WO2017116983A1 - Structure de fibre de polyuréthane - Google Patents

Structure de fibre de polyuréthane Download PDF

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Publication number
WO2017116983A1
WO2017116983A1 PCT/US2016/068302 US2016068302W WO2017116983A1 WO 2017116983 A1 WO2017116983 A1 WO 2017116983A1 US 2016068302 W US2016068302 W US 2016068302W WO 2017116983 A1 WO2017116983 A1 WO 2017116983A1
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WO
WIPO (PCT)
Prior art keywords
fiber
polyurethane
fiber structure
long period
tertiary nitrogen
Prior art date
Application number
PCT/US2016/068302
Other languages
English (en)
Inventor
Toshihiro Tanaka
Hiroshi Takayama
Yasushi Sasaki
Tohru TAKAGAI
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Invista North America S.A R.L.
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Publication date
Application filed by Invista North America S.A R.L. filed Critical Invista North America S.A R.L.
Publication of WO2017116983A1 publication Critical patent/WO2017116983A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

  • the present invention relates to a fiber structure wit excellent heat setting properties, heat resistance, dyeability, recovery properties., and elongation.
  • Fiber structures, containing polyurethane elastic fibers are widely used for elastic clothing applications such as leg wear, inner wear, sportswear, and the like as well as elastic material applications such as disposable diapers and sanitary products and the like because of the excellent elastic characteristics (stretch function).
  • polyurethane elastic fibers in the fiber structure has been steadily increasing in order to expand application and to further improve the stretch function.
  • fiber structures that include polyurethane elastic fibers are being required to have even higher properties.
  • Representative properties that are required include heat setting properties at low temperatures so that processing is possible at lower temperatures in order to conserve energy during the manufacturing process while also having heat resistance at high temperature in order to increase the yield when performing repeated postprocessing, as well as improved dyeability that assumes that the polyurethane elastic fibers are included at a high blending rate, and higher strength, elasticity, and recovery properties,
  • Patent document 1 discloses in detail an example of a Fibe structure analysis based on measuring the small angle x-ray scatter of polyurethane elastic fiber and the corresponding long period, and based on this document in particular, it is know that the long period in this small angle ⁇ -ray scatter measurement observed in polyurethane elastic fibers to date is normally between 7 and 16 nm.
  • An object of the present invention is to provide a fiber structure that further enhances these properties and is suitable for elastic clothin and elastic materials, and to provide a manufacturing method thereof,
  • the fiber structure of the present invention uses any of the following means in order to achieve the aforementioned objective.
  • a fiber structure comprising polyurethane elastic fiber where the first lon period Ql) of the small angle ⁇ -ray scattering measurement of the polyvirethane elastic fiber is 20 to 100 nm, and tertiary nitrogen compounds are contained.
  • the fiber structure of the present invention has excellent heat setting properties, heat resistance, dyeability, recovery properties, a d the elasticity, as: well as excellent appearance, and is suitable for elastic clothing and elastic materials,
  • Fig.. 1 is a small angle x-ray scatter image of PU12 in an embodiment of the present invention.
  • Fig. 2 is a small angle x-ray scatter image of PUX0 i a comparative example. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the present invention is the discovery that the aforementioned problems can be resolved if the polyurethane elastic fiber provides a new scatter image for the image obtained by a small angle X-ray scattering measurement (hereinafter also referred to as a scatter image), or in other words, a first long period (.Jl) in the fiber direction (meridian direction) that is longer than conventional, at 20 to 100 nm, and that the fiber contains a tertiary nitrogen compound.
  • a scatter image small angle X-ray scattering measurement
  • the first long period (Jl) is more preferably between 25 and 70 nm, and this is because if this range is used, the adjustment range of dye fixing properties due to changing the amount of tertiary nitrogen compounds will be significantly broader as compared to fibers of other structures.
  • the crystals are arranged in layers in a cross-section perpendicular to the fiber direction, and that a noncrystalline region exists in the gaps of the layered crystals.
  • the noncrystalline region in the polyurethane elastic fibers (herein also referred to as gap part) is thought to he formed by a segmented poiyurethane-urethane chain or a soft segment chain in a segmented
  • the present invention was achieved by discovering that normally tertiary nitrogen compound that function as a dye seat are stably present in polyurethane elastic fibers that have a fiber structure with a large volume for the ga part, or in other words a fiber structure with a large long period.
  • a plurality of long periods may be present in the fiber direction in the small angle x-ray scatter measurement in the polyurethane elastic fibers that are used in the present invention , but in this case, the first long period in the small angle ⁇ -ray scatter measurement of the polyurethane elastic fibers that are used in the present inventio is the long period with a maximum value for the x-ray scatter intensity that defines the long period , and this corresponds to the brightest peak in the small angle x-ray scatter image. Furthermore, in the present invention, a plurality of long periods is also preferably present in the equatorial direction in addition t the fiber direction, and preferably there are two different types, high intensity and low intensity.
  • the first long period in the fiber direction determined from the peak with the maximum intensity is Jl
  • the second-long period determined from the second highest intensity peak is 32
  • 32 is preferably between 7 and 19 ma, more preferably between 9 and 16 am
  • the ratio of J2 to Jl is preferably close to an integer ratio, from the perspective of elastic properties, and more preferably is close to 2 to 5 (or in other words close to 2, 3, 4, or 5). More preferably, the ratio is close to 2 or 3.
  • close to an integer ratio means within a range of " -A 0.2. If the ratio is close to an integer of 2 or higher, the elastic properties will, be enhanced, and the elastic properties will be more favorable, as a fabric, and if the ratio is close to an integer of 5 or less, the permanent strain will not be excessive, and the elastic properties will be more preferable as a fiber structure.
  • the long cycle observed in a conventional polyurethane elastic fiber is usually less than 15 nm, normally 5 to 10 nm,
  • the long period in the equatorial direction is preferably observed in the range of 10 to 20 nrn, and thereby a fiber structure showing more favorable heat setting properties can be obtained,
  • the method, of measuring the polyurethane elastic fiber using small angle x-ray the long period by measuring the polyurethane elastic fiber with small angle X-ray can be the method described in Patent Document 1, but there is no limitation thereto, f 00030]
  • the lon period J can be determined from the following Bragg equation.
  • ⁇ is the wavelength of the X-ray
  • R is the camera length (distance between the measurement sample and the scatter intensity detector)
  • r is calculated from the method described below in accordance with a conventional method.
  • the long period in the meridian direction may be obtained from the above Bragg's equation, assuming that the distance from the equatorial line 2 to the scatter intensity maximum, peak is r. (Similarly, with respect to the long period in the equatorial direction, the distance from the meridian to the scatter intensity of the scatter intensity maximum peak is r, which can he obtained from the above Bragg's equation.)
  • the scatter intensity detector may be a camera or an imaging plate, but it is more preferable to use radiation light as a light source and to digitize the scatter intensity detection using an imaging plate in order for the polyurethane elastic fiber used in the present- invention in order to show a new scatter image for the small angle X-ray scatter image, to show a long period J of 20 to 100 nm, and to more accurately measure the long period J.
  • radiation light in particular, high energy light sources of the order of tens of keV to several GeV, which are impossible to achieve with the conventional goniometer, can be constantly used, and the measurement time can be shortened, and therefore the temporal influence of deformation and degradation of the elastic yarn due to minute strain and gravity can be minimized during measurement.
  • Preferred examples of radiation light include third generation radiation equipment such as Spriag-8 in Japan, APS in the United States, and ESRF in Europe.
  • third generation radiation equipment such as Spriag-8 in Japan, APS in the United States, and ESRF in Europe.
  • general use research is possible using Spring-8, and specifically, Hyogo prefecture beamline (BL08B2 and BL24XU) and the like are suitable.
  • the scattering angle (referred to as 2 ⁇ ) in the Bragg equation is approximated by ⁇ tan - 1 (r / R) ⁇ , but if the above-mentioned radiation light and detector are used, 2 ⁇ can be detected with higher accuracy.
  • r is more preferably determined from a continuous plot (scatter intensity profile) with the horizontal axis representing the inverse space axis (4 ⁇ / sin ⁇ (run - 1)) along the meridian line 1 and the equatorial line 2, and the vertical axis representing the scattering intensity.
  • the polyurethane resin used in the present invention may be any polyurethane whose main components are polymer diols and diisocyanates, and there is no limitation in particular. Furthermore, the synthesis method is also not restricted. Incidentally, main components refers to components that make up 50 mass % or more of the components that form the polyurethane,
  • examples include a polyurethane urea containing a polymer dioL a diisocyanate, and a diamino compound (low molecular weight diamine) as a chain extender, or a polyurethane containing a polymer diol, a diisocyanate, and a low molecular weight diol as a chain extender.
  • a polyurethane urea using a compound having a hydroxy! group and an amino group in the molecule as a chain extender. It is also preferable to use trifunctional or higher polyfunctional glycols, isocyanates, and the like, so long as the effect of the present invention is not hindered.
  • the polymer diol of the structural unit constituting the polyurethane type resin is preferably a polyether type glycol, polyester type glycol, polycarbonate diol, and the like.
  • a polyether type glycol Is preferably used from the perspective of imparting high elongation, particularly for fibers with deodorizing properties, flexibility, and the like.
  • the polyetherbased glycol preferably contains a copolymerized.
  • diol compound containin a unit represented by the following general formula (I).
  • H R ⁇ where, a and c are integers of 1 to 3, b is an integer of 0 to 8, and B.8 and R4 are II or an alkyl group having I to 3 carbon atoms.
  • polyether glycol compound examples include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethyleiie ether glycol (hereinafter abbreviated as PTMG), tefeeahydrofuraa and
  • modified PTMG which is a copolymer of tetrahydrofuran
  • modified PTMG which is a copolymer of tetrahydrofuran and aeopentyl glycol, and a random copolymer where tetrahydrofuran and ethylene oxide and/or propylene oxide are arranged irregularly, and the like.
  • the polyurethane resin used in the present invention can use one kind of these polyether type glycols, or two or more kinds may be mixed or copolymerized and used. Of these, PTMG and modified PTMG are preferably used.
  • a polyester glycol such as a polyester diol with a side chain obtained by
  • polycarbonate diol or the like derived from a diol component and a dicarboxyiic acid component containing 3,7-dimethyIdecanedioic acid or 3,8-dimethyldecanedioic acid are preferably used from the perspective of enha ncing the abrasion resistance and the light fastness of the polyurethane resin.
  • polymer diols may be used individually, or two or more types may be mixed or copolymerized before use.
  • the diisocyanate of the structural unit constituting the polyurethane -based resin used in the present invention is preferably an aromatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate and the like.
  • aromatic diisocyanate include diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate,
  • alicyclic diisocyanate examples include methylene bis (cyclohexyl isocyaaate) (hereinafter abbreviated as PICM), isophoroae diisocyanate, methyleyclohexane-2.,4"diisocyaaate, methyleyelohexane- 2,6 ⁇ diisocyanate, cyclohexane- 1,4-diisocyanate, hexahydroxylylene diisocyanate, exahydro tolylene diisocyanate, octahydro- 1, 5-imphthalene diisocyanate and the like.
  • An aliphatic diisocyanate can be effectively used especially in suppressin yellowing of the PICM
  • the chain extender of the structural unit constituting the polyurethane-based resin is preferably at least one or more low molecular weight diamine and low molecular weight diol.
  • compounds that have both a hydroxy! group and an amino group in the molecule are also acceptable, such as ethanolamine.
  • the low molecular weight diamine include ethylene diamine (hereinafter abbreviated as EDA), 1,2-propane diamine, 1.3-propane diamine, hexamethylene diamine, p-phenylene diamine, p-xylylene diamine, m-xylylenediamine, ⁇ , ⁇ '" methylene dianiline, 1,3-eyclohexyl diamine, hexahydrometaphenylene diamine, 2-methylpentamethylene diamine, bis(4-ammophenyi) phosphine oxide and the like.
  • EDA is particularly preferable .
  • a resin with more excellent elongation, elastic recovery, and heat resistance can be obtained b using EDA.
  • a triamine compound capable of forming a crosslinked structure such as diethylenetriami ' ne or the like may be added to the chain extender to an extent that the effect is not hindered.
  • ethylene glycol hereinafter abbreviated as EG
  • 1,3-propanediol 1,4-butanediol
  • the most suitable chain extender in the polyurethane that is used in the present invention is a low molecular weight dioi.
  • the polyurethane of the present invention preferably contains one type or a mixture of two or more types of end-capping agents.
  • end-eapping agents include mono-ols such as ethanol, propanol, butanol, isopropanol, allyl alcohol, and cyclopentanol, and monoisocyanates such as phenyl isocyanate, and the like.
  • Examples of the amine type catalyst include N,N-dimet.hylcyc.lohexyl amine,
  • organometallic catalyst examples include tin octanoate, dibutylfcin dilaurate, dibutyl octanoate, and the like.
  • the method of synthesizing the polyurethane used as the polyurethane resin used in the present invention is not particularly restricted, and can be a melt polymerization method or a solution polymerisation method, or the like.
  • the polyurethane can be obtained by synthesis using the aforementioned raw materials in N,N"dimethylacetamide (hereinafter abbreviated as DMAc), dimethyiformamide (DMF), diinethylsulfoxide, M-methyl pyrrolidine, and the like, or a solvent primarily containing the solvents.
  • DMAc N,N"dimethylacetamide
  • DMF dimethyiformamide
  • M-methyl pyrrolidine M-methyl pyrrolidine
  • a method of adding and dissolving the above-mentioned raw materials in such a solvent, heating to an appropriate temperature, and causing a reaction to obtain polyurethane, or a method in which the polymer dioi and diisoeyanate are first melted and reacted, and then reacted with the above-mentioned chain extender to form polyurethane, or the like can be used as particularly preferable methods.
  • the concentra tion of the obtained polyurethane solution is usually preferably hi the range of 30 mass% or more and 80 raass% or less.
  • the first stage is carried out in the absence of a solvent, and. preferably includes a step where after obtaining the theoretical end point prepoiymer. the prepolymer is dissolved in twice or more of its mass of a solvent and temporarily sufficiently diluted.
  • the total amount of the diisoeyanate added in the second and subsequent stages is preferably smaller than the molar ratio of the first stage in terms of the reaction equivalent ratio ( molar ratio,* of the terminal isocyanate groups of the diisoeyanate to the terminal hydroxy! groups of the polymer diol.
  • the timing of introducing the chain extender made of the low molecular weight diol is preferably at the time of or immediately after the introduction of the diisoeyanate in the second stage, and all the reactions are preferably carried out at a low temperature of 1Q0°C or less.
  • the polyurethane elastic fiber that forms the fiber structure of the present invention contains a tertiary nitrogen compound. If the polyurethane elastic fiber does not contain the tertiary nitrogen compound, the fiber structure will not have useful dyeability.
  • the range of adjustment of the dye fixing property can be made broader by increasing or decreasing the amount of the tertiary nitrogen compound, and therehy the upper limit value for adjusting the dye fixing properties can be increased.
  • the content of the tertiary nitrogen compound is preferably 0.05 to 7 meq / kg based on tertiary amine nitrogen atoms, more preferably 0.1% by mass or more and 20% by mass or less, even more preferably 1% by mass or more and 15% by mass or less, and yet even more preferably 3% by mass or more and 8% by mass or less.
  • the amount may be tested in advance based on the application so that the optimum value may be appropriately determined.
  • the tertiary nitrogen compound is not particularly restricted, so long as being a compound that has a tertiary nitrogen in the molecule.
  • a monomelic compound having a relatively low molecular weight of approximately 1000 or less is acceptable.
  • a relatively high molecular weight oligomer or polymer having a molecular weight of approximately 1000 or higher (hereinafter referred to as a polymer h aving a tertiary nitrogen) is also acceptable.
  • a polymer with a N,N"dialkyi semiearbazide on a terminus is also preferable.
  • a polymer having a tertiary nitrogen is preferable from the perspective of dye fastness.
  • polystyrene resin having a tertiary nitrogen
  • polyxrrethaiies and polyurethane ureas obtained from diols containing a tertiary nitrogen or diamines containing a tertiary nitrogen and an organic diisocyanate, which are known as antioxidants for polyurethane elastic fibers.
  • a polymer with a ⁇ , ⁇ -dialkyl semiearbazide end group on the polyurethane or polyurethane urea or the like can also be suggested.
  • Compounds having tertiary nitrogen in the main chain and having N,N-dialkyl semiearbazide on a terminal can exhibit high heat resistance at the time of dyeing, even at low concentration of ⁇ , ⁇ -dialkyl semiearbazide , and higher elastic recoverability and higher strength and elongation can be achieved as compared to when N,N'dialkyl semiearbazide is not added.
  • Preferable specific examples of diols containing a tertiary nitrogen include -riiethyl-NjN-diethanolamine, N-methyl-N,N-dipropanolamine,
  • TBDEA N-methyl-NjN'diisopiOpaiiolaiTune
  • BDEA N-benzyl-N,N-diethandiamine
  • piperazine derivatives such as bishydroxyethyl piperazine and bishydroxyisopropyl piperazine can also be used.
  • TBDEA and BDEA are particularly preferable.
  • MIBPA N-methyl-3,3Kminofois(propy!amine
  • N'butyl-aminobispropylamine N-methyPaminobis-ethylamine, N't'butyl'aininobis-propylamine, piperazine-N,N'-bis(3-aminopropyl) (hereinafter abbreviated as BAPP),
  • organic diisocyanate examples include aliphatic diisocyanates such as PICM, isophorone diisocyanate (hereinafter abbreviated as IPDI), lysine diisocyanate, DDI deri ved from dimer acid, and the like.
  • PICM isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • DDI lysine diisocyanate
  • a substituted hydrazine is preferabl used when reacting with organic diisocyanate to form a terminal semicarbazide group.
  • Specific preferable examples of the substituted hydrazine include ⁇ , ⁇ -dimethylhydrazine (hereinafter abbreviated as UDMH), N,N-diethylhydra3 ⁇ 4ane, N, N-diprppylhydrazine, N, N-diisop ro ylhydr azine, N, N, N'di isobuty I hydrazine ,
  • UDHEH ⁇ , ⁇ -dihydroxyethylhydrazine
  • UDMH and UDHEH are particularly preferable.
  • polyurethane or polyurethane urea can be prepared by completely reacting an
  • the average molecular weight of the polymer having a tertiary nitrogen is preferably 1,000 or higher and 20,000 or lower, and the amount of semicarbazide group in 1 kg of the polymer having N, N-dialkylsemicarbazide at the terminal is preferably within a range of 0.1 to 100 metj (meq / k ).
  • polyurethane obtained by polymerizing TBDEA and PICM with an sxLdition polymer at a ratio of 2' ⁇ 3 to 20: 21 as a tertiary nitrogen compound, or a compound that forms a dimethyl semicarbazide by reacting UDMH on the terminal, or polyurethane urea obtained by a mixture of MIBPA and PICM where the ratio of PICM is between 2 * 3 and 20: 21, or a compound that forms a dimethyl semicarbazide by reacting UDMH with the terminal are suggested.
  • the semicarbazide group is preferably contained in the range of 1 to 200 milliequivalents (meq kg) in 1 kg of yarn.
  • TBDEA and PICM polyurethane include "Me achlor ⁇ registered trademark)" 2462 manufactured by Du Pont, f 00066 ⁇
  • various types of additives described below are preferably added to the polyurethane resin that is used in the present invention.
  • the method of adding the various types of additives can be an arbitrary method.
  • Various types of methods can be used, and examples of representative methods include a method using a static mixer, a method using stirring, a method using a homogenizing mixer, a method using a twin screw extruder, and the like.
  • the various additives to be added are preferably added as a solution, from the perspective of uniform addition to the polyurethane.
  • isob tylroethylamine isopentylmethyla:mine, dibutyiamme, diamylamine, and the like, monools such as ethanol, propanoi, butanol, isopropanol, allyl alcohol and cyclop en tanol, and
  • monoisocyan tes such as phenyl isocyanate, and the like.
  • stabilizers include addition polymers of divinylbenzene and p-eresol ("Metachlor (registered trademark)” 2890 manufactured by DuPont), polyurethane produced by reacting t-butyl diethanolamine and methylene-bis-(4"cyclohexyl isocyanate) ("Metaelor (registered trademark)" 2462 "manufactured by Du Pont Co.);
  • photostabilizers and antioxidants and the like such as double hindered phenol agents like so-called “BHT” and “SUMILIZER (registered trademark)" GA-80 manufactured by Sumitomo Chemical Co., Ltd., benzotriazole agents such as “TJNUVIN (registered trademark)” and the like manufactured by Ciba Geigy AG, benzophenone agents, "SUMILIZER (registered trademark)” P-16 and the like manufactured by Sumitomo Chemical Co., Ltd., various types of hindered amine agents, inorganic pigments such as titanium oxide and carbon black, fluorine resin powders or silicone resin powders, metal soaps such as magnesium stearate, disinfectants and deodorizing agents such as silver, zinc and compounds thereof, lubricants such as silicone, mineral oil and the like, various antistatic agents such as barium sulfate, cerium oxide, betaine and phosphoric acid agents, and the like can be provided by adding or reacting with the polymer.
  • ⁇ 50 manufactured by Nippon Hydrazine Co., Ltd. can be added as a nitrogen oxide scavenger
  • "Sumiiizer (registered trademark)” GA-80 manufactured b Sumitomo Chemical Co., Ltd- can be added as a thermal oxidation stabilizer
  • "Sumisorb (registered trademark) 800 # 622” and the like manufactured by Sumitomo Chemical Co., Ltd. can be added as a photo stabilizer.
  • a particularly preferable polyurethane resin that is used in the present invention is a polyurethane resin obtained by polymerizing a polymer dioi and 8. diisocyanate, from the perspective of obtaining a resin with excellent heat resistance that does not have practical problems including process permeability, and the melting point will be on the low temperature side in a range of-20°C or higher and 20°C or lower and the melting point will be on the high temperature side in a range of 150°C or higher and 800°C or lower .
  • a melting point on the low temperature side and a melting point on. the high temperature side corresponds to the melting point derived from a so-called soft segment of polyurethane or polyurethane urea, and the melting point of hard segment crystals, when measured using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • An example of a method for making the melting point of polyurethane or poly urethane urea on the high temperature side to be within a range of 150°C or higher and 300°C or lower is a method of controlling the ratio of polymer dioi and diisocyanate. For example, when the number average molecular weight of the polymer dioi is 1000 or more, a polyurethane with a melting point on the high temperature side can be obtained by proceeding with polymerization at a ratio of (number of moles of diisocyanate) / (number of moles of polymer dioi) - 1.5 or more.
  • the urethane group concentration of the polyurethane constituting the polyurethane resin used in the present invention is preferably approximately 0.2 mol/kg or more and approximately 3.5 mol/kg or less, more preferably approximately 0.4 mol kg or more and 1.0 mol/kg or less.
  • the urethane group, concentration is calculated by (polymer dioi (rnoi) included in the polyurethane resin) x 2 / (mass of polyurethane resin (kg)).
  • a most preferable composition of the polyurethane of the present invention is a polyurethane obtained by polymerizing a polymer diol ' having a number average molecular weight of 500 or more and 5000 or less, an organic diisocyanate, and a chain extender containing a low molecular weight diol, where the reaction equivalent ratio (molar ratio) of the terminal isoeyanate groups of the diisocyanate to the total of the terminal hydrox 1 groups of the polymer diol and the low molecular weight diol is 2.5 to 4.0 or less, and the mass ratio of the low molecular weight diol to the high molecular weight diol is in the range of 1/9 to 5/5,
  • the molecular weight of the polyurethane in the present invention is preferably in a range of 40,000 or higher and 150,000 or lower, as the number average molecular weight, from the perspective of obtaining fibers with high durability and high strength.
  • molecular weight in the present invention is measured by GPC, and is the value when converted to polystyrene.
  • Examples of the amine type catalyst include N,N"dimethylcyeloh.exyl amine ,
  • N.N.N'.NVN ⁇ pentamethyldiethylene triamine, tetramethyl guanidine, triethylene diamine, N,N''dienderthyipiperazine, N methyl-N'-dimethylaminoethyi-piperazine,
  • 1,2-dimethylxmidazole 4,6-tris (dimethyl aminomethyl) phenol, N.N'dimethylarnino hexanol, triethanolamine and the like.
  • organometallic catalyst examples include ti octanoate, dibutyltin dilaurate, dihutyl octanoate, and the like.
  • the concentration in the obtained polyurethane yarn spinning solution is usuall preferably in the range of 30 mass% or more and 80 mass% or less.
  • additives such as various types of stabilizers, pigments and the like may be added to the polyurethane elastic fiber or to the polyurethane spinning stock solution for spinning the yarn as described below. Examples include
  • photostabiiizers and antioxidants and the like such as hindered phenol agents like 2,6-drt-butyl-p-creosol (BHT) and "SUMILIZER (registered trademark)" GA-80 (product name) manufactured by Sumitomo Chemical Co., Ltd., benzotriazoie agents such as various types of "TINUVIN (registered trademark)'' and the like manufactured by Ciba Geigy AG, ben3 ⁇ 4ophenone agents, "SUMILIZER (registered trademark)” P-16 (p ' roduct name) and the like manufactured by Sumitomo Chemical Co., Ltd., various types of hindered amine agents, various types of inorganic pigments such as iron oxide, titanium oxide, carbon black, and the like, fluorine resin powders and silicone resin powders, metal soaps such as magnesium stearate and the like, disinfectants and deodorizing agents such as silver, zinc and compounds thereof, lubricants such as silicone, mineral oil and the like
  • various inorganic substances or inorganic porous substances may be added within a range that does not impair the effect of the present invention
  • additives may be added directly to the poiyurethane solution at the time of preparing the above-mentioned poiyurethane yarn spinning stock solution, or may be prepared by first prepa ring a dispersion of the additives, and then blending with the poiyurethane solution. The amount of these additives is appropriately determined based on the purpose and the like.
  • the poiyurethane elastic fiber to be used in the present invention can be obtained by, for example, dry spinning, wet spinning, or melt spinning the yarn spinning stock solution constituted as described above and then roiling up the yarn.
  • dry spinning is preferable from the perspective that spinning can be stably performed at an fineness from fine to thick,
  • the yarn may be a monofilament composed of an individual yarn or a multifilament composed of a plurali ty of individual yarns.
  • the cross-sectional sh ape of the yarn may be circular or flat.
  • the dry spinning method is also not particularly restricted, and spinning ma be performed by appropriately selecting the desired properties and spinning conditions
  • the permanent strain rate and the stress relaxation properties of the polyurethane elastic fiber used in the present invention are particularly susceptible to the speed ratio of the godet roller and the winder, so preferably the speed ratio is appropriately determined based on the intended use of the yarn.
  • the speed ratio is appropriately determined based on the intended use of the yarn.
  • the strength of the polyurethane elastic fiber can be improved by increasing the spinning speed, so the spinning speed is preferably 450 in/min or higher in order to obtain a practical strength level.
  • a speed of approximately 450 to 1000 rn mkrute is preferable.
  • the fiber structure of the present, invention containing the polyurethane elastic fiber described above or the polyurethane elastic fiber obtained by the production method described above has excellent processability such as dyeability, elasticity, heat setting properties, and the like, and therefore even when used to obtain a thin cloth, sufficient elasticity and aesthetics can be achieved, so it is possible to obtain clothing with high-class feel and excellent appearance. These properties can be remarkably achieved in knitted fabrics.
  • a circular knitted fabric as the fiber structure of the present invention using the polyurethane elastic fiber described above or a polyurethane elastic fiber obtained by the manufacturing method described above fully utilizes the body fitting properties as clothing, and therefore can also be preferably applied to applications for pursuing aesthetic properties, such as underwear, stockings, tights and the like.
  • fiber structure refers to a woven or knitted fabric, nonwoven fabric, or wad, but there is no restriction thereto.
  • the fabric which is a fiber structure of the present invention is made using a polyurethane elastic fiber as described above.
  • the cloth can exhibit the effects of the present invention even in a mixed elastic fabric containing a mixture of polyester yarn, polyamide yarn (nylon yarn), and the like, for example.
  • Examples of the fiber to be combined with the polyurethane elastic fiber in constructing the fiber structure include synthetic fibers represented by polyester yarn, polyamide y arn (nylon yarn), acrylic synthetic fiber, polypropylene synthetic fiber, semisynthetic fibers represented by aceta te fiber, natural fibers such a s cotton, hemp and wool, or a mixture of two or more types, and the like, and thereby the effects of the present invention can be demonstrated.
  • the mixing ratio, the material fibers to he combined, and the mixing method may be appropriately selected and the fabric ca be made by known manufacturing methods.
  • the elastic fiber may be u sed as is as hare yarn, or one or more types of conventionally known fibers such as synthetic fibers like oly amide fiber, polyester fiber, or acrylic fiber, or natural fibers like cotton, wool, and the like can be freely combined and coated.
  • fibers that can be preferably used include fibers primarily containing repeating units of polyethylene terephthalate, polytrimethylene terephthalate, polyhutylene terephthalate, or ethylene terephthalate (preferably those having approximately 90 mol% or more of repeating units), fibers primarily containing repeating units of triniethylene
  • polyester containing 90 mol % or more of ethylene terephthalate units as a repeating component are preferable, and fibers made of polyester containing approximately 95 mol % or more of repeating units of ethylene terephthalate are more preferable.
  • Polyester containing 90 mol % or more of ethylene terephthalate units as a repeating component are preferable, and fibers made of polyester containing approximately 95 mol % or more of repeating units of ethylene terephthalate are more preferable.
  • polyethylene terephthalate fiber approximately 100 mol % of repeating units of ethylene terephthalate, or in other words fibers made of polyethylene terephthalate are particularly preferable.
  • This polyethylene terephthalate fiber has favorable feel and luster, has easy to care properties such as being difficult to wrinkle and the like, and is suitable as a fiber material for making fabrics with elasticity.
  • the polyethylene terephthalate fiber is suitable for use in combination with the poly re hane urea fiber that is preferably used in the present invention, and it is possible to obtain a favorable fabric.
  • a cationic dyeable polyester fiber is obtained by copolymerizing a compound containing a metal sulfonate group in a polyester molecular structure.
  • Various types and different copolymerization ratios of the compound containing a metal sulfonate group is developed by enhancin dye ability, improving texture, and the like, and the cationic dyeable polyester fiber used in the present invention is not particularly restricted if the fiber indicates dyeing affinity to a normal cationic dye.
  • the section form of the polyester fiber may be round or irregular.
  • a water absorbent quick drying polyester fiber yarn or the like is preferably used.
  • the water absorbent quick drying polyester fiber can be a fiber further provided with many small holes on the wall surface of a hollow fiber, or a modified cross-section shaped fiber or the like provided with many grooves, holes, or the like on the fiber surface or the like, wherein water absorbeney is achieved by moisture being absorbed into the small holes on the fiber, grooves on the fiber surface, and the space in between fibers and in between yarns, which are commercially available by synthetic fiber manufacturers as water absorbent quick drying polyester fiber, can be used.
  • water absorbent quick drying polyester fiber examples include “Coolmax (registered trademark)” manufactured by INVISTA, “Theo a (registered trademark)” manufactured by Toray Industries, and the like.
  • Side-byside type composite fiber cross-section is preferred particularly when polytrimetliylene terephthalate is used.
  • I type cross-section, or + type cross-section can be used, but a semicircular side'byside with a round cross-section is preferabl used for balance between crimp
  • a hollow side-byside is preferably used when aiming for lightweight properties and heat, retaining properties, and triangular cross-section side-by-side is preferably used when aiming for dry texture.
  • a material with little hygroscopic properties is used as a polymer such as polyester fiber, acrylic fiber, or the like, and examples include a hollow fiber shape in a shape of fiber further provided with small holes on the wall surface, a modified cross -section shaped fiber or the like provided with many grooves, holes, or the like on the fiber surface or the like, wherein water absorbeney is achieved by moisture being absorbed into the small holes on the fiber, grooves on the fiber surface, and the space in between fibers and in between y arns, and the like.
  • a polyester conductive fiber or the like can be used as an antistatic synthetic fiber if required.
  • examples of a conductive substance can include a composite polyester fiber that uses carbon black (for example, "Bertroii (registered trademark)" manufactured by Kanebo Synthetic Fibers Ltd.), composite polyester fiber that uses white copper iodide or a metal complex oxide (for example. Ti02, Sn02, Sb202), and the like, but is the substance is not restricted to these.
  • the polyamide fiber in the present invention is fiber or the like made from nylon 6, nylon 66, nylon 12, or the like.
  • polyamide is a resin made from a high molecular weight body wherein a so-called hydrocarbon group is linked to the main chain through an amide bond, and such a polyamide has excellent, mechanical properties, and mainly polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 66) are preferable, and polycaproamide (nylon 6) is more preferable for having good dyeability.
  • components are not particularly restricted, but examples include units such as aminocarboxylic acid, dicarhoxylic acid , diamine, and the like, which are monomers that configure polydodecanoamide, polyhexamethylene adipamide, polyhexamethylene azelamide, polyhexamthylene sebacamide, polyhexamethylene
  • dodecanoamide polymethaxylylene adipamide, polyhexamethylene terephthalamide, polyhexamethylene ieoph.thala.mide, and the like.
  • the synthetic fiber used in the present invention has a fiber surface area preferably approximately 0,02 m2 or more and 0,2 m2 or less per 1 g of textile material, mare preferably approximately 0.1 m2 or more and 0.2 m2 or less, and eve more preferably approximately 0.12 m2 or more and 0,2 m2 or less.
  • the synthetic fiber in the present invention for example, has a single fiber fineness of preferably approximately 3 decitex (dtex) or more and 300 decitex or less, and more preferably 10 decitex or more and 150 decitex or less. Fibers with the fiber surface area and/or single fiber fineness can further enhance dyeability.
  • the polyester fibers used in the present invention may also contain various stabilizers, pigments, and the like within a range that does not impair the effect of the present invention, similarly to the aforementioned polyurethane.
  • various stabilizers, pigments, and the like within a range that does not impair the effect of the present invention, similarly to the aforementioned polyurethane.
  • a addition polymer of divinyifaenzeiie and p-cresol (“ME A CHLOE” (registered trademark) 2390 manufactured by Xhi Pont) and other stabilizers, light stabilizers; double hindered phenolic agents such as the so-called BHT or "SUMILIZER (registered trademark)” manufactured by Sumitomo Chemical Co., Ltd as antioxidants and the like; "TTNUVTN (registered trademark)” manufactured by Ciba Geigy and other benzotriazole and benzophenone drugs!
  • ME A CHLOE divinyifaenzeiie and p-cresol
  • deodorants silicone, mineral oil, and other lubricants; barium sulfate, cerium oxide, betaine, phosphoric acid, and various other antistatic agents, and the like may be added or may be present by reacting with a polymer.
  • nitrogen oxide capturing agents such as
  • thermal oxidation stabilizers such as "SUMIIJZEE. (registered trademark)" GA-80 and the like manufactured by Sumitomo Chemical Co., Ltd.
  • light stabilizers such as "SUMISORB (registered trademark)" 300#622 and other light stabilizers, and the like may be included in order to particularly further enhance the durability of the light, various nitrogen oxides, and the like.
  • the fabric which is the fibrous structure of the present invention may be obtained by manufacturing a fabric in accordance with a conventional method from the polyurethane fibers and other synthetic fibers or the like, and particularly more preferably contains two or more synthetic fibers including the aforementioned polyurethane fibers.
  • the fabric which is the fibrous structure of the present invention may be a woven material, knitter material, or nonwwen material.
  • the synthetic fiber may be covered on the polyurethane elastic fibers to obtain a fabric as a covering fiber, or the polyurethane elastic fibers may be woven and knitted as bare yarn to obtain an interlocked woven fabric.
  • the mixing ratio of the polyurethane elastic fibers in the mixed fabric depends on the counter thread, knitting structure, and woven structure, but may be within a range of
  • Examples of other materials include polyacrylonitirle fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, and polyurethane fibers which are synthetic fibers, acetate fibers which are semi- synthetic fibers, celluiosic fibers including viscose rayon and cupra which are regenerated fibers, protein fibers including milk protein fibers and soybean protein fibers, polylaetic acid fibers, and filament yarn applications, spun yarn applications, and blended yarn, applications thereof plant natural fibers including cotton and hemp, animal natural fibers includin wool, cashmere, and silk, further blended yarn applications thereof, and the like.
  • the fabric which is the fibrous structure of the present invention a woven, material
  • the fabric may be woven using synthetic fibers only, other fibers may be interwoven. Two types or more of the synthetic fibers including the polyurethane fibers are preferred.
  • the s gagture with the polyurethane elastic fiber as the woven material is preferably a plain weave, twill weave, sateen weave, or other three foundation weave, variable plain weave, variable twill weave, variable sateen weave, or other variable structures, a honeycomb weave, mock leno weave, crepe weave, or other special structures, a warp backed weave, weft backed weave, or other one-side backed structures, a reversible figured, hollow weave, double velvet, or other double structures, a belt weave or other multilayer structures, warped velvet, towel, seal, velor, or other warped pile weave, velveteen, weft velvet, velvet, corduroy, or other weft pile weave, a leno, plain gauze, figured gauze, or other knotted structure, or the like, [000106] Weaving is not particularly restricted so long as the effect of the present invention is not impaired, and is preferably performed by a shuttle loom (fly shuttle loom or the like), shuttleless
  • the fabric which is the fibrous structure of the present invention is a knitted material
  • the fabric may also be woven by synthetic fibers only, or other fibers may be interwoven. Two types or more of the synthetic fibers i ncluding the poiyurethane fibers are preferred.
  • the type of knitted material may be a weft knitted material or a warped knitted material.
  • the structure of the knitted material is preferably a plain stitching, rubber knitting, interlock stitching, pearl stitching, tuck stitching, float stitching, one-faced knitting, lace stitching, TENMGU, and the like for weft knitting, and preferably a single denbigh stitching, single atlas stitchin g, double cord stitching, half tricot stitching, lined stitching, jacquard stitching, and the like for warped knitting.
  • the number of layers may include a single layer or multiple layers of two or more.
  • Knitting is not particularly restricted so long as the effect of the present invention is not impaired, and is preferably performed by a circular knitting machine, flat knitting machine, cotton knitting machine or other flat knitting machines, a tricot knitting machine, raschel knitting machine, miianese knitting machines, or the like.
  • the fibrous structure of the present invention is dyed using an acidic dye, cationic dye, dispersion dye, or the like.
  • the dye is not particularly restricted but preferably has high dye fastness.
  • the acidic dyes may be an commercially available acidic dye, and may either be a leveling type, half milling type, milling type, or type containing metal.
  • Examples can include "NYLOSAN (registered trademark. ) E series, "NYLOSAN (registered trademark)” N series, “NYLOSAN (registered trademark ⁇ ” S series, ' “NYLOSAN (registered trademark)” F series, "LANASYN (registered trademark)” M series (aforementioned manufactured by
  • the cationic dye may be any commercially available cationic dye, and may either be a regular type (commonly referred to as raw cation) or dispersion type. Examples can include “KAYACRYL (registered trademark)”, “KAYACRYL (registered trademark)” ED
  • the dispersion dye may he any commercially available dye, and examples can include "KAYALON polyester UT series (manufactured by Nippon Kayaku Co., Ltd.), (registered trademark) "KA ALON polyester (registered trademark)” PUT series (manufactured by Kowa Chemical Industry Co., Ltd.), "TERASIL (registered trademark)” W series (manufactured by Huntsman), and the like.
  • the dyeing machine used for the dyeing treatment of the fiber structure of the present invention is not particularly restricted, and either dyeing or printing may be used, but ordinary liquid flow dyeing machines, beam dyeing machines, paddle dyeing machines, and the like are preferable from the perspective of uniform dyeing.
  • the dyeing temperature is preferably 90°C or higher and 140°C or lower, from the perspective of dye fastness and dye quality.
  • the fiber structure of the present invention has excellent dimensional sta bility, small dimensional change rate and minimal wrinkling, so the temperature for heat setting such as pre-setting and final setting and the like can be reduced, and the heat setting temperature is preferably 120°C or higher and 200°C or lower, from the perspective of material quality and dimensional stability.
  • the fiber structure of the present invention preferably has a laundering fastness according to JIS L-0848:2Q1.1A*2 of grade 4 or higher.
  • the fiber structure of the present invention was not only evaluated for dye fixing properties, or in other word s the balance of dyes after laundering multiple times, but also showed a practical level of resistance to repeated household and industrial laundering at high temperature.
  • a fabric which is a fiber structure of the present invention is used for, for example, outer garments such as coats, kimonos, suits, uniforms, sweaters, skirts, slacks, cardigans, sportswear, dress shirts, casual wear, and the like, a hosiery such as tights, stockings, panty hose, socks, and the like, underclothes such as pajamas, shorts, lingerie, foundation, hosiery, and the like, bedding such as bed sheets, bedding covers, bedding side materials, blankets, pillow covers, and the like, interiors such as sofa covers, table cloths, and the like, and accessories such as gloves, neckties, scarves, shawls, and the like, and in terms of diffusing fragrance ingredients, is preferably used particularly for underclothes, hosiery, bedding, and the like.
  • outer garments such as coats, kimonos, suits, uniforms, sweaters, skirts, slacks, cardigans, sportswear, dress
  • the fabric which is the fiber structure of the present invention contains, for example, synthetic fiber of preferably approximately 2 to 100 mass%, more preferably approximately 50 to 100 ass%, and eve more preferably approximately 80 to 100 mass%. Furthermore, from the viewpoint of ha ving particularly excellent dyeability, fabric in which the fiber component is only synthetic fiber is also preferable. Furthermore, from the viewpoint of baring excellent dyeability, the contained amount of polyure thane elastic fiber based on the entire synthetic fiber is preferably approximately 1 to 30 mass% and more preferably approximately ⁇ to 20 mass%.
  • the fabric which is the fiber structure of the present invention has a basis weight of preferably 80 to 1000 g/ni.2, more preferably 100 to 500 g/i3 ⁇ 42, and even more preferably 100 to 280 g/m2. Furthermore, elongation is preferably 5% or more in the longitudinal direction and/or the lateral direction.
  • the fabric w hich is the fiber structure of the present invention has a dimensional change rate by home laundering of preferably minus 5% and more preferably minus 3%.
  • a sample with a sample length of 5 cm (L I) was extended 300% 5 times at a tension rate of 50 cm/niin, stress at 100, 200, and 300% extension from the 5th time were measured, and the stress at 300% extension was made (Gl).
  • the sample was maintained for 30 seconds at a length of 300% extension.
  • the stress after maintaining for 30 seconds was made (Q2).
  • extension of the sample was restored, stress (recovery stress) at 200 and 100% extension were measured, and the length of the specimen at which the stress became 0 was made (L2).
  • the sample was further extended until the sample was cut during the 6th time. Stress when the sample was cut was made (G3), and the sample length when the sample was cut was made (L3).
  • the aforementioned properties were calculated using the following formulas.
  • Breaking elongation (%) 100 x ((L3) - (Ll))/(L1)
  • Sample thread (length L5) was extended 100% (length ⁇ 2 x (L5)X Treatment was performed for 1 minute at 160°C at this length. Furthermore, the sample thread with the same length was left at room temperature for one day. Next, the stretched state of the sample thread was relieved, and the length (L6) was measured.
  • Heat-setting properties 100 x i(L5)— (L6))/(L5)
  • Heat-setting properties with a higher value is more favorable.
  • Heat resistance of the polyurethane elastic fiber, and return properties after heat-setting was measured by tensile testing the sample thread using the INSTRON 4502 type tensile tester after heat-setting as mentioned above.
  • Heat resistance is better the higher the value is, and the lower the return properties after heat-setting is, the better the elastic property is.
  • the high temperature side melting point or in other words, the melting point of hard segment crystals were measured as one index of heat resistance for polyurethane thread.
  • Tine irreversible heat flow of the polyurethane thread was measured at a temperature elevation rate of 3°C/min using 2920 Modulated DSC manufactured by T.E. Instruments, a d the peak top was made the melting point.
  • the polyurethane elastic fiber was measured using the small angle ⁇ -ray, and the long period was calculated using the following method .
  • synchrotron radiation was made the light source using an imaging plate as the scattering intensity detector in order to more accurately measure the 20 to 100 am long period J.
  • the scattering angle 2 ⁇ in the Bragg equation was approximated to ⁇ tan - l(r/R) r was calculated from a continuous plot (scattering intensity profile) in which the horizontal axis was 4ixA/sinG(nm- 1) which was along meridian line 1 or equatorial line 2 and the vertical axis was scattering intensity.
  • a tubular knitted fabric made from 100 weight% polyurethane fiber was created using a 29 gauge 1 mouth tubular knitting machine. Next, dry heat heat-setting was performed on the tubular ' knitted fabric for 60 seconds at 190°C, and scouring was performed under the conditions of 20 minutes at 8Q°C using 0.1 weight of a scouring agent 'SUNMOLE (registered trademark)" manufactured by WX-HC, NICCA Chemical CO., LTD.). Dyeability was evaluated according to the following two methods using the created tubular knitted fabric. Measuring the dyeing rate
  • the scoured tubular knitted fabric was dyed with 1% owf ' of an acid dye ("RANASIN BLACK (registered trademark)" M"DL, manufactured by Huntsman Coip.) under the conditions of a bath ratio of 1:30, 95°C for 30 minutes using a mini-color dyeing machine manufactured by TEXAM CO., LTD.).
  • RANASIN BLACK registered trademark
  • MDL mini-color dyeing machine manufactured by TEXAM CO., LTD.
  • Absorbance (Al) of the dye liquid concentration before p re-dyeing and the peak wavelength were measured using a spectrophotometer (spectrophotometer manufactured by JASCO Corp ., model V"650) in order to calculate the average value of 3 times
  • absorbance (A2) of the peak wavelength was measured by collecting the residual liquid after dyeing in order to calculate the average value of 3 times
  • dyeing ratio of the dyed tubular knitted fabric after dyeing was calculated using the following equation.
  • 3-methyl-tetrahydrofuran were placed in a reactor attached with a stirring machine, polymerization reaction was performed under a nitrogen seal for 8 hours in the presence of catalyst (a mixture of 70 weight% of perchloric acid and 30 weight% of acetic anhydride) at a temperature of 1Q°C, and copolymerized tetramethylene ether diol (containing 1.2.5 moi% of structural unit (a) derived from 3 - methyHetrahydroguran) with a number average molecular weight of 2500 was used as polyalkylene ether diol which was provided by a eopolymerization method that neutralizes reaction complete solution using a sodium hydroxide aqueous solution .
  • catalyst a mixture of 70 weight% of perchloric acid and 30 weight% of acetic anhydride
  • a DMAc solution containing butanol as a terminal blocking agent was added, and a polyurethane solution pul in which polymer solid content was 35 weight was prepared.
  • the provided solutio had a viscosity of approximately 3800 poise at 40°C.
  • intrinsic viscosity was 0.90.
  • This polyurethane solution was discharged from a spinneret into high temperature (350°C) inert gas (nitrogen gas) as 4 filaments and were dried by passing through the high temperature gas, the 2 filaments were coalesced and spun together at a speed of 600 m/min by passing through an air jet type twisting machine that twists together the thread that is being dried, and 22dtex polyurethane elastic fiber (PUl) was manufactured using the 2 coalesced filaments.
  • high temperature 350°C
  • nitrogen gas nitrogen gas
  • the soft segment melting point (SSTm) of the polyurethane elastic fiber (PU12) was 0 °C
  • the long period of the small angle x-ray scattering measurement in the fiber direction (meridian line direction) was 49 nm
  • the tertiary nitrogen content was 1.6 meq/kg.
  • the soft segment melting point (SSTm) of the polyurethane elastic fiber (PU22) was 5 °C
  • the long period of the small angle ⁇ -ray scattering measurement in the fiber direction (meridian line direction) was 30 nm
  • the tertiary nitrogen content was 1.6 meq/kg.
  • the soft segment melting point (SSTm) of the polyurethane elastic fiber (PTJ3x2) was 3 °C
  • the Jong period of the small angle x-ray scattering measurement in the fiber direction (meridian line direction) was 11.7 am
  • the tertiary nitrogen content was 1.6 meq/kg.
  • a fiber structure was manufactured using polyurethane fibers PU12 to PU26, a ccording to combinations of each fiber containing ratio shown in Table 2.
  • Fiber structure 1 was manufactured according to m nufacturing process - L on Table 3 and fiber structure 2 was manufactured according to manufacturing process— L2 on Table 3. Comparative examples 1 to 12
  • a fiber structure was manufactured using polyurethane fibers PU3X2 to PU3X6 and PU1X to PU1X3, according to combinations of each fiber containing ratio shown in Table 2.
  • Fiber structure IX was manufactured according to manufacturing process - L on Table 3 and fiber structure 2X was manufactured according to ma ufacturing process - L2 on Table 3.
  • the fiber structure of the present invention has heat-setting properties, heat resistance, dyeahility, recoverahility, and elasticity. Furthermore, clothing, nonwoven fabric, or the like using the fiber structure become excellent in regards to desorption property, fitting property, wearing feeling, heat retaining property, outward appearance, and the like.
  • the polyurethane thread used in the present invention can certainly be used independently, but can become excellent stretch fabric with favorable composition, weaving, and siring processing by being combined with various fibers.
  • Specific usable applications include various textile products such as socks, stockings, tights, round braids, tricots, ski pants, work clothes, fireworks clothes, golf pants, wet suits, bras, girdles, gloves, and the like, tightening material, tightening material for leak prevention of sanitary goods such as paper d iapers or the like, bait, artificial flowers, electrical insulating material, wiping cloths, copy cleaners, gaskets, and the like.

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Abstract

L'invention concerne la fourniture d'une structure de fibre ayant d'excellentes propriétés thermodurcissables, de résistance à la chaleur, d'aptitude à la teinture, de récupérabilité et d'élasticité. L'invention concerne également le procédé de fabrication. L'invention concerne une structure de fibre qui constitue une structure de fibre contenant une fibre élastique de polyuréthane, la première longue période (J1) de la mesure de diffusion des rayons X aux petits angles de la fibre élastique de polyuréthane allant de 20 à 100 nm et contenant des composés d'azote tertiaire.
PCT/US2016/068302 2015-12-28 2016-12-22 Structure de fibre de polyuréthane WO2017116983A1 (fr)

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