WO2023204157A1 - Fibre élastique en polyuréthane thermoplastique - Google Patents

Fibre élastique en polyuréthane thermoplastique Download PDF

Info

Publication number
WO2023204157A1
WO2023204157A1 PCT/JP2023/015215 JP2023015215W WO2023204157A1 WO 2023204157 A1 WO2023204157 A1 WO 2023204157A1 JP 2023015215 W JP2023015215 W JP 2023015215W WO 2023204157 A1 WO2023204157 A1 WO 2023204157A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic polyurethane
polyurethane elastic
elastic fiber
metal
less
Prior art date
Application number
PCT/JP2023/015215
Other languages
English (en)
Japanese (ja)
Inventor
宗 大内
英之 後藤
Original Assignee
旭化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭化成株式会社 filed Critical 旭化成株式会社
Publication of WO2023204157A1 publication Critical patent/WO2023204157A1/fr

Links

Classifications

    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products

Definitions

  • the present invention relates to thermoplastic polyurethane elastic fibers.
  • Polyurethane elastic fibers are generally used in clothing and sanitary materials. Polyurethane elastic fibers used in clothing and sanitary materials are required to have yellowing resistance and heat resistance.
  • Patent Document 1 discloses that a polyurethane elastic fiber obtained by dry spinning containing a hindered amine compound can improve the resistance to NOx gas yellowing.
  • Patent Document 2 discloses that the NOx gas yellowing resistance of polyurethane resin can be improved by using a phenolic antioxidant, a hindered amine light stabilizer, a polyester compound, and a benzotriazole light stabilizer in combination. There is.
  • Patent Document 3 describes a prepolymer with isocyanate groups at both ends obtained by reacting a polyol and a diisocyanate, and a prepolymer with hydroxyl groups at both ends obtained by reacting a polyol, a diisocyanate, and a low molecular weight diol. It is disclosed that the heat resistance of polyurethane elastic fibers can be improved by melt spinning a thermoplastic polyurethane resin. Patent Document 4 below discloses that the heat resistance of polyurethane elastic fibers can be improved by using an oil agent made of polydimethylsiloxane in combination with a phenolic antioxidant.
  • JP2006-342448A Japanese Patent Application Publication No. 2009-19062 Japanese Patent Application Publication No. 2006-307409 Japanese Patent Application Publication No. 2003-20521
  • Cited Documents 1 to 4 do not disclose thermoplastic polyurethane elastic fibers that are resistant to NOx gas yellowing and heat resistant.
  • the problem to be solved by the present invention is to provide a thermoplastic polyurethane elastic fiber having excellent resistance to NOx gas yellowing and heat resistance.
  • the inventors of the present application have conducted extensive studies and repeated experiments, and as a result, they have found that 0.05wt of at least one metal compound selected from the group consisting of metal hydroxides, metal carbonates, and metal oxides. % or more and 5.00 wt% or less, and the metal compound contains an alkali metal or an alkaline earth metal.It was unexpectedly discovered that the above problem can be solved by a thermoplastic polyurethane elastic fiber, and the present invention This is what we have come to complete.
  • the present invention is as follows.
  • [1] Contains at least one metal compound selected from the group consisting of metal hydroxides, metal carbonates, and metal oxides in an amount of 0.05 wt% or more and 5.00 wt% or less, and the metal compound is an alkali metal or A thermoplastic polyurethane elastic fiber characterized by containing an alkaline earth metal.
  • [2] The thermoplastic polyurethane elastic fiber according to [1] above, wherein the metal compound contains an alkaline earth metal.
  • [3] The thermoplastic polyurethane elastic fiber according to [2] above, wherein the alkaline earth metal is magnesium.
  • thermoplastic polyurethane elastic fiber according to any one of [1] to [3] above, wherein the metal compound is magnesium hydroxide.
  • the polyurethane constituting the thermoplastic polyurethane elastic fiber is a polyurethane polymerized from a chain extender consisting of a polymer polyol, a diisocyanate, and an active hydrogen compound, according to any one of [1] to [4] above.
  • thermoplastic polyurethane elastic fiber [6] The thermoplastic polyurethane elastic fiber according to [5] above, wherein the chain extender is a diol having a molecular weight of 60 or more and 120 or less.
  • thermoplastic polyurethane elastic fiber according to [5] or [6], wherein the diisocyanate is 4,4'-diphenylmethane diisocyanate (MDI).
  • MDI 4,4'-diphenylmethane diisocyanate
  • thermoplastic polyurethane elastic fiber according to any one of [5] to [7], wherein the ratio of the hard segment (Mh fraction) consisting of the chain extender and the diisocyanate is 20% or more and 40% or less.
  • Mh fraction hard segment
  • thermoplastic polyurethane elastic fiber according to any one of [1] to [9] above which has a total fineness of 160 dtex or more and 2000 dtex or less.
  • thermoplastic polyurethane elastic fiber according to any one of [1] to [10] above which is a multifilament.
  • thermoplastic polyurethane elastic fiber according to any one of [1] to [11] above which has a coefficient of variation in fineness unevenness in the yarn length direction of 3.0% or more and 10.0% or less.
  • thermoplastic polyurethane elastic fiber according to any one of [1] to [12], wherein the difference between the maximum fineness and the minimum fineness in the yarn length direction is 10 dtex or more and 150 dtex or less.
  • thermoplastic polyurethane elastic fiber that is one embodiment of the present invention is a thermoplastic polyurethane elastic fiber that has the above structure and has excellent NOx gas yellowing resistance and heat resistance.
  • this embodiment a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail.
  • the present invention is not limited to the following embodiment, but can be modified and implemented within the scope of the gist.
  • the thermoplastic polyurethane elastic fiber of the present embodiment contains at least one metal compound selected from the group consisting of metal hydroxides, metal carbonates, and metal oxides at 0.05 wt% or more and 5.00 wt% or less, preferably 0. It is characterized by containing .10 wt% or more and 1.00 wt% or less, more preferably 0.30 wt% or more and 0.50 wt% or less.
  • metal compound selected from the group consisting of metal hydroxides, metal carbonates, and metal oxides in an amount of 0.05 wt% or more and 5.00 wt% or less, NOx gas yellowing resistance and heat resistance are improved. It will be excellent.
  • the metal element preferably contains an alkali metal or an alkaline earth metal. Moreover, it is more preferable that an alkaline earth metal is included. Further, the alkaline earth metal is preferably calcium or magnesium, and more preferably magnesium. If the metal element is an alkali metal or an alkaline earth metal, the effect of improving NOx gas yellowing resistance will be even higher. The reason why the NOx gas yellowing resistance can be improved by using an alkaline earth metal as the metal element of the metal compound is not yet clear, but the inventors speculate as follows.
  • alkaline earth metals Since alkaline earth metals have a large electric charge, they easily adsorb NOx gas and suppress the attack of NOx gas on thermoplastic polyurethane elastic fibers, which is estimated to improve the NOx gas yellowing resistance of thermoplastic polyurethane elastic fibers. ing.
  • the metal compound is magnesium hydroxide because the effect of improving the NOx gas yellowing resistance is further increased.
  • the reason why the NOx gas yellowing resistance can be improved by using magnesium hydroxide as the metal compound is not yet clear, but the inventors speculate as follows. Magnesium hydroxide is a solid base with high base strength and easily reacts with acidic NOx gas, so it is estimated that the NOx gas yellowing resistance is improved.
  • thermoplastic polyurethane constituting the thermoplastic polyurethane elastic fiber may have a structure polymerized from diisocyanates, polymer polyols, diols, diamines, etc., and has thermoplasticity, in particular. It is not limited. Moreover, the polymerization method is not particularly limited either.
  • the thermoplastic polyurethane may be, for example, a polyurethane polymerized from a low molecular weight diamine as a chain extender consisting of a diisocyanate, a polymer polyol, and an active hydrogen compound; It may also be a polyurethane (hereinafter also referred to as "polyurethane urethane") polymerized from a low molecular weight diol as a chain extender consisting of. Trifunctional or higher functional glycols and isocyanates may be used as long as they do not interfere with the desired effects of the present invention.
  • thermoplastic means that it can be melted by heating below the decomposition temperature, exhibits plastic flow while in a molten state, and has the reversible property of solidifying upon cooling. means. Generally, polyurethane resins begin to decompose at temperatures above 230°C.
  • polymer polyol examples include, but are not limited to, polymer diols such as polyether diols, polyester diols, and polycarbonate diols. From the viewpoint of hydrolysis resistance, the polymer polyol is preferably a polyether polyol.
  • polyether polyols examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, copolymer diols that are copolymers of tetrahydrofuran (THF) and neopentyl glycol, and copolymers of THF and 3-methyltetrahydrofuran. Certain copolymer diols are mentioned. These polyether polyols may be used alone or in combination of two or more. Further, from the viewpoint of easily obtaining elastic fibers with excellent elongation, stretch recovery properties, and heat resistance, the number average molecular weight of the polymer diol is preferably 1000 or more and 8000 or less.
  • the polyether polyol is preferably polytetramethylene ether glycol, a copolymerized diol that is a copolymer of THF and neopentyl glycol, and a polyol that is a blend of these.
  • diisocyanates examples include aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates.
  • aromatic diisocyanates include, but are not limited to, diphenylmethane diisocyanate (hereinafter also referred to as "MDI"), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, and the like. It will be done.
  • alicyclic diisocyanates and aliphatic diisocyanates include methylene bis(cyclohexyl isocyanate) (hereinafter also referred to as "H12MDI”), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, and cyclohexane.
  • H12MDI methylene bis(cyclohexyl isocyanate)
  • isophorone diisocyanate methylcyclohexane 2,4-diisocyanate
  • methylcyclohexane 2,6-diisocyanate methylcyclohexane 2,6-diisocyanate
  • cyclohexane examples include 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, and octahydro 1,5-na
  • the diisocyanate is preferably an aromatic diisocyanate, and more preferably MDI. Further, by using MDI, a cyclic structure is introduced into the polymer skeleton, thereby increasing rigidity and improving heat resistance.
  • the chain extender made of an active hydrogen compound is preferably at least one selected from the group consisting of low molecular weight diamines and low molecular weight diols. Note that the chain extender may have both a hydroxyl group and an amino group in its molecule, such as ethanolamine. From the viewpoint of obtaining a thermoplastic polyurethane suitable for melt spinning, the active hydrogen compound is preferably a low molecular weight diol.
  • Examples of the low molecular weight diamine as a chain extender made of an active hydrogen compound include hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,2 -diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2, 2-dimethylbutane, 2,4-diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis(4-aminophenyl)phosphine oxide, hexamethylenediamine, 1,3-cyclohexyldiamine , hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis(4-
  • Examples of the low molecular weight diol as a chain extender consisting of an active hydrogen compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1 , 2-ethanediol, 1,6-hexanediol, 1,8-octanediol and the like. These low molecular weight diols may be used alone or in combination of two or more.
  • the chain extender is preferably a diol with a molecular weight of 60 or more and 120 or less, from the viewpoint of stretch recovery of elastic fibers and from the viewpoint of improving heat resistance and NOx gas yellowing resistance.
  • the active hydrogen compound which is a diol with a molecular weight of 60 or more and 120 or less is preferably ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, More preferred are 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol, and most preferred is 1,4-butanediol.
  • Thermoplastic polyurethane can be obtained using a known polyurethanization reaction technique, and may be produced by either a one-shot method or a prepolymer method.
  • the prepolymer method the polymer polyol and diisocyanate are placed in a reaction tank equipped with a nitrogen purge, a hot water jacket, and a stirrer in a molar ratio of preferably 1.0:1.8 to 3.0, more preferably 1.0: By adding at a concentration of 2.0 to 2.5 and reacting, a prepolymer having isocyanate groups at both ends is obtained.
  • a chain extender is added to this prepolymer with isocyanate groups at both ends to perform a chain extension reaction.
  • solid phase polymerization is performed to obtain polyurethane having a predetermined molecular weight.
  • the polymer may be obtained continuously or semi-continuously using a cylindrical pipe or a twin-screw extruder, followed by solid phase polymerization.
  • the total number of moles of the chain extender and the polymer polyol is 1.001 times or more and 1.100 times or less of the number of moles of the diisocyanate, since heat resistance and NOx gas yellowing resistance can be achieved at the same time.
  • the reason why resistance to NOx gas yellowing and heat resistance can be improved by setting the total number of moles of the chain extender and polymer polyol to 1.001 times or more and 1.100 times or less relative to the number of moles of diisocyanate is still unclear. However, the inventors estimate as follows.
  • the total number of moles of the chain extender and polymer polyol is 1.001 times or more of the number of moles of diisocyanate, it is possible to reduce the amount of diisocyanate-derived structures in the molecule that easily adsorb NOx gas, thereby improving NOx resistance. Gas yellowing is improved.
  • the total number of moles of the chain extender and the polymer polyol is 1.100 times or less of the number of moles of the diisocyanate, ligand exchange between the hydroxyl group of the thermoplastic polyurethane and the metal salt becomes difficult to occur, and the metal salt Since it becomes easier to exhibit the NOx gas yellowing resistance effect, the NOx gas yellowing resistance is improved.
  • the molecular weight of the thermoplastic polyurethane tends to increase, thereby improving heat resistance.
  • the spinning method is not particularly limited as long as the desired physical properties can be obtained; for example, in addition to the method of feeding thermoplastic polyurethane chips into an extruder, heating, and melt-spinning, After that, a method of mixing and spinning a polyisocyanate compound, adding a reaction product of a prepolymer with isocyanate groups at both ends and an active hydrogen compound to the prepolymer with isocyanate groups at both ends, and continuously producing it without going through chipping.
  • An example is a spinning method.
  • the polyurethane charged into the extruder is metered by a metering pump and introduced into the spinning head. If necessary, foreign matter is removed by filtration using a wire mesh or glass beads in the spinning head, and then it is discharged from the spinneret, air-cooled in a cold air chamber, and treated with a treatment agent, and then passed through a godet roll. It is wound up.
  • the temperature of the die, cold air speed, cold air temperature, focusing position, and spinning speed are adjusted to precisely control the fiber temperature profile and spinning tension.
  • the temperature of the die is preferably 180°C to 220°C, more preferably 200°C to 210°C.
  • a common melt spinning cooling method such as applying cold air perpendicularly to the running direction of the yarn from directly below the spinneret is used, and the wind speed of the cold air is preferably 0.2 m/s to 2.0 m/s, more preferably 0.5 m/s to 1.2 m/s, and the cold air temperature is preferably 5°C to 20°C, more preferably 7°C to 15°C.
  • One way to focus multifilaments is to install a false twister between the spinneret and the godet roll, propagate the twist from the bottom depending on the strength of the twist, focus the filaments together, and control the height of the focus point.
  • a general method can be selected, such as air false twisting using an air nozzle or a ring false twisting machine that brings the material into contact with a rotating ring.
  • the method of containing at least one metal compound consisting of a metal hydroxide, a metal carbonate, and a metal oxide in an amount of 0.05 wt% or more and 5.00 wt% or less is particularly limited.
  • there is a method in which it is added during the preparation of raw materials before the prepolymer reaction between a polymer polyol and diisocyanate a method in which it is added in the middle of the chain extension reaction process between a prepolymer and an active hydrogen compound, and a masterbatch containing a metal compound.
  • a method of adding 100% during spinning can be mentioned.
  • thermoplastic polyurethane elastic fiber of this embodiment may contain polymers other than polyurethane and additives, such as antioxidants, light stabilizers, ultraviolet absorbers, gas discoloration prevention agents, as long as the desired effects of the present invention are not lost. It may contain agents, dyes, activators, matting agents, pigments, lubricants, etc.
  • the thermoplastic polyurethane elastic fiber of this embodiment may contain a processing agent such as an oil agent from the viewpoint of unwinding property, processability, etc.
  • a processing agent such as an oil agent from the viewpoint of unwinding property, processability, etc.
  • the processing agent include, but are not limited to, silicone oils such as dimethyl silicone, mineral oils, and combinations thereof.
  • the method of applying the treatment agent is not particularly limited, and examples thereof include a method of applying the treatment agent using an oiling roller or the like.
  • the ratio of hard segments consisting of a chain extender and diisocyanate (hereinafter referred to as Mh fraction) is preferably 20% or more and 40% or less, more preferably 20% or more and 35%. Below, it is more preferably 22% or more and 30% or less.
  • Mh fraction is 20% or more and 40% or less, both heat resistance and NOx gas yellowing resistance can be improved. The reason why the NOx gas yellowing resistance and heat resistance can be improved by setting the Mh fraction to 20% or more and 40% or less is not yet clear, but the inventors speculate as follows.
  • the Mh fraction When the Mh fraction is 20% or more, hydrogen bonds between urethane bonds increase, heat resistance improves, and the presence of metal salts around the hard segment increases, improving NOx gas yellowing resistance. do.
  • the Mh fraction when the Mh fraction is 40% or less, when the diisocyanate contains aromatic rings, the amount of aromatic rings that yellow due to adsorption of NOx gas decreases, thereby improving resistance to NOx gas yellowing. Note that a detailed method for calculating the Mh fraction will be described later.
  • the total fineness of the polyurethane elastic fiber of this embodiment is preferably 160 dtex or more and 2000 dtex or less, more preferably 300 dtex or more and 1500 dtex or less, and even more preferably 600 dtex or more and 1000 dtex or less.
  • the polyurethane elastic fiber of this embodiment may be either a monofilament or a multifilament, but is preferably a multifilament.
  • the number of single yarns is preferably 14 or more and 140 or less.
  • the coefficient of variation in fineness unevenness in the yarn length direction of the thermoplastic polyurethane elastic fiber of the present embodiment is preferably 3.0% or more and 10.0% or less, more preferably 3.0% or more and 9.5% or less, and even more preferably It is 3.5% or more and 9.0% or less. If the variation coefficient of fineness unevenness is 3% or more and 10% or less, both NOx gas yellowing resistance and heat resistance can be improved. Although it is not yet clear why the NOx gas yellowing resistance and heat resistance are improved by having a fineness unevenness variation coefficient of 3.0% or more and 10.0% or less, the inventors estimate as follows. There is.
  • variation coefficient of fineness unevenness is 3.0% or more, light is likely to be diffusely reflected on the fiber surface, making the fiber appear opaque, making it difficult to visually recognize yellowing inside the fiber, and making the yellowing appear faint. If the unevenness variation coefficient of fineness is 10.0% or less, yarn breakage due to heat reception at fine fineness points can be suppressed, and heat resistance is improved.
  • the method of controlling the variation coefficient of fineness unevenness is not particularly limited as long as the desired physical properties can be obtained; for example, a method of enlarging the diameter of the spinneret used for melt spinning to generate draw resonance, Examples include a method of increasing the amount of yarn to cause shark skin or melt fracture, and a method of changing the cooling intensity during the spinning process to cause yarn shaking.
  • the difference between the maximum fineness and the minimum fineness in the yarn length direction of the thermoplastic polyurethane elastic fiber of this embodiment is preferably 10 dtex or more and 150 dtex or less, more preferably 15 dtex or more and 100 dtex or less, and even more preferably 20 dtex or 80 dtex or less. If the difference between the maximum fineness and the minimum fineness is 10 dtex or more and 150 dtex or less, both NOx gas yellowing resistance and heat resistance can be improved. The reason why the NOx gas yellowing resistance and heat resistance are improved due to the difference between the maximum fineness and the minimum fineness of 10 dtex or more and 150 dtex or less is not yet clear, but the inventors speculate as follows.
  • the difference between the maximum fineness and the minimum fineness is 10 dtex or more, light is likely to be diffusely reflected on the fiber surface, making the fiber appear opaque, making it difficult to visually recognize the yellowing inside the fiber, making the yellowing appear faint. If the difference between the maximum fineness and the minimum fineness is 150 dtex or less, yarn breakage due to heat reception at fine fineness points can be suppressed, and heat resistance is improved.
  • the method of controlling the difference in fineness is not particularly limited as long as the desired physical properties can be obtained. For example, there may be a method of enlarging the diameter of the spinneret used for melt spinning to generate draw resonance, or a method of increasing the discharge amount. Examples include a method of increasing the number of yarns, causing shark skin or melt fracture, and a method of changing the cooling intensity during the spinning process to cause yarn shaking.
  • the thermoplastic polyurethane elastic fiber of this embodiment preferably has an outflow start temperature measured by a flow tester of 150°C or more and 220°C or less, more preferably 150°C or more. The temperature is below 200°C.
  • the reason why heat resistance and NOx gas yellowing resistance can be improved by setting the outflow start temperature to 150° C. or more and 220° C. or less is not yet clear, but the inventors estimate as follows.
  • the outflow start temperature By setting the outflow start temperature to 150°C or higher, the structural change of the thermoplastic polyurethane due to heat reception is reduced, so heat resistance can be improved.On the other hand, by setting the outflow start temperature to 220°C or lower, the viscosity at the time of melting is reduced. By improving wettability, metal salts are uniformly dispersed, and NOx gas yellowing resistance is improved.
  • thermoplastic polyurethane ⁇ Quantification of constituent components of thermoplastic polyurethane>
  • the structure of the chain extender consisting of an active hydrogen compound and the diisocyanate constituting the thermoplastic polyurethane contained in the thermoplastic polyurethane elastic fiber was specified using NMR. Specifically, NMR was measured under the following conditions to identify the structures of the diisocyanate and chain extender. The structures of the diisocyanate and chain extender can be determined from the peak positions determined by NMR measurement.
  • Measuring device Bruker Biospin Avance600 Measurement nucleus: 1H Resonance frequency: 600MHz Number of accumulations: 256 times Measurement temperature: Room temperature Solvent: Deuterated dimethylformamide Measurement concentration: 1.5% by weight Chemical shift standard: dimethylformamide (8.0233ppm)
  • Hh Integral value derived from the methylene group of the active hydrogen compound adjacent to the urethane bond
  • Hs Integral value derived from the methylene group of the polymer polyol adjacent to the urethane bond
  • Hi Integral value derived from the hydrogen compound in the diisocyanate x: Total hydrogen of the diisocyanate is the number of
  • Ms number average molecular weight of soft segment portion
  • Mdo number average molecular weight of polymer polyol
  • Mdi molecular weight of isocyanate
  • N1 molar ratio of isocyanate to polymer polyol N0: molar ratio of unreacted isocyanate to polymer polyol
  • Mh number of hard segment portions
  • Average molecular weight Mda Molecular weight of chain extender (number average molecular weight when using a mixture of two or more types)
  • Mdi Molecular weight of isocyanate.
  • Thermoplastic polyurethane elastic fibers are wrapped around a glass plate and analyzed by XRD (Rigaku Ultima-IV), and the chemical composition of the metal compound contained can be identified by comparing the analyzed spectrum with data on the database.
  • XRD Ribonuclear Resonance Desorption spectroscopy
  • a sample is prepared by wrapping thermoplastic polyurethane elastic fibers tightly around a PP film with holes in the center, and analyzed by XRF (Rigaku ZSX-100e) to determine the composition of the metal compound.
  • the content of the metal compound can be determined from the detection intensity of the element.
  • a calibration curve using the same metal compound as the contained metal compound may be used, if necessary.
  • thermoplastic polyurethane elastic fibers ⁇ Measurement of outflow start temperature of thermoplastic polyurethane elastic fibers>
  • the outflow start temperature of the thermoplastic polyurethane elastic fiber is measured using a flow tester model CFT-500D (manufactured by Shimadzu Corporation).
  • the thermoplastic polyurethane elastic fibers are not pre-treated to remove processing agents such as oil agents, and 1.5 g of the thermoplastic polyurethane elastic fibers are sampled per measurement to measure the outflow start temperature.
  • a die (nozzle) with a diameter of 0.5 mm and a thickness of 1.0 mm was used, an extrusion load of 49 N was applied, and after a preheating time of 240 seconds at an initial setting temperature of 120 °C, the temperature was increased to 250 °C at a rate of 3 °C/min. Find a curve of stroke length (mm) and temperature when the temperature increases rapidly. As the temperature increases, the polymer within the toner heats up and begins to flow out of the die. The temperature at this time is defined as the outflow start temperature.
  • ⁇ Measurement method of fineness unevenness variation coefficient> The measurement of the variation coefficient of fineness unevenness is carried out by adjusting the rotational speed of two godet rolls so that the thermoplastic polyurethane elastic fiber is stretched twice, and by setting the following device between the godet rolls.
  • the outer diameter of the elastic fiber was measured from two directions perpendicular to each other using a laser, and the ratio of the average deviation of the diagonal length calculated from the Pythagorean theorem to the average value was defined as the coefficient of variation in fineness unevenness.
  • the measurement data used was the average value of 50,000 points of data measured at 160 points/second.
  • thermoplastic polyurethane elastic fibers are cut vertically, the yarn cross section is observed using the following equipment and conditions, and the total cross-sectional area of the yarn is calculated by automatic area measurement, and the fineness per unit length is calculated.
  • the following formula (6): d D ⁇ 1.1(g/cm 3 ) ⁇ 10 6 ...Formula (6) ⁇ where d is the fineness (dtex) and D is the total cross-sectional area (cm 2 ) of the yarn. ⁇ Calculated using.
  • Measuring device VHX-7000 (manufactured by Keyence Corporation) Lens used: VH-Z100R Magnification: 500x Measurement: Automatic area measurement Extraction method: Brightness ⁇ Method for measuring the difference between the maximum and minimum fineness of polyurethane elastic fibers> To measure the difference between the maximum fineness and the minimum fineness, the thermoplastic polyurethane elastic fiber is cut vertically, the yarn cross section is observed using the following equipment and conditions, and the total cross-sectional area of the yarn is calculated by automatic area measurement. The fineness per unit length was calculated from the difference between the maximum fineness and the minimum fineness when the fineness per unit length was calculated at 10 points using the above formula (6) at intervals of 5 mm in the yarn length direction.
  • thermoplastic polyurethane elastic fiber was held in a state of being stretched to twice its original size, and when it was pressed against a heat source of 110° C., the time until the fiber broke (the number of seconds for thermal cutting) was evaluated as an index of heat resistance.
  • thermoplastic polyurethane elastic fibers yellowed by the method 1 above were compared with the color code and evaluated on a 10-point scale. Specifically, a total of 18 people, 10 in their 20s and 2 in their 30s to 60s, were asked to select the color code closest to the color of yellowed thermoplastic polyurethane elastic fibers, and the average The points were taken as the evaluation score for yellowing visibility.
  • the color codes and evaluation scores used are as follows, and the higher the evaluation score, the less likely it is to yellow.
  • Both the ⁇ YI value and yellowing visibility evaluation are evaluations of NOx gas yellowing resistance.
  • the ⁇ YI value is not affected by human visibility, and conversely, the yellowing visibility is affected by the human visibility, so by comparing the yellowing visibility of samples with the same ⁇ YI value, it is possible to determine the human visibility.
  • the NOx gas yellowing resistance can be evaluated based on the following.
  • thermoplastic polyurethane resin > 2400 g of polytetramethylene ether diol having a number average molecular weight of 1800 and 750.78 g of 4,4'-diphenylmethane diisocyanate were reacted with stirring at 60° C. for 3 hours in a dry nitrogen atmosphere to obtain a terminal capped product with isocyanate. A polyurethane prepolymer was obtained. 151.20 g of 1,4-butanediol was added to this polyurethane prepolymer and stirred for 15 minutes to obtain a polyurethane with a viscosity of 2000 poise (30° C.).
  • thermoplastic polyurethane resin Thereafter, it was dispensed onto a Teflon (registered trademark) tray, and the polyurethane was annealed in a hot air oven at 110° C. for 16 hours while remaining in the tray to obtain a thermoplastic polyurethane resin.
  • thermoplastic polyurethane resin thus obtained was pulverized into a powder of approximately 3 mm using a UG-280 pulverizer manufactured by Horai. After drying the crushed chips in a dehumidifying dryer at a temperature of 110°C to a moisture content of 100 ppm, polyurethane resin powder and magnesium hydroxide were put into a hopper at a predetermined ratio, melted into strands in an extruder, and heated at a temperature of 20°C. The mixture was cooled in a water bath at 10°C and pelletized using a plastic processing machine SCF-100 manufactured by Isuzu Kakoki to obtain a masterbatch of magnesium hydroxide containing 10 wt% of the active ingredient.
  • thermoplastic polyurethane elastic fiber ⁇ Preparation of thermoplastic polyurethane elastic fiber>
  • Magnesium hydroxide-containing polyurethane resin powder which is a mixture of thermoplastic polyurethane resin powder and magnesium hydroxide masterbatch at a weight ratio of 95:5, is weighed and pressurized using a gear pump installed in the head, filtered through a filter, and then passed through a die. The liquid was discharged at a temperature of 210° C. from a nozzle with a diameter of 0.23 mm and 60 holes at a discharge rate of 620 dtex.
  • melt spinning was performed by blowing cold air from a cold air chamber whose temperature was adjusted to 15 to 17°C and the speed of the cold air to 0.8 to 1.0 m/s, and applying it perpendicularly to the fibers. Thereafter, the multifilament is twisted using a ring-type false twisting machine, and wound into a paper tube while applying a treatment agent mainly composed of polydimethylsiloxane and mineral oil to a 620 dtex/60 A spool of filament thermoplastic polyurethane elastic fiber was obtained.
  • thermoplastic polyurethane elastic fiber Magnesium hydroxide contained in this thermoplastic polyurethane elastic fiber is 0.50wt%, Mh fraction is 24%, fineness variation coefficient is 4.0%, OH/NCO is 1.010, and thermal cutting time is 600%.
  • the thermoplastic polyurethane elastic fiber had a ⁇ YI value of 8, a difference between the maximum fineness and the minimum fineness of 30 dtex, an outflow start temperature of 160° C., and a yellowing visibility evaluation of 10 points. The results are also shown in Table 1 below.
  • Examples 2 to 6 Thermoplastic polyurethane elastic fibers were obtained in the same manner as in Example 1, except that the ratio of the polyurethane resin and masterbatch was adjusted to increase or decrease the amount of magnesium hydroxide contained in the polyurethane elastic fibers. The results are shown in Table 1 below.
  • Example 7 The metal compounds were magnesium carbonate (Example 7), magnesium oxide (Example 8), calcium hydroxide (Example 9), calcium carbonate (Example 10), sodium carbonate (Example 11), and potassium carbonate (Example 12).
  • a thermoplastic polyurethane elastic fiber was obtained in the same manner as in Example 1 except that The results are shown in Table 1 below.
  • Example 18 Thermoplastic polyurethane elastic fibers were obtained in the same manner as in Example 1, except that methylene bis(cyclohexyl isocyanate) (H12MDI) (Example 18) and 1,6-hexamethylene diisocyanate (HDI) (Example 19) were used. .
  • H12MDI methylene bis(cyclohexyl isocyanate)
  • HDI 1,6-hexamethylene diisocyanate
  • Example 20 to 26 Thermoplastic polyurethane elastic fibers were obtained in the same manner as in Example 1, except that the Mh fraction of the thermoplastic polyurethane elastic fibers was increased or decreased by adjusting the molar ratio of polymer polyol and diisocyanate. The results are shown in Table 1 below.
  • thermoplastic polyurethane elastic fiber was obtained in the same manner as in Example 1, except that the molar ratio of the polymer polyol, diisocyanate, and diol was adjusted to change the OH/NCO of the thermoplastic polyurethane elastic fiber. The results are shown in Table 2 below.
  • Examples 34-41 Thermoplastic polyurethane elastic fibers were produced in the same manner as in Example 1, except that the spinning temperature, spinneret diameter, discharge rate, cooling conditions, and winding conditions during spinning were adjusted to change the variation coefficient of fineness unevenness of the thermoplastic polyurethane elastic fibers. I got it. The results are shown in Table 2 below.
  • Example 42 to 49 The same method as in Example 1 was used except that the spinning temperature, spinneret diameter, discharge rate, cooling conditions, and winding conditions during spinning were adjusted to change the fineness difference (maximum fineness - minimum fineness) of the thermoplastic polyurethane elastic fibers. A thermoplastic polyurethane elastic fiber was obtained. The results are shown in Table 2 below.
  • thermoplastic polyurethane elastic fibers were obtained in the same manner as in Example 1, except that the molecular weight of the thermoplastic polyurethane was adjusted by adjusting the molecular weight of the polymer polyol, and the outflow start temperature of the thermoplastic polyurethane elastic fibers was changed. The results are shown in Table 3 below.
  • thermoplastic polyurethane elastic fiber according to the present invention can be suitably used for clothing such as innerwear, stockings, and compression wear, and sanitary materials such as gather members and diapers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une fibre élastique de polyuréthane thermoplastique ayant une excellente résistance au jaunissement induite par un gaz de NOx et une excellente résistance à la chaleur. La présente invention concerne une fibre élastique de polyuréthane thermoplastique caractérisée en ce qu'elle comprend 0,05 % en poids à 5,00 % en poids d'au moins un composé métallique choisi dans le groupe constitué par un hydroxyde métallique, un carbonate métallique et un oxyde métallique, le composé métallique comprenant un métal alcalin ou un métal alcalino-terreux.
PCT/JP2023/015215 2022-04-22 2023-04-14 Fibre élastique en polyuréthane thermoplastique WO2023204157A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-071050 2022-04-22
JP2022071050 2022-04-22

Publications (1)

Publication Number Publication Date
WO2023204157A1 true WO2023204157A1 (fr) 2023-10-26

Family

ID=88419804

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/015215 WO2023204157A1 (fr) 2022-04-22 2023-04-14 Fibre élastique en polyuréthane thermoplastique

Country Status (2)

Country Link
TW (1) TW202346668A (fr)
WO (1) WO2023204157A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003113303A (ja) * 2001-10-04 2003-04-18 Toyobo Co Ltd ポリウレタン組成物およびポリウレタン弾性繊維
JP2003268629A (ja) * 2002-03-12 2003-09-25 Nisshinbo Ind Inc イオン放射性ポリウレタン弾性繊維の製造方法及びイオン放射性ポリウレタン弾性繊維
JP2005048316A (ja) * 2003-07-28 2005-02-24 Nisshinbo Ind Inc ポリウレタン弾性繊維の製造方法
JP2006028453A (ja) * 2004-07-21 2006-02-02 Nisshinbo Ind Inc ポリウレタン弾性体及び弾性繊維
JP2012132130A (ja) * 2010-12-24 2012-07-12 Toray Opelontex Co Ltd ポリウレタン弾性糸およびその製造方法
JP2014095162A (ja) * 2012-11-08 2014-05-22 Asahi Kasei Fibers Corp ポリウレタン弾性繊維及びその繊維製品
WO2019103013A1 (fr) * 2017-11-21 2019-05-31 旭化成株式会社 Fibre élastique de polyuréthane et corps enroulé associé
JP2022514184A (ja) * 2018-11-12 2022-02-10 ザ ライクラ カンパニー ユーケー リミテッド 視認性を低下させたスパンデックス繊維

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003113303A (ja) * 2001-10-04 2003-04-18 Toyobo Co Ltd ポリウレタン組成物およびポリウレタン弾性繊維
JP2003268629A (ja) * 2002-03-12 2003-09-25 Nisshinbo Ind Inc イオン放射性ポリウレタン弾性繊維の製造方法及びイオン放射性ポリウレタン弾性繊維
JP2005048316A (ja) * 2003-07-28 2005-02-24 Nisshinbo Ind Inc ポリウレタン弾性繊維の製造方法
JP2006028453A (ja) * 2004-07-21 2006-02-02 Nisshinbo Ind Inc ポリウレタン弾性体及び弾性繊維
JP2012132130A (ja) * 2010-12-24 2012-07-12 Toray Opelontex Co Ltd ポリウレタン弾性糸およびその製造方法
JP2014095162A (ja) * 2012-11-08 2014-05-22 Asahi Kasei Fibers Corp ポリウレタン弾性繊維及びその繊維製品
WO2019103013A1 (fr) * 2017-11-21 2019-05-31 旭化成株式会社 Fibre élastique de polyuréthane et corps enroulé associé
JP2022514184A (ja) * 2018-11-12 2022-02-10 ザ ライクラ カンパニー ユーケー リミテッド 視認性を低下させたスパンデックス繊維

Also Published As

Publication number Publication date
TW202346668A (zh) 2023-12-01

Similar Documents

Publication Publication Date Title
JP6133254B2 (ja) ２成分スパンデックス
JP5168401B2 (ja) ポリウレタン弾性糸およびその製造方法
JP5467466B2 (ja) ポリウレタン弾性糸およびその製造方法
US9567694B2 (en) Elastic fabric comprising a polyurethane elastic fiber made from a polyether based polyol
TWI610957B (zh) 聚胺基甲酸酯彈性絲及其製造方法
MXPA05014237A (es) Monofilamento o cinta elastica de hilado fundido y proceso.
JP5168672B2 (ja) ポリウレタン弾性糸およびその製造方法
TWI758322B (zh) 以熱塑性聚胺甲酸酯為主之熔紡複絲、其製造及用途
WO2018066592A1 (fr) Procédé de production de fibre élastique en polyuréthane
KR20130132937A (ko) 엘라스토머 수지, 이의 섬유 및 직물, 및 이들의 용도
WO2008075605A1 (fr) Fil élastique en polyuréthanne et procédé de production
JP7467648B2 (ja) ポリウレタン弾性繊維、並びにそれを含むギャザー部材、及び衛生材料
KR20180014766A (ko) 공중합체 폴리올을 포함하는 폴리우레탄 섬유
JP5659781B2 (ja) ポリウレタン弾性糸およびその製造方法
WO2023204157A1 (fr) Fibre élastique en polyuréthane thermoplastique
JP3826377B2 (ja) ポリウレタン糸およびその製造方法
JP7470229B1 (ja) ドープ用添加剤及び繊維
JP5141975B2 (ja) ポリウレタン弾性糸およびその製造方法
JP2023097202A (ja) 熱可塑性ポリウレタン弾性繊維並びにそれを含む巻糸体及び衛生材料
EP4232622A1 (fr) Fibre élastique de polyuréthane-urée et son procédé de production
JP6075036B2 (ja) ポリウレタン弾性糸およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23791805

Country of ref document: EP

Kind code of ref document: A1