated at 130℃for 1 hour.
R. deodorant (acetaldehyde concentration)
In a conditioned environment at a temperature of 20℃and a humidity of 65% RH, 1g of the woven fabric after the functional processing processed in Q was put in a 5L Li bag, and acetaldehyde 3L was injected into the Li bag at a concentration of 30ppm, and the concentration of gas (ppm) in the Li bag after 10 minutes was measured using a gas detection tube (manufactured by Koshi Tech Co., ltd.).
S. content of functional substance
The woven fabric before processing was dried at 110℃for 2 hours, and the weight (W1) was measured. The woven fabric after the functional processing processed in the above Q was dried at 110℃for 2 hours, and the weight (W2) was measured. The content (%) of the functional substance was calculated from the weights before and after the processing by the following formula.
Functional substance content (%) = (W2-W1)/w1×100
T, content of functional substance after washing
The woven fabric after the functional processing processed in Q above was subjected to 50 cycles in the order of washing (15 minutes) →dehydration (1 minute) →rinsing (6 minutes) →dehydration (1 minute) →drying. The washing conditions were water temperature 40 ℃, bath ratio 1: the lotion was 0.5g/l (manufactured by kui-tan corporation). The flushing condition was set to water temperature 20℃and the bath ratio was set to overflow.
The washed woven fabric was dried at 110℃for 2 hours, and the weight (W3) was measured. The content (%) of the functional substance was calculated from the weights before and after the processing and the following formula.
The content (%) = (W3-W1)/w1×100 of the functional substance after washing
Example 1
As component A, polyethylene terephthalate (PET, melt viscosity: 120 Pa.s, melting point: 254 ℃ C., SP value: 21.4 MPa) was prepared 1/2 ) And as a component B, polyethylene terephthalate (SSIA-PEG copolymerized PET, melt viscosity) copolymerized with 8.0 mol% of sodium isophthalic acid-5-sulfonate and 9wt% of polyethylene glycol was prepared: 95 Pa.s, melting point: 233 ℃, SP value: 22.9MPa 1/2 )。
After the component A and the component B were melted at 290℃respectively, the composite ratio of the component A/B was set to 90/10, and the components were fed into a spinning pack incorporating a composite die 10 as illustrated in FIG. 8, and a composite polymer stream was discharged from a discharge port. The composite sheet F has a fine flow path H in which two components can be alternately laminated into 1024 layers, and 2 kinds of polymers as shown in fig. 1 are discharged so as to be a composite form in which the two components are alternately laminated in one direction. After cooling and solidifying the discharged composite polymer stream, an oiling agent was applied, and the resultant was wound at a spinning speed of 1000 m/min, whereby an undrawn yarn of 200dtex-24 filaments (total discharge amount of 20 g/min) was used. The wound undrawn fiber was drawn 3.6 times between rolls heated to 90℃and 130℃to obtain a drawn fiber of 56dtex-24 filaments. The U% (H) as an index of the fineness unevenness was 0.6%, and the uniformity of the thickness in the fiber axis direction was excellent.
The cross section of the resulting composite fiber was observed, resulting in a total interface length/fiber cross-sectional area of 0.0557nm -1 The sum of the lengths of the interfaces with respect to the fiber cross-sectional area is extremely large, and the same interface is continuous in the fiber axis direction. The average layer thickness of the component B was 4nm, the layer thickness variation was 32%, and the component B was divided into extremely thin film elements.
The woven fabric obtained by weaving the obtained composite fiber was evaluated for peel resistance, and as a result, no generation of fibrils was observed even when the number of rubbing was 100 or more. Incidentally, the cross section of the composite fiber after abrasion resistance evaluation was observed by a Scanning Electron Microscope (SEM) manufactured by hitachi corporation, and as a result, separation between components was not confirmed.
The tubular knitted fabric of the composite fiber thus obtained was immersed in a 1% strength aqueous sodium hydroxide solution (bath ratio: 1:50) heated to 90℃for 30 minutes, and as a result, the reduction rate was 0.6%.
The results are shown in table 1.
Examples 2, 3, 4, 5, 6
The method described in example 1 was performed in the same manner as in example 1 except that the method was changed to a composite board having a minute flow path in which the total number of layers of the a component and the B component was laminated to 512 layers (example 2), 256 layers (example 3), 128 (example 4), 64 (example 5), and 32 (example 6). The evaluation results of these composite fibers are shown in table 1.
The composite fibers of examples 2 to 6 were a composite structure as shown in fig. 1 in which 2 kinds of polymers were alternately laminated in one direction, and the same interface was continuous in the fiber axis direction. In example 2, even though no fibril generation was observed when the number of friction times was set to 100 or more, in examples 3 to 6, as compared with example 2, the total interface length/fiber cross-sectional area value was reduced as the number of layers of 2 polymers in the fiber cross-section was reduced, so that fibrils were observed in several monofilaments when the number of friction times was set to 50 or more. The cross section of the fibrillated composite fiber was observed by the same method as described above, and as a result, 2 kinds of polymers were cut in the direction in which they were bonded, and it was estimated that the fibers were caused by separation between components. In examples 2 and 3, the reduction rate slightly increased with the decrease in the sum of the interface lengths and the fiber cross-sectional area, but was less than 2.0%, and the chemical resistance was excellent. On the other hand, in examples 5 and 6 in which the sum of the interface lengths and the fiber cross-sectional area were further reduced, the reduction rate was increased to 5.0% or more, and the chemical resistance was reduced as compared with examples 1 to 3.
Comparative example 1
The method described in example 1 was performed in the same manner as in example 1 except that the method was changed to a composite board having a minute flow path in which 8 layers (comparative example 1) were laminated on the total number of layers of the component a and the component B. The evaluation results of these composite fibers are shown in table 1.
The composite fiber of comparative example 1 has a composite structure in which 2 kinds of polymers are alternately laminated in one direction as shown in fig. 1, but the number of divisions (the number of layers) is significantly smaller than that of the composite fiber of the present invention, and the sum of interface lengths and the value of fiber cross-sectional areas are small, so that fibrils are observed in a plurality of single fibers when the number of friction times is 20 or more, and abrasion resistance is poor. Further, the tubular knitted fabric of the obtained composite fiber was evaluated for chemical resistance, and as a result, the reduction rate was 10.0% or more, and the chemical resistance was poor. Incidentally, the tubular knitted fabric after the chemical resistance evaluation was dyed under the same conditions as described above, and as a result, the tubular knitted fabric was not dyed, and it was estimated that substantially the entire amount of the SSIA-PEG copolymerized PET constituting the readily soluble composite fiber was dissolved by the chemical resistance evaluation.
Example 7
In the method described in example 1, the component B was polyethylene terephthalate (SPG-CHDC copolymerized PET having a melt viscosity of 75 Pa.s and a melting point: none [ glass transition temperature: 76 ℃ C.)]SP value: 23.0MPa 1/2 ) The procedure of example 1 was repeated except that the mixture was melted at 285℃to give a composite ratio of the A/B components of 50/50. The evaluation results of the composite fiber are shown in table 2.
The composite fiber of example 7 was a composite structure as shown in fig. 1 in which 2 kinds of polymers were alternately laminated in one direction, and the same interface was continuous in the fiber axis direction. The woven fabric of the obtained composite fiber was evaluated for peel resistance, and as a result, no generation of fibrils was observed even when the number of rubs was 100 or more. Further, the resultant twisted strands of the composite fibers were treated with a hot air dryer at 160℃for 15 minutes, and as a result, the dry heat shrinkage was less than 15.0%, and the thermal dimensional stability was excellent, and although SPG-CHDC copolymerized PET having an amorphous property and a glass transition temperature of not higher than the treatment temperature of the hot air dryer was used, no fusion between fibers was observed.
Examples 8 and 9
The method described in example 7 was performed in the same manner as in example 7 except that the method was changed to a composite board having a minute flow path in which the total number of layers of the a component and the B component was laminated to 512 layers (example 8) and 256 layers (example 9). The evaluation results of these composite fibers are shown in table 2.
In example 8, no fibril generation was observed even when the number of friction times was 100 or more, but in example 9, as the number of layers of 2 polymers in the fiber cross section was reduced, the sum of the interface lengths/the value of the fiber cross section was reduced, compared with example 8, so that fibrils were observed in several single fibers when the number of friction times was 50 or more. Further, the compounding ratio of SPG-CHDC copolymer PET, which is inferior in heat resistance, was increased, and the dry heat shrinkage was increased, and the heat resistance was lowered although the level was not problematic in example 9. In example 9, 2 polymers having different properties were alternately laminated in a layer thickness such that thin film interference of visible light occurred, and therefore the resulting composite fiber structure was blue in color.
Comparative example 2
The method described in example 7 was performed in the same manner as in example 7 except that a composite sheet having a minute flow path in which the total number of layers of the a component and the B component was laminated to 8 layers was used. The evaluation results of these composite fibers are shown in table 2.
The composite fiber of comparative example 2 has a composite structure in which 2 kinds of polymers are alternately laminated in one direction as shown in fig. 1, but the number of divisions (the number of layers) is significantly smaller than that of the composite fiber of the present invention, and the sum of the interface lengths and the value of the fiber cross-sectional area are small, so that when the number of times of friction is 20 or more, fibrils are observed in a plurality of single fibers, and abrasion resistance is poor. Further, the heat resistance of the tubular knitted fabric of the obtained composite fiber was evaluated, and as a result, the dry heat shrinkage was 20.0% or more, and the fusion between fibers was remarkable, and the hand feeling of the twisted yarn was very hard.
Examples 10, 11 and 12
In the method described in example 7, the component B was polyamide-6 (N6, melt viscosity 100 Pa.s, melting point 225 ℃ C.)]SP value: 23.7MPa 1/2 ) A composite plate having a fine flow path in which two components were laminated in 1024 layers (example 10), 512 layers (example 11), and 256 layers (example 12) was used, and the melting was performed at 280 ℃. The evaluation results of these composite fibers are shown in table 3.
In examples 10 to 12, since the composite fibers were formed by compounding polymers having a large difference in solubility parameter, fibrils were observed in several single fibers when the number of friction times was 50 or more, but abrasion resistance was substantially good.
Examples 13 and 14
The method described in example 10 was carried out in the same manner as in example 10 except that the method was changed to a composite plate having a minute flow path in which the total number of layers of the a component and the B component was laminated to 256 layers, and the flow path arrangement was changed so as to have a concentric laminated structure (example 13) and a radial laminated structure (example 14). The evaluation results of these composite fibers are shown in table 3.
In example 13, a composite structure as shown in fig. 4 was formed in which 2 kinds of polymers were alternately laminated in concentric circles, and in example 14, a composite structure as shown in fig. 3 was formed in which 2 kinds of polymers were alternately laminated in radial circles, and the same interface was continuous in the fiber axis direction. Since the composite fiber is formed by compounding polymers having large differences in solubility parameters, fibrils are observed in a plurality of single fibers when the number of times of friction is 50 or more, but abrasion resistance is substantially good.
Comparative example 3
The method described in example 10 was performed in the same manner as in example 10, except that a composite sheet having a minute flow path in which the total number of layers of the a component and the B component was laminated to 8 layers was used. The evaluation results of the composite fiber are shown in table 3.
The composite fiber of comparative example 3 has a composite structure in which 2 kinds of polymers are alternately laminated in one direction as shown in fig. 1, but the number of divisions (the number of layers) is significantly smaller than that of the composite fiber of the present invention, and the sum of the interface lengths and the value of the fiber cross-sectional area become smaller, so that fibrils are generated in a plurality of single fibers even when the number of friction times is 20 or less, and abrasion resistance is poor. In addition, fibrillation also occurs in the weaving process, breakage frequently occurs, and there is a problem in high-grade processing passability.
Comparative example 4
The method described in comparative example 3 was performed in the same manner as in comparative example 3 except that a composite plate in which only the flow path for discharging the component a was provided around the fine flow path in which the two components were laminated in 8 layers was used. As shown in table 3, the evaluation result of the composite fiber was that the multilayer laminated structure was coated with the a component (coated unidirectional laminated fiber 6) as shown in fig. 9, but the number of laminated layers was significantly smaller than that of the composite fiber of the present invention, and the sum of the interface lengths and the value of the fiber cross-sectional area were smaller, so that even when the coating was provided on the fiber surface, the plurality of single fibers were fibrillated at a rubbing number of 20 or less, and the abrasion resistance was poor.
Example 15
As component A, polyethylene terephthalate (PET, melt viscosity: 120 Pa.s, melting point: 254 ℃ C., SP value: 21.4 MPa) was prepared 1/2 ) And as a component B, polyethylene terephthalate (SSIA-PEG copolymerized PET, melt viscosity) copolymerized with 8.0 mol% of sodium isophthalic acid-5-sulfonate and 9wt% of polyethylene glycol was prepared: 95 Pa.s, melting point: 233 ℃, SP value: 22.9MPa 1/2 ). The difference in solubility parameter of these polymers was 1.5MPa 1/2 。
After the component A and the component B were melted at 290℃respectively, the composite ratio of the component A/B was set to 80/20, and the components were fed into a spinning pack incorporating a composite die 10 as illustrated in FIG. 8, and a composite polymer stream was discharged from a discharge port. The composite sheet F is provided with the minute flow paths H in which the two components can be alternately laminated into 128 layers, and is discharged so as to be a composite form in which 2 kinds of polymers as shown in fig. 1 are alternately laminated in multiple layers in one direction. After cooling and solidifying the discharged composite polymer stream, an oiling agent was applied, and the yarn was wound at a spinning speed of 1000 m/min, and an undrawn yarn of 300dtex-24 filaments (total discharge amount of 30 g/min) was used. The wound undrawn fiber was drawn 3.6 times between rolls heated to 90℃and 130℃to obtain a drawn fiber of 84dtex-24 filaments. The U% (H) as an index of the fineness unevenness was 0.6%, and the uniformity of the thickness in the fiber axis direction was excellent.
The cross-sectional morphology of the obtained composite fiber was observed, and as a result, it was confirmed that the composite fiber had a plate-like laminated structure in which the lamination directions were aligned as shown in fig. 1.
The woven fabric obtained by weaving the obtained composite fiber was evaluated for peel resistance, and as a result, no generation of fibrils was observed even when the number of rubbing was 50 or more. Incidentally, the cross section of the composite fiber after abrasion resistance evaluation was observed by a Scanning Electron Microscope (SEM) manufactured by hitachi corporation, and as a result, separation between components was not confirmed, and the composite fiber was excellent in abrasion resistance.
The composite fiber was immersed in a 1% sodium hydroxide aqueous solution (bath ratio 1:50) heated to 90 ℃ for 30 minutes or longer, whereby 99% or more of the SSIA-PEG copolymerized PET as the B component was removed, and a multifilament composed of flat ultrafine fibers was obtained. The same procedure was also performed for the woven fabric obtained by weaving the composite fibers, and a woven fabric composed of flat ultrafine fibers was obtained.
The cross section of the obtained flat ultrafine fiber was observed, and as a result, it was a band-shaped cross section having a length of a major axis and a minor axis which were significantly different, the flatness was 80, and the average thickness was 225nm. The thickness of the cross section was varied by 36%, the roughness was 30%, the thickness was moderately varied, and the surface was moderately uneven.
The cross section of the woven fabric of the obtained flat ultrafine fibers was also observed, and as a result, a plurality of flat ultrafine fibers were superimposed in the direction of the minor axis, and a dense fiber bundle structure was formed. In addition, each flat ultrafine fiber is coagulated so as to be exactly bonded, and extremely fine voids of several nm to several hundreds nm exist between the fibers.
A woven fabric made of flat ultrafine fibers was immersed in a dye solution in which a non-dyeing dye (acid black dye) was adjusted to 10% owf, and the bath ratio was 1:50, the treatment temperature was 30℃and the treatment time was 30 minutes, and as a result, the flat ultrafine fibers were colored black in cross section, and the fiber bundles were impregnated with the dye, and the woven fabric surface was also colored black.
A woven fabric comprising flat ultrafine fibers was prepared by using a 10% aqueous solution of dodecanedioic dihydrazide at a solid content of 20% owf, bath ratio of 1: 20. the woven fabric was treated at 130℃for 1 hour, and was subjected to deodorizing function. The acetaldehyde removal ability was evaluated, and as a result, the concentration was reduced from the initial concentration of 30ppm to 2ppm at 10 minutes, and the deodorizing property was high. The content of the functional substance was 5.0%, and the content after washing was 4.2%, so that the functional substance was not significantly reduced, adsorbed in a large amount, and was not easily detached, and the durability was high.
The results are shown in table 4.
Examples 16 and 17
The method described in example 15 was performed in the same manner as in example 15 except that the method was changed to a composite board having a minute flow path in which the total number of layers of the a component and the B component was laminated to 64 layers (example 16) and 32 layers (example 17). These composite fibers were subjected to the same dissolving treatment as described above to produce flat ultrafine fibers. The evaluation results of these composite fibers and flat ultrafine fibers are shown in table 4.
In example 16 and example 17, the thin cross-sectional shapes with high flatness were obtained although the degree of the deviation was different, and the deviation and the unevenness of the length of the minor axis were moderate. In addition, as in example 15, the fiber bundle had a dense fiber bundle structure in which flat ultrafine fibers were overlapped in the same direction, but compared with example 15, the fiber bundle had a smaller flatness and an increased average layer thickness, so that the inter-fiber voids of the fiber bundle were coarse and the aggregated portions of the single fibers were small. Immersed in the non-dyeable dye, the dye is distributed in such a way as to be encapsulated in the fiber bundle. Further, since the specific surface area was reduced as compared with example 15, the content of the functional substance was slightly reduced, but the high content was maintained, and sufficient deodorizing ability was exhibited. In addition, the content of the functional substance is maintained high after washing, and the functional substance is not easy to fall off.
Examples 18 and 19
The method described in example 15 was performed in the same manner as in example 15 except that the method was changed to a composite board having a minute flow path in which the total number of layers of the a component and the B component was laminated to 256 layers (example 18) and 512 layers (example 19). These composite fibers were subjected to the same dissolving treatment as described above to produce flat ultrafine fibers. The evaluation results of these composite fibers and flat ultrafine fibers are shown in table 4.
In examples 18 and 19, the cross section was an extremely thin strip with extremely high flatness, and the cross section had moderate variation in the length of the minor axis and the roughness. In addition, as in example 15, the fiber bundle had a dense fiber bundle structure in which flat ultrafine fibers were overlapped in the same direction, but compared with example 15, the fiber bundle had an increased flatness and a reduced average length of the short axis, so that the inter-fiber voids of the fiber bundle were several nm to several tens nm, and were extremely minute, and the single fibers were aggregated so as to be exactly bonded to the whole fiber bundle. Immersed in the non-dyeable dye, the dye is distributed in such a way as to be entrapped in the fiber bundles. In the case of functional processing, the average length of the short axis is extremely short, and therefore the woven fabric is excessively soft and has poor operability. The specific surface area was increased as compared with example 15, and therefore the content of the functional substance was increased, and the deodorizing ability was excellent. Further, the fiber bundle has a strong aggregation structure in which the functional substance is contained, so that the content of the functional substance after washing is not easily reduced, and the durability is high, thereby enabling the functional substance to be retained.
Comparative example 5
The same procedure as in example 15 was repeated except that polyethylene terephthalate (PET, melt viscosity: 120 Pa.s, melting point: 254 ℃, SP value: 21.4MPa 1/2) was used, and the polyethylene terephthalate was melted at 290℃and then fed into the spin pack alone to be discharged from the discharge orifice. The evaluation results of the individual fibers are shown in table 4.
Comparative example 5 was a fiber with a circular cross section having a general fiber diameter, and had a small specific surface area, and was a structure in which the distance between individual fibers was long as the fiber bundle. Even when immersed in a non-dyeable dye, no adhesion of the dye was observed. Further, since the specific surface area is small, the content of the functional substance is extremely small, and the deodorizing property is poor. Further, the content of the functional substance is reduced to approximately 0 by washing, and the functional substance attached to the fiber surface is easily detached.
Comparative example 6
A spinning pack using an 8-island type sea-island composite die having an island component a and a sea component B was produced in the same manner as in example 15, except that the spinning pack was used. The island-in-sea composite fiber is subjected to the same dissolution treatment as described above to produce a very fine fiber. The evaluation results of the ultrafine fibers are shown in table 4.
Comparative example 6 was a very fine fiber having a greatly reduced fiber diameter and a large specific surface area. Further, for the fiber bundle, the distance between the individual fibers is close. Immersed in the non-dyeable dye, the woven fabric was not colored, and no adhesion of the dye between the fibers was observed. As a result of the functional processing, the specific surface area increases due to the miniaturization, and therefore functional substances adhere to the substrate to a moderate extent, but the functional substances do not exhibit high deodorizing ability to a high extent, and the adsorption amount of the functional substances is greatly reduced by washing.
Comparative example 7
The method described in example 15 was performed in the same manner as in example 15 except that the method was changed to a composite board having a fine flow path in which 8 layers were laminated on the total number of layers of the component a and the component B. The composite fiber is subjected to the same dissolving treatment as described above to produce a flat fiber. The evaluation results of the composite fiber and the flat fiber are shown in table 4.
As shown in fig. 10, the flat fiber 7 of comparative example 7 has a cross-sectional shape with low flatness. Further, since the flatness is low, the direction of the flat fibers 7 as shown in fig. 11 is not uniform in the multifilament, and the fiber bundle structure has a long distance between the individual fibers. Even when immersed in a non-dyeable dye, no adhesion of the dye was observed. Further, since the specific surface area is small, the content of the functional substance is extremely small, and the deodorizing property is poor. Further, the content of the functional substance is reduced to approximately 0 by washing, and the functional substance attached to the fiber surface is easily detached.
Example 20
The method described in example 15 was performed in the same manner as in example 15, except that a composite plate having a different flow path diameter from the minute flow path having the merging portion and the branching portion was used. The composite fiber was subjected to the same dissolving treatment as described above to produce flat ultrafine fibers. The evaluation results of the composite fiber and the flat ultrafine fiber are shown in table 5.
In example 20, although the same as in example 15, the flow path design of the composite plate was changed, and the thickness of the composite plate was changed, so that the thickness of the composite plate was uniform. Further, although the fiber bundle had a dense fiber bundle structure in which flat ultrafine fibers were overlapped in the same direction as in example 15, the ratio of fine voids between fibers of the fiber bundle of several nm to several hundred nm was large compared with example 15 because the uneven degree was small. The fiber bundle was impregnated with the non-dyeable dye, and as a result, the dye was not uniformly distributed throughout the fiber bundle, and a part of the non-dye-encapsulated portion was observed. Further, the dispersibility of the single fibers was lower than that of example 15, so that the content of the functional substance was somewhat poor, but the functional substance was not easily detached by washing.
Example 21
In the method described in example 15, the A component was made to be polyamide-6 (N6, melt viscosity: 100 Pa.s, melting point: 225 ℃ C., SP value: 23.7 MPa) 1/2 ) The component B was polyethylene terephthalate (SSIA-PEG copolymer PET, melt viscosity) in which 8.0 mol% of isophthalic acid-5-sodium sulfonate and 9wt% of polyethylene glycol were copolymerized: 95 Pa.s, melting point: 233 ℃, SP value: 22.9MPa 1/2 ) Spinning at 280 deg.c, exceptAll other operations were performed in the same manner as in example 1. The solubility parameter difference of the combined polymer was 0.8MP 1/2 . The composite fiber was subjected to the same dissolving treatment as described above to produce flat ultrafine fibers. The evaluation results of the composite fiber and the flat ultrafine fiber are shown in table 5.
Example 21 has an extremely thin cross-sectional shape having a high flatness similar to example 15, but because of the inter-fiber hydrogen bonding, the fiber bundle has a structure that is more densely aggregated than example 15. The functional processing was performed, and as a result, the content of the functional substance equivalent to that in example 15 was shown, and the fibers were connected by hydrogen bonds, so that the functional substance was swollen and easily redispersed in single fibers at the time of washing, and the functional substance was easily detached by washing in comparison with example 15.
Example 22
In the method described in example 15, the component A was polypropylene (PP, melt viscosity: 70 Pa.s, melting point: 165 ℃, SP value: 16.8MPa 1/2 ) The component B was polyethylene terephthalate (SSIA-PEG copolymer PET, melt viscosity) in which 8.0 mol% of isophthalic acid-5-sodium sulfonate and 9wt% of polyethylene glycol were copolymerized: 95 Pa.s, melting point: 233 ℃, SP value: 22.9MPa 1/2 ) The procedure of example 15 was repeated except that the spinning was performed at 280 ℃. The solubility parameter difference of the combined polymer was 6.1MPa 1/2 . The cross-sectional morphology of the composite fiber was observed, and as a result, the solubility parameter was greatly different, and the cross-sectional formability became unstable, and the composite fiber had an irregular laminated structure having a local laminated direction of the cross section varied, unlike example 15. The composite fiber was subjected to the same dissolving treatment as described above to produce flat ultrafine fibers. The evaluation results of the composite fiber and the flat ultrafine fiber are shown in table 5.
In example 22, the flatness was lower than in example 15, and the specific surface area was reduced, so that the content of the functional substance was reduced, but the content was high, and the functional substance was not easily detached by washing.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
The present application has been described in detail using specific schemes, but it is apparent to those skilled in the art that various modifications and variations can be made without departing from the intention and scope of the application. The present application is based on japanese patent application (japanese patent application 2020-210112) filed on 18 months of 2020, 12, which is incorporated by reference in its entirety.
Description of symbols
1: unidirectional laminated fiber
2: radiation laminated fiber
3: concentric circular laminated fiber
4: flat ultrafine fiber
5: multifilament yarn
6: film-coated unidirectional laminated fiber
7: flat fiber
10: composite die
A: component A
B: component B
D: functional substance
E: metering plate
F: composite board
G: discharge plate
H: a minute flow path.
Claims (11)
1. A composite fiber made of 2 or more polymers having a fiber cross section in which a plurality of interfaces are formed, the value obtained by dividing the sum of the interface lengths formed by 2 polymers by the area of the fiber cross section being 0.0010nm -1 The above, the interface is continuous in the fiber axis direction.
2. The composite fiber according to claim 1, wherein the value obtained by dividing the sum of interface lengths formed of 2 polymers by the area of the fiber cross section is 0.0050nm -1 The above.
3. The composite fiber according to claim 1 or 2, which has a cross section of a multi-layer laminated structure in which 2 polymers are alternately laminated.
4. The conjugate fiber according to any one of claims 1 to 3, wherein the layer thickness of at least 1 polymer has a CV value of 10% or more.
5. The conjugate fiber according to any one of claims 1 to 4, wherein at least 1 polymer has an average layer thickness of 1000nm or less.
6. A multifilament yarn made of flat ultrafine fibers composed of 1 polymer remaining after 1 polymer out of 2 polymers constituting the multilayer laminated structure is removed from the composite fiber according to claim 3.
7. The multifilament yarn according to claim 6, wherein the fiber cross section of the flat ultrafine fiber has a flat shape, the flatness as a value obtained by dividing the length of the major axis of the fiber cross section by the length of the minor axis is 15 or more, and the average thickness of the flat ultrafine fiber is 1000nm or less.
8. The multifilament yarn according to claim 6 or 7, wherein the flat ultrafine fiber has a variation in thickness, i.e., a CV value of 10% or more.
9. A multifilament yarn according to any one of claims 6-8, wherein the polymer constituting the flat ultra fine fiber comprises at least 1 polymer selected from the group consisting of polyesters, polyamides and polyolefins.
10. A multifilament yarn according to any one of claims 6 to 9, wherein a functional substance is encapsulated in a fiber bundle composed of the flat ultrafine fibers.
11. A fibrous article comprising in at least a portion the composite fiber of any one of claims 1-5 or the multifilament yarn of any one of claims 6-10.
Applications Claiming Priority (3)
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| JP2020-210112 | 2020-12-18 | ||
| JP2020210112 | 2020-12-18 | ||
| PCT/JP2021/046396 WO2022131312A1 (en) | 2020-12-18 | 2021-12-15 | Composite fiber and multifilament |
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| CN116583634A true CN116583634A (en) | 2023-08-11 |
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| CN202180084298.7A Pending CN116583634A (en) | 2020-12-18 | 2021-12-15 | Composite fiber and multifilament |
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| US (1) | US20240110314A1 (en) |
| EP (1) | EP4265828A1 (en) |
| JP (1) | JPWO2022131312A1 (en) |
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| CN (1) | CN116583634A (en) |
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| JPS60246725A (en) * | 1985-03-05 | 1985-12-06 | カネボウ株式会社 | Cleaning cloth and knitted fabric |
| JPH01132812A (en) | 1987-11-16 | 1989-05-25 | Toray Ind Inc | Multileaf-type fiber |
| JPH0726433A (en) * | 1993-07-07 | 1995-01-27 | Toyobo Co Ltd | Composite multifilament |
| JP3158830B2 (en) * | 1993-12-29 | 2001-04-23 | 日産自動車株式会社 | Structure that reflects one or both of near ultraviolet and near infrared |
| JPH08246337A (en) * | 1995-03-07 | 1996-09-24 | Kanebo Ltd | Fibrillated fiber or web |
| JPH11181630A (en) | 1997-05-02 | 1999-07-06 | Teijin Ltd | Conjugated fiber |
| JP3386994B2 (en) * | 1997-12-24 | 2003-03-17 | 田中貴金属工業株式会社 | Method for producing composite fiber structure and spinneret for production |
| JP3839613B2 (en) | 1999-03-31 | 2006-11-01 | 株式会社クラレ | Joined composite staple fiber and method for producing the same |
| JP6679921B2 (en) * | 2015-12-22 | 2020-04-15 | 東レ株式会社 | Multi-layer laminated fiber |
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| WO2022131312A1 (en) | 2022-06-23 |
| US20240110314A1 (en) | 2024-04-04 |
| KR20230119647A (en) | 2023-08-16 |
| EP4265828A1 (en) | 2023-10-25 |
| TW202233919A (en) | 2022-09-01 |
| JPWO2022131312A1 (en) | 2022-06-23 |
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