JP2023032004A - Fiber, and fiber product and electric and electronic apparatus including the same - Google Patents

Abstract

To provide a fiber having conductive and antistatic properties, as well as excellent flexibility, and fiber products and electric and electronic apparatuses including the same.SOLUTION: A fiber has a hollow cross section and contains ionic liquid.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to fibers having excellent flexibility in addition to conductivity and antistatic properties, and textile products and electric/electronic devices using the same.

In recent years, there has been an increasing demand for smart textiles, in which electronic components such as various devices, sensors, and IC chips are incorporated into textiles such as knitted and woven fabrics. These smart textiles are expected to be worn in various scenes because they can be designed according to the purpose, from sports use to medical use.

In smart textiles incorporating these electronic components, electrical wiring with low resistance is required for the transmission of electricity, which is the driving source of devices, and the transmission of electrical signals from sensors. When ordinary copper wire is used for this electrical wiring, although it exhibits sufficient conductivity for power transmission and signal transmission, copper wire lacks flexibility, so it cannot follow deformation such as bending and expansion and contraction of textiles. difficult. Therefore, for example, when copper wires are incorporated into clothing, there is a problem that they cause a sense of discomfort and hinder human movement.

In addition, in smart textiles incorporating electronic components, when it is necessary to suppress the effects of static electricity, there is a demand for materials that have antistatic properties and excellent flexibility.

Against this background, attention has been paid to the excellent ionic conductivity of ionic liquids, and various proposals have been made so far for fiber materials imparted with antistatic properties using ionic liquids. For example, fibers having antistatic properties have been proposed by incorporating an ionic liquid into the fibers (see Patent Documents 1 and 2). Further, a fiber having antistatic properties is proposed by coating the surface layer of a fiber containing carbon nanotubes with an ionic liquid (see Patent Document 3).

JP 2013-76081 A Japanese translation of PCT publication No. 2010-510402 JP 2013-244673 A

According to the technique of Patent Document 1, a fiber having antistatic properties is obtained by melt-blending an ionic liquid into a thermoplastic polymer and performing melt spinning. However, since the content of the ionic liquid relative to the thermoplastic polymer is as small as 0.1 to 10% by weight, there is a problem of insufficient antistatic properties.

According to the technique of Patent Document 2, a fiber having antistatic properties is obtained by dissolving polyurethane in an ionic liquid, performing solution spinning, and leaving the ionic liquid in the fiber. However, since the amount of the ionic liquid remaining in the fiber is as small as less than 10% by mass with respect to the total weight of the fiber, there is a problem that the antistatic property is insufficient.

According to the technique of Patent Document 3, a fiber having antistatic properties can be obtained by coating the surface layer of a fiber containing carbon nanotubes with an ionic liquid. However, since the fiber contains carbon nanotubes, the fiber lacks flexibility. In addition, since the ionic liquid is exposed on the fiber surface layer, the ionic liquid peels off due to friction or the like, resulting in poor durability.

Therefore, the object of the present invention has been made in view of the above circumstances, and provides a fiber having excellent flexibility in addition to conductivity and antistatic properties, and textile products and electric/electronic devices using the same. to provide.

As a result of the studies conducted by the present inventors, it is necessary to suppress the effects of static electricity in smart textiles that incorporate electronic components, such as when used for power transmission and signal transmission from sensors, and in smart textiles that incorporate electronic components. In some cases, it was confirmed that in addition to conductivity, antistatic properties, and electrical property stability against deformation, it is important to have excellent flexibility so that it follows the movement of the textile without discomfort. .

Therefore, as a result of intensive studies to achieve the above performance, the present inventors have found that by making a fiber having a hollow cross section and containing an ionic liquid inside it, in addition to deformation followability and electrical property stability, The present inventors have found that excellent flexibility that does not cause discomfort even when incorporated into textiles is exhibited, and have completed the present invention.

The above problem is solved by the present invention, ie a fiber with a hollow cross-section and containing an ionic liquid in its interior.

The fiber has a hollow portion area of 10 to 98% of the fiber cross-sectional area, a primary yield point elongation of 5 to 300%, a fiber diameter of 5 to 5000 μm, and a volume resistivity of 1 × It is preferably 10 ⁻³ to 1×10 ⁶ Ω·cm.

In addition, at least one of the fiber ends is provided with a liquid sealing portion that suppresses the outflow of the ionic liquid, at least two points are provided with current-carrying portions that contact the ionic liquid and conduct electricity, and It can be suitably adopted that the stopping portion and the current-carrying portion are integrated.

It is preferable that at least a part of the textile product or electric/electronic device of the present invention is composed of the above fibers.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain fibers having excellent flexibility in addition to conductivity and antistatic properties, and textile products and electric/electronic devices using the same.

It is an explanatory view of how to obtain the primary yield point elongation in the present invention.

The fiber of the present invention has a hollow cross-section and contains an ionic liquid therein. The constituent elements will be described in detail below, but the present invention is not limited to the scope described below as long as it does not exceed the gist of the present invention.

[fiber]
It is important that the fibers of the present invention have a hollow cross-section and contain the ionic liquid inside. By continuously filling the interior (that is, the hollow portion in the hollow section) with the ionic liquid in the fiber axis direction, it is possible to reduce the volume resistivity of the fiber, and the fiber has conductivity and antistatic properties. can be obtained. Moreover, when the environmental temperature is higher than the melting point of the ionic liquid, the ionic liquid has fluidity inside the fiber. Therefore, the ionic liquid can be uniformly present inside, and the uniformity of conductivity and antistatic properties in the direction of the fiber axis is excellent. Furthermore, even if the fiber is deformed by bending, stretching, or the like, it can be deformed so that the ionic liquid is uniformly present inside the fiber in a manner that follows the deformation. Excellent uniformity of antistatic properties. In addition, unlike metal materials such as copper, aluminum, and stainless steel used for ordinary metal wires, ionic liquids are organic compounds, so the fibers of the present invention are resistant to deformation such as bending and stretching regardless of the environmental temperature. It becomes a flexible fiber that is easy to follow. Therefore, when the fiber of the present invention is incorporated into textile products or electric/electronic devices, it enables flexible movement. is also suppressed, and a fiber excellent in wearing comfort can be obtained.

The ionic liquid in the present invention is a compound composed of cations and anions.

Cations constituting the ionic liquid include imidazole, pyridine, ammonia, pyrroline, pyrazole, carbazole, indole, lutidine, pyrrole, pyrazole, piperidine, pyrrolidine, 1,8-diazabicyclo[5.4.0]undec-7-ene. , 1,5-diazabicyclo[4.3.0]-5-nonene and other compounds in which protons or alkyl groups are bonded to nitrogen atoms and derivatives thereof, and compounds in which protons or alkyl groups are bonded to sulfur atoms such as sulfides and derivatives thereof, compounds in which protons or alkyl groups are bonded to phosphorus atoms such as phosphine, and derivatives thereof, but are not limited thereto. Moreover, the cations constituting the ionic liquid may contain a plurality of heteroatoms such as nitrogen, sulfur, phosphorus, and oxygen. Among them, imidazolium cations or pyridinium cations having imidazole or pyridine in the skeleton can be preferably used because of their excellent electrical properties.

Specific examples of cations constituting the ionic liquid include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, 1-tetradecyl-3-methylimidazolium, 1-hexadecyl-3-methylimidazolium, 1-octadecyl-3-methylimidazolium, 1-allyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-hexyl-2,3-dimethylimidazolium, 1-ethylpyridinium , 1-butylpyridinium, 1-hexylpyridinium, 1-butyl-4-methylpyridinium, 1-butyl-3-methylpyridinium, 1-hexyl-4-methylpyridinium, 1-hexyl-3-methylpyridinium, 1-octyl -4-methylpyridinium, 1-octyl-3-methylpyridinium, 1-butyl-3,4-dimethylpyridinium, 1-butyl-3,5-dimethylpyridinium, trimethylpropylammonium, methylpropylpiperidinium and the like. but not limited to these.

Examples of anions constituting the ionic liquid include, but are not limited to, halogen anions, pseudohalogen anions, carboxylate anions, superacid anions, sulfonate anions, and phosphate anions. Among them, a superacid anion and a sulfonate anion can be preferably used because of their excellent electrical properties.

Halogen anions include fluorine anions, chlorine anions, bromine anions, and iodine anions.

Pseudohalogen anions include, but are not limited to, cyan anions, thiocyanate anions, cyanate anions, flumate anions, azide anions, and the like.

Carboxylate anions include, but are not limited to, monocarboxylate anions or dicarboxylate anions having 1 to 18 carbon atoms. Specific examples of carboxylate anions include, but are not limited to, formate anion, acetate anion, propionate anion, butyrate anion, valerate anion, fumarate anion, oxalate anion, lactate anion, pyruvate anion, and the like. .

Examples of superstrong acid anions include borofluorate anion, tetrafluoroborate anion, perchlorate anion, hexafluorophosphate anion, hexafluoroantimonate anion, and hexafluoroarsenate anion. is not limited to

Examples of sulfonate anions include, but are not limited to, sulfonic acids having 1 to 26 carbon atoms. Specific examples of sulfonate anions include methanesulfonate anion, p-toluenesulfonate anion, octylbenzenesulfonate anion, dodecylbenzenesulfonate anion, laurylbenzenesulfonate anion, octadecylbenzenesulfonate anion, and eicosylbenzenesulfonate anion. Examples include, but are not limited to, anions, octanesulfonate anions, dodecanesulfonate anions, eicosanesulfonate anions, and the like.

Phosphate anions include, but are not limited to, phosphate anions, phosphate ester anions having 1 to 40 carbon atoms, and the like. Specific examples of the phosphate anion include phosphate anion, methyl phosphate monoester anion, octyl phosphate monoester anion, octyl phosphate diester anion, lauryl phosphate monoester anion, lauryl phosphate diester anion, and stearyl phosphate monoester anion. Examples include, but are not limited to, anions, stearyl phosphate diester anions, eicosyl phosphate monoester anions, eicosyl phosphate diester anions, and the like.

Various ionic liquids can be obtained by combining these cations and anions. Specific examples of ionic liquids include 1,3-dimethylimidazolium methanesulfonate, 1,3-dimethylimidazolium fluorohydrogenate, 1-ethyl-3-methyl-imidazolium chloride, 1-ethyl-3-methyl-imidazolium Lithium bromide, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium dicyanamide , 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium fluorohydrogenate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium acetate , 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium chloride, 1 -Allyl-3-methylimidazolium chloride, 1-ethyl-2,3-dimethylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-hexyl-2,3-dimethylimidazolium chloride , 1-ethylpyridinium bromide, 1-butylpyridinium bromide, 1-butyl-3-methylpyridinium chloride, 1-butylpyridinium hexafluorophosphate, 1-hexylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium tetrafluoroborate , 3,5-dimethylbutylpyridinium chloride, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butylpyridinium nitrate, dimethylmethyl-2-methoxyethylammonium tetrafluoroborate, dimethylmethyl-2-methoxyethylammonium bistrifluoromethanesulfonylimide, trimethylpropylammonium bistrifluoromethanesulfonylimide, methylpropylpiperidinium bistrifluoromethane sulfonylimides and the like, but these include Not limited. Among them, 1,3-dimethylimidazolium fluorohydrogenate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium tetrafluoroborate Chloroaluminate and 1-ethyl-3-methylimidazolium fluorohydrogenate are preferably used because of their excellent electrical properties.

The ionic liquid in the present invention preferably has a melting point of 200° C. or less. By setting the melting point to preferably 200° C. or lower, more preferably 100° C. or lower, and even more preferably 40° C. or lower, the ionic liquid has fluidity inside the fiber when the environmental temperature is higher than the melting point of the ionic liquid. Therefore, in addition to being flexible, the ionic liquid can be uniformly present inside, resulting in a fiber with excellent uniformity in conductivity and antistatic properties in the fiber axial direction. Furthermore, even if the fiber is deformed by bending, stretching, or the like, it can be deformed so that the ionic liquid is uniformly present inside the fiber in a manner that follows the deformation. It becomes a fiber excellent in antistatic uniformity. Considering that the fiber of the present invention is used for textile products, particularly clothing, the melting point of the ionic liquid is more preferably room temperature (25° C.) or less. By keeping the melting point of the ionic liquid below room temperature (25°C), when it is used in textile products such as clothing, it is less likely to cause discomfort and inhibits human movement, making it highly comfortable to wear. fiber.

The ionic liquid in the present invention includes inorganic oxides such as titanium oxide, silica, and barium oxide, carbon-based compounds such as carbon black and carbon nanotubes, gold, silver, copper, and aluminum for the purpose of improving the electrical properties of fibers. , potassium, magnesium, rhodium, sodium, molybdenum, iridium, tungsten, cobalt, brass, zinc, beryllium, nickel, ruthenium, potassium, cadmium, osmium, indium, lithium, iron, platinum, tin, chromium and palladium. , polyacetylene, polyaniline, polythiophene, and polypyrrole.

The fiber of the present invention contains an ionic liquid in the hollow portion of the hollow cross-section fiber, and the hollow cross-section fiber is preferably made of a thermoplastic polymer. Since the hollow cross-section fiber is made of a thermoplastic polymer, it is possible to use a melt spinning method for its production, so that it is easy to mold into a fiber shape, contains an ionic liquid inside, and has a uniform shape in the fiber axis direction. It is possible to obtain fibers having

Examples of thermoplastic polymers used in the fiber of the present invention include polyester polymers such as "polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate" and copolymers thereof, and "polylactic acid, polyethylene succinate". polybutylene succinate, polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate copolymer, polycaprolactone” and other aliphatic polyester polymers and copolymers thereof, “polyamide 6, polyamide 66, polyamide 610, polyamide 10, polyamide 12, polyamide 6-12” and other aliphatic polyamide polymers and copolymers thereof, polyolefin polymers and their copolymers such as “polyethylene, polypropylene, polybutene, polymethylpentene”, “ethylene Elastomers such as water-insoluble ethylene-vinyl alcohol copolymer containing 25 mol% to 70 mol% units, polystyrene, polydiene, chlorine, polyolefin, polyester, polyurethane, polyamide, fluorine, etc. It is a system polymer, etc., and can be used by selecting from among these. Among them, polyester-based polymers and their copolymers, aliphatic polyamide-based polymers and their copolymers, polyolefin-based polymers and their copolymers are preferably used in view of their excellent mechanical properties and durability, particularly polyethylene terephthalate. , polyamide 6, polyamide 66 and polypropylene are preferably used. Elastomer-based polymers are preferably used because of their excellent stretchability, and polyurethane-based elastomers are particularly preferably used. These thermoplastic polymers may be used alone or in combination of two or more.

The fiber of the present invention contains inorganic oxides such as titanium oxide, silica and barium oxide, carbon-based compounds such as carbon black and carbon nanotubes, gold, silver, copper, aluminum, potassium, magnesium, rhodium, sodium, molybdenum, iridium, tungsten, cobalt, brass, zinc, beryllium, nickel, ruthenium, potassium, cadmium, osmium, indium, lithium, iron, platinum, tin, chromium and Various additives such as metal particles such as palladium, colorants such as dyes and pigments, flame retardants, fluorescent brighteners, antioxidants, and ultraviolet absorbers may be included.

The hollow cross-section fiber in the present invention is not particularly limited in terms of the cross-sectional shape of the fiber as long as it has a hollow portion, and can be appropriately selected according to the application and required properties. It may also be of non-circular cross-section. Examples of non-circular cross-sections include, but are not limited to, multi-lobed, polygonal, flattened, elliptical, and the like. Moreover, in a circular cross section, it may be a concentric hollow type in which the hollow portions are arranged concentrically, or an eccentric hollow type in which the hollow portions are arranged in an eccentric shape. Furthermore, the cross section may be a multi-hollow section having a plurality of hollow portions. Whether there is one hollow portion or a plurality of hollow portions, the shape of the hollow portion in the cross section of the fiber is not particularly limited, and may be a perfect circular cross section or a non-circular cross section. Examples of non-circular cross-sections include, but are not limited to, multi-lobed, polygonal, flattened, elliptical, and the like.

In the fiber of the present invention, the area of the hollow portion is preferably 10 to 98% of the cross-sectional area of the fiber. The hollow area is preferably 10% or more of the fiber cross-sectional area, more preferably 20% or more of the fiber cross-sectional area, and still more preferably 30% or more of the fiber cross-sectional area, so that a certain amount or more of ionic liquid is contained. It is possible to impart antistatic properties and conductivity to the fibers. In addition, the area of the hollow portion is preferably 98% or less of the fiber cross-sectional area, more preferably 90% or less of the fiber cross-sectional area, further preferably 80% or less of the fiber cross-sectional area, so that the hollow containing the ionic liquid in the cross section The proportion occupied by the part is reduced, and mechanical properties such as strength are improved.

The fiber of the present invention preferably has a primary yield point elongation of 5 to 300%. By setting the primary yield point elongation to preferably 5% or more, more preferably 10% or more, and even more preferably 20% or more, the fiber becomes flexible and easily follows deformation such as bending and stretching. It enables flexible movement when incorporated into products and electrical/electronic devices, and in particular, when incorporated into textiles such as clothing, it does not create a sense of discomfort and inhibits human movement, making it comfortable to wear. fiber with excellent properties. Further, by setting the primary yield point elongation to preferably 300% or less, more preferably 250% or less, and even more preferably 200% or less, it is possible to suppress the change in resistance during expansion and contraction.

In addition, the primary yield point elongation in the present invention means that the fiber sealed by attaching an adhesive so as to cover the openings at both ends of the fiber end described later is subjected to tension using a Tensilon tensile tester. The fiber is set without stress, and the sample length is 200 mm and the tensile speed is 200 mm / min. It is calculated as elongation (see FIG. 1), measured five times per level, and obtained from the arithmetic mean value.

The fiber of the present invention preferably has a volume resistivity of 1×10 ⁻³ to 1×10 ⁶ Ω·cm. By setting the volume resistivity to preferably 1×10 ⁻³ Ω·cm or more, more preferably 1×10 ⁻² Ω·cm or more, substantially the proportion of the hollow portion containing the ionic liquid in the cross section of the fiber is increased. It becomes smaller, and mechanical properties such as strength are improved. In addition, by setting the volume resistivity to preferably 1×10 ⁶ Ω·cm or less, more preferably 1×10 ⁵ Ω·cm or less, and even more preferably 1×10 ⁴ Ω·cm or less, in addition to antistatic properties, conductivity can be obtained.

The fiber of the present invention preferably has a liquid sealing portion on at least one end of the fiber in order to prevent the ionic liquid inside from flowing out from the end of the fiber. The liquid sealing part is formed by injecting a fluid resin or adhesive into the opening of the fiber end and then solidifying it, by attaching the resin or adhesive so as to cover the opening of the fiber end, or by If it is possible to close the opening (hollow part) at the end of the fiber by inserting a solid material such as metal, resin or mineral into the opening in the part, twisting, tying, or crushing the fiber itself Any form is acceptable. By doing so, it is possible to suppress the outflow of the ionic liquid from the fiber ends.

Resins used for the liquid sealing portion include, but are not limited to, epoxy resins, urethane resins, modified silicones, polyester resins, nylon resins, polypropylene resins, polystyrene resins, and polylactic acid.

Examples of the adhesive used for the liquid sealing portion include, but are not limited to, inorganic, organic, natural, and synthetic adhesives.

Metals used for the liquid sealing portion include gold, silver, copper, aluminum, potassium, magnesium, rhodium, sodium, molybdenum, iridium, tungsten, cobalt, brass, zinc, beryllium, nickel, ruthenium, potassium, cadmium, and osmium. , indium, lithium, iron, platinum, tin, chromium, and palladium. From the viewpoint of corrosiveness, gold or silver alone, or the above metals plated with gold or silver are preferred.

Preferably, the fiber of the present invention is provided with at least two current-carrying portions that contact the ionic liquid inside the fiber from the outside and conduct electricity. The current-carrying part may penetrate from the surface of the fiber and come into contact with the ionic liquid inside, or contact the ionic liquid inside at the opening at the end of the fiber. can be in any form.

Current-carrying materials include gold, silver, copper, aluminum, potassium, magnesium, rhodium, sodium, molybdenum, iridium, tungsten, cobalt, brass, zinc, beryllium, nickel, ruthenium, potassium, cadmium, osmium, indium, and lithium. , metals such as iron, platinum, tin, chromium, and palladium, and carbon-based materials such as carbon, graphene, fullerene, and carbon nanotubes, as long as they are conductive. Alternatively, the resin may contain such metals or carbon-based particles and be processed so as to obtain electrical conductivity. When using the above metals, from the viewpoint of corrosiveness, gold or silver alone, or the above metals plated with gold or silver are preferable.

In the present invention, the liquid sealing portion and the conducting portion may be integrated. For example, by preparing two cylindrical metals having approximately the same diameter as the diameter of the hollow portion of the fiber and inserting them into the openings at both ends of the fiber until they come into contact with the ionic liquid and fixing them, the ionic liquid inside the fiber ends As a result, it is possible to conduct electricity through the ionic liquid between the columnar metals at both ends. As the columnar metal, those mentioned above as the material of the current-carrying portion can be preferably used.

The resistance value, resistivity and volume resistivity in the present invention are obtained as follows.
(1) The fiber is fixed without applying tension or stretched to an arbitrary elongation rate, and the probe of the resistance meter set to the resistance measurement range is set to contact the ionic liquid inside the fiber, Measure the resistance (Ω).
(2) Divide the resistance value (Ω) obtained in (1) above by the fiber length (cm) to obtain the resistivity (Ω/cm).
(3) The resistivity (Ω/cm) obtained in (2) above is multiplied by the cross-sectional area A (cm ² ) of the fiber subjected to measurement by the method described later to obtain a value.
(4) The above measurement is performed 5 times at different measurement locations for each level, and the arithmetic average value is defined as the volume resistivity (Ω·cm).

In the fiber of the present invention, if the volume resistivity of the ionic liquid is known, the resistance value of the fiber can be calculated arithmetically. The resistance value R (Ω) of the fiber when the volume resistivity of the ionic liquid is ρ (Ω cm), the length is L (cm), and the cross-sectional area of the enclosed ionic liquid is S (cm ² ) is It becomes possible to obtain by the formula (1).
R=ρ×L/S (1)

The fiber of the present invention changes its resistance value as the fiber is stretched. To explain this using the above formula (1), when the fiber length is doubled, L (cm) is doubled and S (cm ² ) is halved, so the resistance value R ( Ω) is four times that before stretching. Therefore, it can be used as an elongation rate sensor utilizing the ability to convert the elongation rate simply by measuring the resistance value. On the other hand, since the resistance value changes according to the elongation rate of the fiber, when using the fiber for power transmission or signal transmission, secure the cross-sectional area of the ionic liquid so that it has a sufficient resistance value even when it is stretched. There is a need.

The fiber of the present invention preferably has a total fineness of 10 to 300,000 dtex when made into a multifilament. By setting the total fineness to preferably 10 dtex or more, more preferably 20 dtex or more, and even more preferably 30 dtex or more, the breaking strength of the fiber is increased, so that the fiber has good processability and excellent durability during use. . In addition, by setting the total fineness to preferably 300,000 dtex or less, more preferably 100,000 dtex or less, and even more preferably 10,000 dtex or less, the fibers become flexible and easily follow deformation such as bending, so that textile products and electric/electronic devices can be obtained. When incorporated into a textile, the fiber can be moved flexibly, and in particular, even when incorporated into textiles such as clothing, the fiber does not feel uncomfortable and is highly comfortable to wear.

The total fineness in the present invention is obtained by taking 100 m of fiber, multiplying the mass of the skein by 100, calculating the total fineness (dtex), measuring 5 times per level, and calculating the arithmetic average value. is. If the fiber is shorter than 100 m or cannot be skeined, measure the length (m) and mass (g) of the fiber, and calculate the total fineness ( dtex) may be calculated.

The fibers of the present invention preferably have a fiber diameter of 5 to 5000 μm. By setting the fiber diameter to preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more, the strength of the fiber is increased, so that thread breakage due to abrasion such as friction is reduced, and the process passability is good and during use. It becomes a fiber with excellent durability. In addition, by setting the fiber diameter to preferably 5000 μm or less, more preferably 3000 μm or less, and even more preferably 1000 μm or less, the fiber becomes flexible and easily follows deformation such as bending. In particular, when incorporated into textiles such as clothing, the fibers do not feel uncomfortable and are highly comfortable to wear.

The cross-sectional area, fiber diameter, and hollow area in the present invention are obtained as follows.
(1) A single fiber is cut in the direction perpendicular to the fiber axis, and an image is taken with a scanning electron microscope at a magnification that allows observation of the entire cross section of the single fiber.
(2) For the photographed image, using image analysis software, measure the cross-sectional area (cm ² ) ^formed by the cross-sectional contour of the single fiber. μm) is calculated.
(3) Randomly sampled 20 locations, and take the arithmetic mean value as the fiber diameter (μm).
(4) Using image analysis software, measure the area (cm ² ) of the hollow portion formed by the interface contour between the inner wall of the hollow portion of the single fiber and the ionic liquid.

The fiber of the present invention preferably has a breaking strength of 1.0 cN/dtex or more. By setting the breaking strength to preferably 1.0 cN/dtex or more, more preferably 1.5 cN/dtex or more, and even more preferably 2.0 cN/dtex or more, yarn breakage in post-processing steps such as weaving and knitting, electrical・In addition to reducing yarn breakage when incorporated into electronic equipment, yarn breakage is also reduced when textile products and electrical/electronic equipment are used, resulting in fibers with good processability and excellent durability during use. On the other hand, the upper limit of the breaking strength in the present invention is not particularly limited, but about 10.0 cN/dtex is a substantial upper limit.

In addition, the breaking strength in the present invention refers to the tensile strength described in JIS L1013: 2010 8.5 of the fiber sealed by attaching an adhesive so as to cover the openings at both ends of the fiber as described above. And based on the elongation rate, set the fiber without applying tension, measure the strength (cN) at break under the conditions of a sample length of 200 mm and a tensile speed of 200 mm / min, and divide by the total fineness (dtex) The intensity (cN/dtex) is calculated, five measurements are performed per level, and the arithmetic average value is obtained.

The fiber of the present invention preferably has a breaking elongation of 15 to 500%. By setting the breaking elongation to preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more, yarn breakage in post-processing steps such as weaving and knitting, and yarn when incorporated into electrical and electronic equipment In addition to reducing breakage, yarn breakage during use of textile products and electric/electronic equipment is also reduced, resulting in a fiber that has good process passability and excellent durability during use. In addition, by setting the breaking elongation to preferably 500% or less, more preferably 450% or less, and even more preferably 400% or less, the fibers are less likely to be plastically deformed when stretched, so that the durability during use is excellent. fiber.

In addition, the breaking elongation in the present invention refers to the tensile strength described in JIS L1013:2010 8.5 of the fiber sealed by attaching an adhesive so as to cover the openings on both ends of the fiber as described above. Based on the thickness and elongation rate, set the fiber without applying tension, measure the elongation (%) at break under the conditions of a sample length of 200 mm and a tensile speed of 200 mm / min, and measure 5 times per level. , is obtained from the arithmetic mean value thereof.

The fibers of the present invention preferably have a 10% modulus of 1.50 cN/dtex or less. By setting the 10% modulus to preferably 1.50 cN/dtex or less, more preferably 1.00 cN/dtex or less, and even more preferably 0.50 cN/dtex or less, the stress caused by deformation is reduced, so that the flexibility can be improved. It becomes a fiber excellent in On the other hand, although the lower limit of the 10% modulus in the present invention is not particularly limited, 0.00 cN/dtex is a substantial lower limit.

In addition, the 10% modulus in the present invention means that the fiber sealed by attaching an adhesive so as to cover the openings at both ends of the fiber as described above is subjected to the tensile strength described in JIS L1013:2010 8.5. Based on the thickness and elongation rate, set the fiber without applying tension, measure the stress (cN / dtex) when elongating 10% under the conditions of a sample length of 200 mm and a tensile speed of 200 mm / min. Measurement is performed 5 times, and the arithmetic average value is obtained.

Since the fiber of the present invention has excellent flexibility in addition to conductivity, antistatic properties, and stability of electrical properties against deformation, it can be used as an antistatic material for stockings and tights. , clothing such as dustproof clothing, textiles such as curtains, carpets and mats for indoors and outdoors, and in vehicles, and flooring materials. It can be suitably used for smart textiles such as power transmission and electric signal transmission from sensors. In addition, by incorporating the fiber of the present invention into parts that require movement such as stretching and bending in electrical and electronic equipment, it can be suitably used for power transmission and electrical signal transmission from sensors. , the fibers of the present invention themselves can be used as sensors, heaters, and the like.

By using an ionic liquid whose melting point is higher than the environmental temperature, the fiber of the present invention can be freely changed in shape with a heat source such as body temperature or a dryer. It can be a textile that maintains This property can be used for objects that can be freely changed in shape, screens that can be expanded in a plane when necessary, and so on.

[Fiber products]
The textile product of the present invention is at least partially composed of the fiber of the present invention. Textile products include textiles such as woven fabrics and knitted fabrics, as well as clothing made from these fabrics. By including the fiber of the present invention in at least a part thereof, textiles and clothing that are comfortable to wear without, or hardly cause, discomfort when worn can be obtained.

The clothing of the present invention is an article worn to partially or wholly cover the body, and includes not only clothing such as upper and lower garments, kimonos and coveralls, but also hats, gloves, socks and the like. Among them, by applying it to smart textiles, which are clothing incorporating electronic parts such as various devices, sensors, and IC chips, the fibers of the present invention such as conductivity and antistatic properties, as well as electrical property stability against deformation and flexibility. It is more preferable because it is possible to fully exhibit the characteristics.

For example, when the fiber of the present invention is applied to smart textiles, unlike ordinary metal wires such as copper, aluminum, and stainless steel, it is possible to bend and stretch due to the high flexibility caused by the fiber material and the ionic liquid inside. It is easy to follow the deformation of , there is no or less discomfort when worn, and hindrance to human movement is suppressed, making it a smart textile with excellent wearing comfort. Furthermore, depending on the volume resistivity of the fiber, the fiber of the present invention is capable of transmitting electricity that serves as a drive source for devices, transmitting electrical signals from sensors, suppressing the effects of static electricity, and the like. Excellent stability of characteristics. Therefore, the fibers of the present invention can be applied to smart textiles for various uses.

When the fiber of the present invention is used to transmit electricity, the clothing of the present invention is suitable because the surface material of the fiber is made non-conductive to prevent electric shock, leakage, etc. when worn.

[Electrical/electronic equipment]
The electric/electronic device of the present invention is at least partially composed of the fiber of the present invention. By including the fiber of the present invention in at least a part thereof, an electric device or electronic device can smoothly perform operations such as bending and expansion and contraction, and has excellent electrical property stability against deformation.

Depending on the volume resistivity of the fiber, the fiber of the present invention can be used to transmit electricity, which is the driving source of devices, to transmit electrical signals from sensors, to suppress the effects of static electricity, etc. In addition, it has stable electrical characteristics against deformation. It is also excellent in sex. Therefore, the fiber of the present invention can be applied to electrical and electronic devices for various purposes that require motions such as bending and stretching.

When the fiber of the present invention is used for power transmission, the electrical/electronic device of the present invention is suitable because the surface material of the fiber is made non-conductive to prevent electric leakage and the like.

The fibers of the present invention can be used by bundling a plurality of fibers. A plied yarn, a covered yarn, a braided cord, or the like is preferable because the fibers can be bundled into a compact size and the handleability is improved. Further, by using the fibers as warp and/or weft of a fabric, it can be used as a flat cable, and by using both warp and weft as fibers, a matrix-like flat cable can be obtained.

[Method for manufacturing textiles, textile products, and electric/electronic devices]
Next, preferred embodiments for producing the fiber of the present invention will be specifically described.

The method for producing the fiber of the present invention can be selected from a melt spinning method, a solution spinning method, and the like, but it is preferable to apply the melt spinning method because of its low environmental load and ease of production.

The thermoplastic polymer used in the present invention is preferably dried before spinning for the purpose of preventing water contamination and removing oligomers, in order to improve spinning properties. As drying conditions, vacuum drying at 80 to 200° C. for 1 to 24 hours is usually used.

For melt spinning, a melt spinning method using an extruder such as a pressure melter type, single-screw or twin-screw extruder type can be applied. The extruded thermoplastic polymer passes through a pipe and is weighed by a weighing device such as a gear pump. After passing through a foreign matter-removing filter, it is guided to a spinneret and discharged in a shape having a hollow cross section.

When polyester or polyamide is used as the thermoplastic polymer, the temperature (spinning temperature) from the polymer pipe to the spinneret is preferably the melting point of the thermoplastic polymer + 20 ° C. or higher in order to increase the fluidity, and the thermal decomposition of the thermoplastic polymer. In order to suppress it, it is preferable to set the temperature to 320° C. or less.

When the ambient temperature is lower than the melting point of the ionic liquid and the ionic liquid is solidified, the ionic liquid used in the present invention is melted by heating the container containing the ionic liquid with a band heater or hot water bath. can be used. After melting, the ionic liquid can be metered by a positive displacement pump such as a gear pump or tube pump, a syringe pump, etc., is guided to a spinneret via a pipe, and fills the inside of the thermoplastic polymer with a hollow cross section. Dispensed. The melting temperature of the ionic liquid is preferably the melting point of the ionic liquid plus 20° C. or higher in order to increase fluidity.

The undrawn fibers discharged from the spinneret are preferably cooled and solidified by blowing cooling air (air). The temperature of the cooling air can be determined in balance with the cooling air velocity from the viewpoint of cooling efficiency, and is preferably 30° C. or less. By setting the temperature of the cooling air to preferably 30° C. or less, the solidification behavior due to cooling is stabilized, and fibers with high uniformity in fiber diameter can be obtained.

The undrawn fibers discharged from the spinneret may be led to a cooling bath and quenched. The temperature of the cooling bath is preferably 10-90°C. If the temperature of the cooling bath is 10° C. or higher, the fibers do not meander in the cooling bath and fibers with high uniformity in fiber diameter can be obtained, which is preferable. On the other hand, if the temperature of the cooling bath is 90° C. or lower, solidification behavior by cooling is stabilized, and fibers with high uniformity in fiber diameter can be obtained, which is preferable. Also, the cooling time can be appropriately adjusted according to the discharge amount, take-up speed, and the like.

The coolant for the cooling bath is a substance that can be easily removed from the fiber surface, does not give physical or chemical changes to the fiber, and is liquid within the temperature range of the cooling bath, and is used without particular limitation. be able to. Specific examples of cooling bath coolants include, but are not limited to, water, paraffin, ethylene glycol, glycerin, amyl alcohol, xylene, and the like.

Moreover, it is preferable to flow the cooling air in a direction substantially perpendicular to the undrawn fibers discharged from the spinneret. At this time, the speed of the cooling air is preferably 10 m/min or more from the viewpoint of cooling efficiency and fiber diameter uniformity, and preferably 100 m/min or less from the viewpoint of spinning stability.

The cooled and solidified undrawn fiber may be directly wound by a winder, or may be taken by a roller rotating at a constant speed (godet roller) and then wound by a winder.

The undrawn fibers thus obtained may be subjected to a drawing step after being once wound up or continuously after being taken up. Stretching is carried out by running the film over a heated first roller or a heating device provided between the first and second rollers, such as a heating bath or a hot plate. The drawing conditions are determined by the mechanical properties of the undrawn fibers obtained, and the drawing temperature is determined by the temperature of the heated first roller or the heating device provided between the first roller and the second roller. The draw ratio is determined by the ratio of the peripheral speeds of the first roller and the second roller.

Furthermore, after passing through the second roller, the drawn fiber can be heated by a heated third roller or a heating device provided between the second roller and the third roller to perform heat setting. . Heat setting promotes crystallization, resulting in fibers with excellent shape stability.

The fibers obtained by the manufacturing method described above are incorporated into textiles such as woven and knitted fabrics. When incorporated into a woven or knitted fabric, a method of using the fiber of the present invention as part or all of the fibers used in the manufacturing process, or sewing the fiber of the present invention onto a gray fabric or knitted fabric composed of other fibers. methods and the like. The textile (woven fabric or knitted fabric) thus obtained is used to sew the clothing of the present invention. Another example is a method of directly sewing the fiber of the present invention onto clothing. Furthermore, when incorporating the fiber of the present invention into an electric/electronic device, the same method as for ordinary electric wiring such as copper wire can be adopted.

The present invention will now be described in detail based on examples. However, the present invention is not limited only to these examples. In the measurement of each physical property, unless otherwise specified, the measurement was performed according to the method described above.

(1) Fiber Diameter, Cross-Sectional Area, and Hollow Area A single fiber was imaged using a scanning electron microscope "S-5500" manufactured by Hitachi High-Technologies Corporation at a magnification that allows observation of the entire cross section of the single fiber. After that, as image analysis software, "WinROOF2015" manufactured by Mitani Shoji Co., Ltd. was used, and the measurement was performed as described above.

(2) Resistance Value, Resistivity, and Volume Resistivity The resistance value was measured as described above using a resistance meter "RM3544" manufactured by Hioki Electric Co., Ltd. Also, the resistivity and volume resistivity were calculated as described above.

(3) Primary yield point elongation For the primary yield point elongation, the fiber sealed by attaching an adhesive so as to cover the openings at both ends of the fiber end is measured using a Tensilon tensile tester. I took measurements along the way.

(4) Flexibility 5 fibers obtained in Examples and Comparative Examples were arranged in parallel at intervals of 1 cm in the course direction of a knitted fabric made of polyester (pique knitting, basis weight 170 g/m ² ), each 10 cm long. Sewn ((parallel stitching, 0.5 cm interval). Twenty subjects evaluated the flexibility of the knitted fabric with the fibers sewn, and 5 points were "extremely flexible and there is no discomfort", and "very soft 4 points for "flexible and almost no discomfort", 2 points for "hard and slightly uncomfortable", and 1 point for "extremely hard and uncomfortable". , the average score of the scores given by each of the 20 subjects was calculated, and an average score of 3.0 or more was regarded as a pass.

(5) Deformation followability The knitted fabric produced in the evaluation of (4) above was stretched in the course direction by 20 subjects to evaluate the deformation followability. 5 points, "Very high deformation followability, no discomfort" 4 points, "High deformation followability, almost no discomfort" 3 points, "Low deformation followability, slightly uncomfortable" 2 points A score of 1 point was given for "extremely low conformability to deformation, giving a sense of discomfort", and the average score given by each of the 20 subjects was calculated.

(6) Quality The quality of the knitted fabric produced in the evaluation of (4) above was evaluated by 20 subjects. 4 points for "Very good quality", 3 points for "Excellent quality with almost no sliminess or stickiness", 2 points for "Slimy or sticky, poor quality", 2 points for "Very slimy or sticky, extremely high quality""Inferior" was defined as 1 point, and the average score of the scores given by each of the 20 subjects was calculated.

[Example 1]
We designed and fabricated a spinneret with a structure (a so-called core-sheath structure) that can eject a polymer in a cylindrical shape and an ionic liquid inside it. Polyurethane "Lycra" T-127 manufactured by Toray Operontex Co., Ltd. is used as the thermoplastic polymer of the hollow cross-section fiber, 1-ethyl-3-methylimidazolium tetrafluoroborate is used as the internal ionic liquid, and the spinning temperature is 220. It was melt spun at °C. In melt spinning, the polyurethane was weighed by a weighing method using a gear, and the ionic liquid was weighed by a syringe pump and introduced to the spinneret. Thereafter, a single yarn was discharged from a spinneret nozzle at a volume of 0.037 mL/minute of polyurethane and 0.037 mL/minute of ionic liquid, and wound with a winder at 200 m/minute to obtain a fiber. Table 1 shows the evaluation results of the obtained fibers.

[Examples 2 to 4]
In Example 2, the single yarn discharge volume was 1.48 mL/min of polyurethane, the ionic liquid was 1.48 mL/min, and the winding speed was 100 m/min. Minutes, ionic liquid 2.22 mL / min, winding speed 20 m / min, in Example 4, the volume of single yarn discharge is polyurethane 20.4 mL / min, ionic liquid 20.4 mL / min, winding speed 5 m / min A fiber was obtained in the same manner as in Example 1, except that the amount was changed to 10 minutes. Table 1 shows the evaluation results of the obtained fibers.

[Examples 5 to 8]
In Example 5, the single yarn discharge volume was 3.13 mL/min of polyurethane and 0.17 mL/min of ionic liquid, and in Example 6, the volume of single yarn discharge was 2.54 mL/min of polyurethane and 0.64 mL/min of ionic liquid. In Example 7, the single yarn discharge volume was 0.94 mL/minute of polyurethane and 2.18 mL/minute of ionic liquid. Fibers were obtained in the same manner as in Example 2, except that the rate was changed to 94 mL/min. Table 1 shows the evaluation results of the obtained fibers.

[Examples 9 to 13]
Fibers were obtained in the same manner as in Example 7, except that the ionic liquid was changed as shown in Table 2. Table 2 shows the evaluation results of the obtained fibers.

[Examples 14 to 16]
In Example 14, polyethylene terephthalate "T701T" manufactured by Toray Industries, Inc. was used as the thermoplastic polymer, the volume of the single yarn discharged was polyethylene terephthalate 0.98 mL/min, the ionic liquid was 2.28 mL/min, and the spinning temperature was 290°C. In 15, nylon 6 ""Amilan"CM1017" manufactured by Toray Industries, Inc. was used as the thermoplastic polymer, the volume of single yarn discharge was nylon 6 0.94 mL / minute, the ionic liquid was 2.18 mL / minute, and the spinning temperature was 260 ° C. In Example 16, polypropylene "Novatec"MA2" manufactured by Japan Polypropylene Co., Ltd. was used as the thermoplastic polymer, the volume of single yarn discharge was changed to 0.90 mL/min for polypropylene, the ionic liquid was changed to 2.11 mL/min, and the spinning temperature was changed to 240°C. A fiber was obtained in the same manner as in Example 7, except that Table 2 shows the evaluation results of the obtained fibers.

[Comparative Example 1]
Polyurethane ""Lycra"T-127" manufactured by Toray Operontex Co., Ltd. is used as a thermoplastic polymer, and a spinneret with a discharge hole diameter of 0.18 mm, a discharge hole length of 0.23 mm, a hole number of 1, and a round hole is used. was melt-spun at a spinning temperature of 220°C. In melt spinning, the polyurethane was metered by a gear metering method and led to the spinneret. Thereafter, the single yarn was discharged from a spinneret nozzle at a volume of 3.17 mL/min, and was wound by a winder at 100 m/min to obtain a fiber having a solid cross section without hollow portions. Table 3 shows the evaluation results of the obtained fibers. The resulting fiber had a high volume resistivity and extremely poor electrical properties.

[Comparative Example 2]
We designed and fabricated a spinneret with a core-sheath structure that can eject ionic liquid in a cylindrical shape and polymer inside. 1-ethyl-3-methylimidazolium tetrafluoroborate is used as the ionic liquid, and polyurethane "Lycra" T-127 manufactured by Toray Operontex Co., Ltd. is used as the internal thermoplastic polymer, and the spinning temperature is 220 ° C. spun. In the melt spinning, the ionic liquid was weighed by a syringe pump, and the polyurethane was weighed by a weighing method using a gear, and guided to the spinneret. Thereafter, the single yarn was spun by discharging the ionic liquid at a volume of 1.48 mL/min and the polyurethane at a volume of 1.48 mL/min in the spinneret, and wound with a winder at 100 m/min to obtain a fiber. Table 3 shows the evaluation results of the obtained fibers. Since the ionic liquid was exposed on the surface of the fiber, the obtained fiber was extremely slimy and sticky, and was extremely inferior in quality.

[Comparative Example 3]
80.0% by weight of polyurethane "Lycra" T-127 manufactured by Toray Operontex Co., Ltd. as a thermoplastic polymer, and 20.0% by weight of 1-ethyl-3-methylimidazolium tetrafluoroborate as an ionic liquid. The compounding ratio was adjusted and kneading was carried out at a kneading temperature of 220° C. using a twin-screw extruder. After the strand discharged from the twin-screw extruder was water-cooled, it was cut into lengths of about 5 mm by a pelletizer to obtain pellets. The obtained pellets were melt-spun at a spinning temperature of 220° C. using a spinneret having a discharge hole diameter of 0.18 mm, a discharge hole length of 0.23 mm, 1 hole, and a round hole. In melt spinning, the polyurethane was metered by a gear metering method and led to the spinneret. Thereafter, the single yarn was discharged from a spinneret nozzle at a volume of 3.18 mL/min, and was wound by a winder at 100 m/min to obtain a fiber having a solid cross section without hollow portions. Table 3 shows the evaluation results of the obtained fibers. The obtained fiber was slimy and sticky because the ionic liquid was exposed on the fiber surface, and was inferior in quality.

Claims (10)

A fiber that has a hollow cross-section and contains an ionic liquid in its interior. The fiber according to claim 1, characterized in that the area of the hollow portion is 10-98% of the cross-sectional area of the fiber. 3. The fiber according to claim 1, wherein the primary yield point elongation is 5 to 300%. The fiber according to any one of claims 1 to 3, characterized in that the fiber diameter is 5 to 5000 µm. The fiber according to any one of claims 1 to 4, characterized in that it has a volume resistivity of 1 x 10 ^-3 to 1 x 10 ⁶ Ω·cm. 6. The fiber according to any one of claims 1 to 5, wherein at least one of the ends of the fiber is provided with a liquid sealing portion for suppressing outflow of the ionic liquid. 7. The fiber according to any one of claims 1 to 6, wherein at least two points are provided with current-carrying parts that are in contact with the ionic liquid and conduct electricity. 8. The fiber according to claim 7, wherein the liquid-sealing portion and the current-carrying portion are integrated. A textile product at least partially composed of the fiber according to any one of claims 1 to 8. An electric/electronic device at least partially composed of the fiber according to any one of claims 1 to 8.

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