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
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
  • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
• • 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
  • C08G18/3225—Polyamines
  • C08G18/3228—Polyamines acyclic
• • 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
  • C08G18/4858—Polyethers containing oxyalkylene groups having more than 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
  • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/12—Applications used for fibers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
  • D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/06—Load-responsive characteristics
  • D10B2401/061—Load-responsive characteristics elastic
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/06—Load-responsive characteristics
  • D10B2401/062—Load-responsive characteristics stiff, shape retention

Definitions

• the present invention relates to a polyurethane resin composition and a polyurethane elastic fiber and particularly relates to a polyurethane elastic fiber having high stress during shrinkage, that is, high recovery stress, as well as excellent antioxidative properties and high durability.
• Polyurethane resins have excellent stretchability and thus are widely deployed in paint, coating agents, sealing materials, glues, adhesives, fiber processing agents, artificial leathers and synthetic leathers, raw materials for elastomers such as rollers, fiber products, and the like.
• thermosetting properties decrease particularly when making fibers
• compositions with high oxidizing properties have been required for fibers having large surface areas.
• a polyurethane structure composed of a diisocyanate and a copolyether diol of tetrahydrofuran and 3-alkyl tetrahydrofuran may be a soft segment having higher stress during shrinkage, that is, higher recovery stress, than the former (patent documents 1 and 2).
• Patent Document 1 JP H2-19511 A
• Patent Document 2 JP H9-136937 A
• Patent Document 3 JP 2008-69506 A
• Patent Document 4 WO 2009/011189
• Patent Document 5 JP 2014-522446 A (Translation of PCT Application)
• Patent Document 6 JP 2021-152139 A
• Spherary of Invention [Problem to Be Solved by Invention]
• a problem of the present invention is to provide a high durability polyurethane resin composition and a polyurethane elastic fiber having high stress during shrinkage, that is, high recovery stress, as well as excellent antioxidative properties.
• the present inventors examined cases wherein an alkyl group is present on a carbon atom adjacent to an ether group in a tetramethylene ether. That is, this is a polyurethane structure composed of a diisocyanate and a copolyether diol of tetrahydrofuran and 2- alkyl tetrahydrofuran.
• a 2-alkyl group had higher recovery stress than a 3-alkyl group in the polyurethane resin composition and in the polyurethane elastic fiber. Furthermore, the present inventors found that, compared to a 3-alkyl group, a completely different heat resistant behavior is exhibited when using a 2-alkyl group. In other words, it was found that in the case of a 2-alkyl group, a nitrogen-containing aromatic compound maximizes heat resistance at a specific added amount.
• a polyurethane elastic fiber provided with a polyurethane having a polyether structure in its backbone and a nitrogen-containing aromatic compound, wherein the polyether structure satisfies the following general formula (1), and the polyurethane elastic fiber contains no less than 0.05% by mass to no more than 2.0% by mass of the nitrogen-containing aromatic compound.
• An article comprising a polyurethane elastic fiber having a polyether structure in its backbone and a nitrogen-containing aromatic compound, wherein the polyether structure is represented by the following general formula (1), and the polyurethane elastic fiber contains no less than 0.05% by mass to no more than 2.0% by mass of the nitrogen-containing aromatic compound [Formula 1] (R 1 is an alkylene group having 2 to 6 carbon atoms, R 2 is an alkyl group having 1 to 2 carbon atoms, and l, m, and n satisfy 4 ⁇ n/(l+m+n) ⁇ 100 ⁇ 50 ). (8) The article of claim 7, wherein the article is selected from the group consisting of a fiber, a fabric, a film, and combinations thereof.
• the present invention it is possible to provide a high durability polyurethane elastic fiber having high stress during shrinkage, that is, high recovery stress, as well as excellent antioxidative properties.
• the present invention will be described in detail below along with embodiments. First, the polyurethane used in the polyurethane resin composition and the polyurethane elastic fiber of the present invention will be described.
• the polyurethane described herein is preferably used as a main component, and the term main component as described herein is a component contained in the polyurethane resin composition the polyurethane elastic fiber in an amount exceeding 50% by mass.
• the polyurethane used in the present invention has a polyether structure in its backbone.
• the polyurethane having a polyether structure in its backbone has a structure in which a polymer diol having a polyether structure and a diisocyanate serve as the starting material.
• the phrase "having a structure in which...serve as starting material” refers to the structure of the relevant portion of the starting material in order to describe its backbone structure of the polymer, and the starting material and synthesis method thereof are not particularly limited.
• the starting material may be, for example, a polyurethane urea composed of a polymer diol, a diisocyanate, and a low molecular weight diamine as a chain extender, or may be a polyurethane urethane composed of a polymer diol, a diisocyanate, and a low molecular weight diol as a chain extender.
• polyurethane urea which uses a compound having a hydroxyl group and an amino group in the molecule, may be used as a chain extender. It is also preferable that trifunctional or higher polyfunctional glycols, isocyanates, and the like be used to the extent that they do not impede the effects of the present invention.
• the processing method is not particularly limited either. That is, the polyurethane may be recycled through remolding and re-spinning.
• the polyether structure of a polymer diol having a polyether structure satisfies the following general formula (1).
• R 1 is an alkylene group having 2 to 6 carbon atoms
• R 2 is an alkyl group having 1 to 2 carbon atoms
• l, m, and n satisfy 4 ⁇ n/(l+m+n) ⁇ 100 ⁇ 50
• l, m, and n in the foregoing general formula (1) satisfy 6 ⁇ n/(l+m+n) ⁇ 100 ⁇ 16
• l, m and n represent only the ratio. That is, respective units are not limited to only block bodies having l, m, and n as repeating units, but respective units may be random bodies connected at random.
• n is defined as the number of - (CH 2 CH 2 CH 2 CHR 2 -O)n- in the foregoing general formula (1) at terminals of the foregoing general formula (1)
• the balance between stress during extension and stress during extension recovery is more favorable, and durability, that is, resistance to thermal oxidation degradation, resistance to ultraviolet degradation, resistance to chlorine degradation, and a combined resistance to these is improved due to a synergistic action with the nitrogen-containing aromatic compound.
• R 1 take carbon atoms in a number other than 4, such as 2, 3, 5, or 6.
• a number other than 4 such as 2, 3, 5, or 6.
• water vapor permeability increases, and moisture absorption and water absorption functions are imparted, while in the case of 6, hydrophobicity is imparted.
• odd carbon numbers of 3 and 5 crystals during elongation (strain-induced crystals) in the soft segment may be suppressed, thereby contributing to elongation recovery.
• THF and 2-MeTHF which are the raw materials for structural units of (CH 2 CH 2 CH 2 CH 2 -O) and (CH 2 CH 2 CH 2 CHR 2 -O), be used as the raw materials for components derived from carbon-neutral biomass resources suitable for thermal recycling.
• the degree to which components derived from biomass resources are used as raw materials is expressed as the bio-conversion rate.
• the bio-conversion rate can be obtained using ISO 16620- 2, which is a radiocarbon (carbon-14) concentration measurement identification method.
• the radioactive carbon (carbon-14) concentration measurement identification method of ISO 16620-2 described above may be simply referred to as carbon isotope ratio measurement.
• the polyurethane resin composition and polyurethane elastic fiber of the present invention have a bio-conversion rate of 3% or more in carbon mass ratio as determined by carbon isotope ratio measurement.
• the other polymer diol contains a polyether-based, polyester-based diol, polycarbonate diol, or the like.
• a polyether-based diol is particularly preferably used from the perspective of imparting flexibility and elongation to a molded body obtained from the polyurethane resin composition of the present invention and to a polyurethane elastic fiber obtained from the polyurethane resin composition of the present invention.
• two or more types of these polymer diols may be used in combination.
• the number average molecular weight is preferably 1,000 or more and more preferably 3,000 or more from the perspective of obtaining elongation, strength, heat resistance, and the like when made into an elastic fiber.
• a polyol having a number average molecular weight of 30,000 or less is preferable, and 6,000 or less is more preferable.
• a polyol having a molecular weight in this range an elastic fiber having excellent elongation, elastic recovery capabilities, heat resistance, and durability due to synergistic effects with a nitrogen-containing aromatic compound can be obtained.
• aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter also abbreviated as MDI), tolylene diisocyanate, benzene 1,4-diisocyanate, xylylene diisocyanate, 2,6-naphthalene diisocyanate, and the like are suitable for synthesizing polyurethane having particularly high heat resistance and strength.
• MDI diphenylmethane diisocyanate
• tolylene diisocyanate benzene 1,4-diisocyanate
• xylylene diisocyanate benzene 1,4-diisocyanate
• 2,6-naphthalene diisocyanate 2,6-naphthalene diisocyanate
• alicyclic diisocyanate for example, methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane 2,4- diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalene diisocyanate, and the like are preferable.
• Alicyclic diisocyanates may be particularly effectively used to suppress yellowing of molded articles obtained from the polyurethane resin composition of the present invention and polyurethane elastic fibers obtained from the polyurethane resin composition of the present invention. Furthermore, these diisocyanates may be used alone, or two or more types may be combined.
• a molded article obtained from the polyurethane resin composition may be referred to as a polyurethane resin molded article.
• at least one type of low molecular weight diamine or low molecular weight diol be used as the chain extender used in synthesizing the polyurethane.
• a type having both a hydroxyl group and an amino group in one molecule such as ethanolamine
• preferable low molecular weight diamines include ethylenediamine, 1,2- propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p- xylylenediamine, m-xylylenediamine, p,p'-methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis(4- aminophenyl)phosphine oxide, and the like. It is preferable to use one or two or more of these.
• Ethylenediamine is particularly preferable.
• ethylenediamine By using ethylenediamine, an elastic fiber having excellent elongation, elastic recovery, and heat resistance can be easily obtained.
• typical examples of low molecular weight diols include ethylene glycol, 1,3- propanediol, 1,4-butanediol, bishydroxyethoxy benzene, bishydroxyethylene terephthalate, and 1- methyl-1,2-ethanediol. It is preferable to use one or two or more of these.
• the molecular weight of the polyurethane in the present invention is preferably within a range of no less than 30,000 to no more than 150,000 in terms of the number average molecular weight from the perspective of obtaining a polyurethane resin molded article and polyurethane elastic fiber having high durability and strength. Note that the molecular weight is measured by GPC and converted using polystyrene.
• terminal blocking agents include: monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, and diamylamine; monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, and cyclopentanol, and monoisocyanates such as phenyl isocyanate.
• monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, and diamylamine
• monools such as ethanol, propan
• the polyurethane resin composition and polyurethane elastic fiber of the present invention contain no less than 0.05% by mass to no more than 2.0% by mass of a nitrogen-containing aromatic compound. This synergistically exhibits high durability with polyurethane having the polyether structure of the foregoing general formula (1) in its backbone, in particular, high durability with excellent antioxidative properties.
• a value of no less than 0.05% by weight to no more than 2.0% by weight of the content of the nitrogen-containing aromatic compound generally corresponds to the nitrogen-containing aromatic compound being present in a range of 0.25 to 13.3 milliequivalents (meq/kg) per 1 kg of elastic fiber.
• an aromatic ring containing a nitrogen atom easily undergoes thermal decomposition, when the content of the nitrogen-containing aromatic compound is too high (that is, when the aromatic ring nitrogen atom exceeds 13.3 milliequivalents), radical generation due to thermal decomposition will be more dominant than the synergistic effect of polyurethane having the polyether structure of general formula (1) in its backbone, heat resistance will be reduced, and a quinone structure will be formed, causing thermal discoloration.
• the content of the nitrogen-containing aromatic compound be an appropriate amount that is not too great, and the preferable range is no less than 0.1% by mass to no more than 1.0% by mass, and more preferably no less than 0.2% by mass to no more than 0.8% by mass.
• n' is defined as the number of -(CH 2 CH 2 CH 2 CHR 2 - O)n- in the polyurethane having the polyether structure of the foregoing general formula (1) in its backbone at terminals
• 5 ⁇ n'/(l+m+n) ⁇ 100 ⁇ 30 be satisfied.
• the effect of antioxidative properties with the nitrogen-containing aromatic compound may be synergistically exhibited.
• 10 ⁇ n’/(l+m+n) ⁇ 100 ⁇ 15 is more preferable, and the nitrogen-containing aromatic compound is more effective at a smaller amount.
• the content of the nitrogen- containing aromatic compound is preferably no less than 0.1% by mass to no more than 0.6% by mass.
• the contained nitrogen-containing aromatic compound is a compound having a nitrogen-containing aromatic heterocyclic ring in which nitrogen atoms are arranged on an aromatic ring in the molecule.
• chemical structural backbones include: pyrrole, pyridine, carbazole, and quinoline, which have a one-nitrogen aromatic heterocyclic ring; imidazole, pyrazole, pyridazine, pyrazine, pyrimidine, naphthyridine, and phenanthroline, which have a two-nitrogen aromatic heterocyclic ring; triazine, benzotriazole, and naphthyridine, which have a three-nitrogen aromatic heterocyclic ring; and the like, and heteroatoms other than nitrogen may also be included, such as in benzothiazole and benzoxazole.
• benzotriazole compounds and triazine compounds known as ultraviolet light absorbers are preferable, and more specifically, examples include compounds such as 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxyphenyl)-5- chlorobenzotriazole, 2-(2-hydroxy-3,5-bisphenyl)benzotriazole, 2,4-di(2', 4'-dimethylphenyl)-6- (2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazine, and 2,2'-(1,4-phenylene)bis[4H-3,1-benzoxazin-4- one].
• Examples of product names include: “Tinuvin”-P, “Tinuvin”-213, “Tinuvin”-234, “Tinuvin”- 327, “Tinuvin”-328, “Tinuvin”-571, and “Tinuvin”-1577 manufactured by Ciba-Geigy; “Sumisorb” 250 manufactured by Sumitomo Chemical Co., Ltd.; “Cyasorb” UV-5411, UV-1164, and UV-3638 manufactured by American Cyanamid; “Adeka Stab” LA-31 manufactured by Asahi Denka Corporation; and the like.
• the content of nitrogen-containing aromatic compound must be no less than 0.05% by weight to no more than 2.0% by weight.
• nitrogen-containing aromatic compounds a group of compounds having a molecular weight of 300 or more is preferable from the perspective of suppressing loss through volatilization during spinning.
• the compound it is more preferable that the compound have two or more nitrogen atoms in the aromatic ring, and this is assumed to facilitate the formation of a complex with a heavy metal and to demonstrate a chelating effect.
• the chemical structural backbone of the nitrogen-containing aromatic compound is preferably triazine.
• testing be conducted in advance depending on the molecular weight of the nitrogen-containing aromatic compound which is actually to be used, as well as the number of effective nitrogen atoms in the aromatic ring, the application, and the like, and that an optimal value be appropriately determined.
• 2,4-di(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazine is preferred as the nitrogen-containing aromatic compound in order to obtain a polyurethane elastic fiber that has particularly high heat resistance during dyeing.
• the compound used as the nitrogen-containing aromatic compound is preferably a liquid compound with a viscosity of no less than 100 cP to no more than 10,000 P at 20°C, from the perspective of accelerated dispersion and dissolution of the compound into the polyurethane, the imparting of desired properties to the produced polyurethane elastic fiber, the possibility of obtaining a polyurethane elastic fiber having an appropriate degree of transparency, the content of these compounds not decreasing even when heated or the like during the spinning process, and discoloration and yellowing of the polyurethane elastic fiber not occurring.
• the polyurethane used in the present invention preferably contains a mixture of one or two or more terminal blocking agents.
• the terminal blocking agent is preferably: a monoamine such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, or diamylamine; a monool such as ethanol, propanol, butanol, isopropanol, allyl alcohol, or cyclopentanol; a monoisocyanate such as phenyl isocyanate; or the like.
• a monoamine such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, or diamylamine
• various stabilizers other than those mentioned above, such as hindered phenol-based, sulfur-based, and phosphorus-based antioxidants, hindered amine- based, triazole-based, benzophenone-based, benzoate-based, nickel-based, and salicylic-based antioxidants light stabilizers, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, fluorescent brightening agents, fillers, flame retardants, flame retardant aids, pigments, and the like may be contained in the polyurethane elastic fiber or polyurethane spinning solution within ranges that do not impede the effects of the present invention.
• antioxidants such as hindered phenol-based, sulfur-based, and phosphorus-based antioxidants, hindered amine- based, triazole-based, benzophenone-based, benzoate-based, nickel-based, and salicylic-based antioxidants light stabilizers, antistatic agents, lub
• light resistant agents and antioxidants contain the following: 2,6-di-t-butyl-p-cresol (BHT) and benzophenone- based drugs, various hindered amine-based drugs, various pigments such as iron oxide and titanium oxide, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide, and carbon black, fluorine-based or silicone-based resin powders, metal soaps such as magnesium stearate, disinfectants, deodorants, antibacterial agents containing silver, zinc, and these compounds, lubricants such as silicone and mineral oil, and various antistatic agents such as barium sulfate, cerium oxide, betaine, and phosphoric acid-based agents. It is also preferable to react these with a polymer.
• BHT 2,6-di-t-butyl-p-cresol
• benzophenone- based drugs various hindered amine-based drugs
• various pigments such as iron oxide and titanium oxide
• inorganic substances such as zinc oxide, cerium oxide, magnesium oxide, and carbon black
• nitric oxide scavengers such as HN-130 and HN-150 manufactured by Japan Finechem Co., Inc., for example, are preferably used to further increase durability, particularly to light and various types of nitric oxides. Furthermore, from the perspective of facilitating an increase in the spinning speed during the dry spinning process, fine particles of a metal oxide such as titanium dioxide, zinc oxide, or the like may be added to the spinning dope.
• inorganic materials and inorganic porous materials may be added within a range that does not inhibit the effect of the present invention.
• These additives may be added when preparing the spinning dope by mixing a polyurethane solution and the above modifiers, or may be added beforehand in the polyurethane solution or dispersion before mixing. The content of these additives is appropriately determined according to the purpose and the like.
• a content of no less than 0.002% by mass to no more than 5.0% by mass is preferable when an antioxidant is included.
• an antioxidant is included.
• Particularly preferable antioxidants are hindered phenol compounds, and examples include phenol compounds generally known as antioxidants.
• the hindered phenol compound having such a high molecular weight include an addition polymer of divinylbenzene and cresol, an addition polymer isobutylene adduct of dicyclopentadiene and cresol, and a polymer of chloromethylstyrene and a compound such as cresol, ethylphenol, and t-butylphenol.
• divinylbenzene and chloromethylstyrene may be p- or m-.
• cresol, ethylphenol, and t-butylphenol may be o-, m-, or p-.
• the compound have a molecular weight of 300 or more.
• 1,3,5-tris(4- t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is particularly preferable.
• a triazine compound is selected as compound (a) and compound (c)
• a particularly high synergistic effect may be obtained in terms of heat resistance during dyeing.
• the compound (a) be 1,3,5-tris(4-t-butyl-3-hydroxy-2,6- dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and the compound (c) be 2,4-di(2',4'- dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazine.
• a partially hindered phenol compound is preferably included in the polyurethane elastic fiber of the present invention.
• the partially hindered phenol compound is preferably a compound containing at least two partially hindered hydroxyphenyl groups and having a backbone selected from bis-esters and alkylidenes.
• the alkyl group present at the ring position adjacent to the hydroxyl group in the hydroxyphenyl group is preferably a tertiary butyl group, and the equivalent of the hydroxyl group is more preferably 600 or less.
• a partially hindered phenol compound is also preferable as the phenol compound in the present invention.
• ethylene-1,2-bis(3,3-bis[3-t-butyl-4- hydroxyphenyl]butyrate) (chemical formula 1 below) having a structure in which a partially hindered hydroxyphenyl group is covalently bonded to a bis-ester backbone is preferable as the partially hindered phenol compound.
• the foregoing partially hindered phenol compound can enhance the effect of suppression of the deterioration of characteristics.
• this type of hindered phenol compound acts to specifically suppress the molecular weight of the polyurethane constituting the polyurethane elastic fiber and is effective when washing and bleaching are performed at a high frequency, such as for underwear.
• the partially hindered phenol compound is preferably contained in an amount of 0.15 to 4% by mass and more preferably in an amount of 0.5 to 3.5% by mass relative to the urethane elastic fiber, and rupture strength/elongation, combined durability, yellowing resistance, and in some cases, light resistance, are ensured.
• a more preferable content of the antioxidant is in the range of no less than 0.2% by mass to no more than 3.0% by mass, and further preferably in the range of no less than 0.5% by mass to no more than 2.0% by mass.
• the content of the antioxidant in the polyurethane elastic fiber is preferably in the range of no less than 0.1% by mass to no more than 5.0% by mass.
• the content of the antioxidant in the polyurethane elastic fiber is more preferably in the range of no less than 0.2% by mass to no more than 3.0% by mass, and further preferably in the range of no less than 0.5% by mass to no more than 2.0% by mass. More specifically, a hindered phenol compound having a molecular weight of 1,000 or more which is known as an antioxidant agent for a polyurethane elastic fiber is preferably used as the contained antioxidant. There are no particular restrictions with regard to the hindered phenol compound other than a relatively high molecular weight of 1,000 or more.
• the hindered phenol compound having such a high molecular weight include an addition polymer of divinylbenzene and cresol, an addition polymer isobutylene adduct of dicyclopentadiene and cresol, and a polymer of chloromethylstyrene and a compound such as cresol, ethylphenol, or t-butylphenol.
• divinylbenzene and chloromethylstyrene may be p- or m-.
• cresol, ethylphenol, and t-butylphenol may be o-, m-, or p-.
• a hindered phenol compound of a polymer derived from cresol is preferable from the perspective of stabilizing the viscosity of the raw material spinning solution of the polyurethane elastic fiber and obtaining good spinnability. Furthermore, in order to efficiently exhibit a high spinning speed, heat resistance during dyeing, resistance to unsaturated fatty acids, and resistance to heavy metals, it is preferable to include a certain amount of the high molecular weight hindered phenol compound; however, from the perspective of obtaining better basic properties as a polyurethane elastic fiber, it is preferable that this not be too much.
• the content of a degradation product of the antioxidant described above is preferably regulated to 1.0% by mass or less.
• a preferred content of degradation products of the antioxidant is in the range of 1.0% by mass or less, and more preferably in the range of 0.5% by mass or less.
• a content of no less than 0.2% by mass to no more than 5.0% by mass is preferable when a tertiary amine compound is included.
• properties of the polyurethane elastic fiber that are practically preferable, as well as spinnability, dyeability, durability, and resistance to yellowing are improved.
• the tertiary amine compound used in the present invention is not particularly limited so long as it is a compound which has an amino group in the structure, but from the perspective of resistance to chlorine degradation and resistance to yellowing of the urethane elastic fiber, a compound having only tertiary amino groups in the molecule from among primary to tertiary amino groups is particularly preferable.
• the number average molecular weight of the tertiary amine compound is less than 2,000, water repellency deteriorates due to shedding as a result of friction with the guide or the knitting needle during knitting of the polyurethane elastic fiber or due to outflow during processing in a bath such as dyeing. Therefore, the number average molecular weight must be 2,000 or more.
• the number average molecular weight is preferably in a range of 2,000 to 10,000. More preferably, it is in the range of 2,000 to 4,000.
• Inclusion of the tertiary amine compound can enhance the performance of the polyurethane elastic fiber, particularly the performance in terms of preventing yellowing. From the perspective of ensuring that this effect is sufficient and of not adversely affecting the physical properties of the fiber, the tertiary amine compound is preferably contained in an amount of no less than 0.2% by mass to no more than 5.0% by mass and more preferably in an amount of no less than 0.5% by mass to no more than 4.0% by mass relative to the mass of the fiber.
• a more preferable content of the tertiary amine compound is in the range of no less than 0.5% by mass to no more than 3.0% by mass, and further preferably in the range of no less than 0.5% by mass to no more than 2.0% by mass.
• the contained tertiary amine compound may be a linear polymer compound with a number average molecular weight of 2,000 or more that is produced by a reaction of t-butyl diethanolamine and methylene-bis-(4-cyclohexyl isocyanate), polyethyleneimine, a polymer compound having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group in the molecular backbone, or the like.
• the content of a degradation product of the tertiary amine compound described above is preferably regulated to 1.0% by mass or less.
• the content of the degradation product of the tertiary amine compound is within this range, properties of the polyurethane elastic fiber that are practically favorable, and a particularly favorable wound body shape, combined durability, and resistance to yellowing are ensured.
• a more preferable content of the degradation product of the tertiary amine compound is in the range of 1.0% by mass or less, and further preferably in the range of 0.5% by mass or less.
• a content of no less than 0.002% by mass to no more than 2.0% by mass is preferable when a crosslinked structure regulator is included.
• the crosslinked structure regulator is an agent that is added after the polyurethane polymerization terminator is added and the polymerization is completed.
• a more preferable content of the crosslinked structure regulator is in the range of no less than 0.02% by mass to no more than 1.5% by mass, and further preferably in the range of no less than 0.2% by mass to no more than 1.0% by mass.
• Examples of the contained crosslinked structure regulator include monoamines and/or diamines. More specifically, examples of monoamines include dimethylamine, diethylamine, cyclohexylamine, and the like, and examples of diamines include ethylenediamine, 1,2- propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p- xylylenediamine, m-xylylenediamine, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and the like. Combined use of a monoamine and a diamine is particularly preferable. It is effective to do so.
• the index it is preferable to blend a polyurethane having no peaks or shoulders in the detection intensity curve in a region wherein the number average molecular weight based on gel permeation chromatography (GPC) is no less than 20,000 to no more than 120,000 and the molecular weight based on GPC is 30,000 or less.
• the number average molecular weight is preferably in the range of no less than 30,000 to no more than 100,000. More preferably, it is in the range of no less than 40,000 to no more than 80,000.
• the detection intensity curve is a differential molecular weight distribution curve (the horizontal axis is a molecular weight, and the vertical axis is a value wherein a concentration fraction is differentiated by a logarithmic value of the molecular weight), and the shoulder is a shoulder peak.
• the number average molecular weight is preferably in the range of no less than 10,000 to no more than 50,000.
• the molecular weight is measured by GPC and converted using polystyrene.
• the method for producing the polyurethane elastic fiber of the present invention will be described in detail.
• the method for producing the polyurethane solution and the polyurethane which is the solute in the solution may be either of a melt polymerization method or a solution polymerization method, or may be any other method.
• a more preferred method is solution polymerization.
• a solution polymerization method the generation of foreign matter such as gel and the like in the polyurethane is minimal, and therefore, spinning is easy, and it is easy to produce a polyurethane elastic fiber having low linear density.
• An article may be formed comprising a polyurethane elastic fiber according to any of the embodiments of the present invention described herein. Specific examples of articles formed may include a fiber, a fabric, a film, and combinations thereof. Examples of the fabric may include a knit, a woven, and a non-woven.
• the polyurethane elastic fiber of the present invention may be used in various applications.
• the polyurethane elastic fiber may be suitably used in areas where elastic stretching force is required.
• Examples (Examples 1 to 18 and Comparative Examples 1 to 10)
• the production and evaluation of polyurethane elastic fibers and elastic fibers to which the nitrogen-containing aromatic compound has been added will be described below in regard to Examples 1 to 18 and Comparative Examples 1 to 10 illustrated in Tables 1 to 4.
• Comparative Example 1 In Comparative Example 1, which is conventional art, 87.5 mol of dehydrated tetrahydrofuran and 4.0 mol of dehydrated 3-methyl-tetrahydrofuran were placed in a reactor with a stirrer.
• a polymerization reaction was performed for 8 hours under a nitrogen seal in the presence of a catalyst (a mixture of 70% by weight perchloric acid and 30% by weight acetic anhydride) at a temperature of 10°C, and a copolymerized tetramethylene ether diol with a number average molecular weight of 3,500 (including 4.0% by mole of structural unit (a) derived from 3-methyl-tetrahydrofuran) obtained by means of a copolymerization method of neutralization with an aqueous sodium hydroxide solution in a reaction termination solution was used as a polyalkylene ether diol.
• a catalyst a mixture of 70% by weight perchloric acid and 30% by weight acetic anhydride
• a DMAc solution containing 60% by mole of ethylenediamine (EDA) and 40% by mole of 1,2- propanediamine (1,2-PDA) as a chain extender was added to a solution in which the reaction product was dissolved, and a DMAc solution containing diethylamine as a terminal sequestering agent was also added to prepare a polyurethane urea solution with a polymer solid content of 25% by weight.
• the resulting solution had a viscosity of approximately 2,400 poise at 40°C.
• the polymer had an intrinsic viscosity of 0.90 when measured at 25°C at a solution concentration of 0.5 g/100 mL in DMAc.
• the polyurethane urea solution was discharged from a spinneret into an inert gas (nitrogen gas) at a high temperature (350°C) using four filaments, dried by passing through the high temperature gas, passed through an air jet-type twisting machine so that the yarn was twisted during drying, fused with four filaments, and wound at a speed of 540 m/minute. Four filaments were then fused to produce a polyurethane urea fiber of 44 dtex.
• the glass transition point (Tg) was -74°C. Note that the urethane group concentration of the polyurethane urea constituting the polyurethane urea fiber was 0.49 mol/kg, and the effective terminal amine concentration was 18 meq/kg.
• the foregoing solution PUUX1, the additive solution (B), and the nitrogen-containing aromatic compound (C) were uniformly mixed at 99% by mass, 1.0% by mass, and 0.2% by mass, respectively, and were made to be the spinning solution (D).
• dry spinning was carried out at a dry nitrogen temperature of 300°C or higher so that DMAc and floating ethylene diamine in the spinning solution were 1/100 or lower of the content of the spinning dope.
• the 22 dtex/3 fil multifilament polyurethane elastic fiber was spun with the speed ratio of the godet roller and the winder set to 1:1.20, and the treatment agent (oil agent) described below was supplied to the roller by the oiling roller before winding.
• the polyurethane elastic fiber was wound using a surface drive winder via a traverse guide providing a winding width of 38 mm to a cylindrical paper tube with a winding speed of 600 m/min and a length of 58 mm, and a dry spun polyurethane elastic fiber was obtained as a 500 g wound body.
• the obtained polyurethane elastic fiber was a spliced yarn made by splicing three filaments together.
• the rotational speed of the oiling roller was adjusted so that the amount of treatment agent applied was a predetermined amount relative to the yarn. Furthermore, the amount of treatment agent added was measured using n-hexane as an extraction solvent in accordance with JIS-L1073 (synthetic fiber filament yarn testing method).
• composition of the treatment agent used herein is a mixture of 80 parts by mass of polydimethylsiloxane having a viscosity of 1 ⁇ 10 -5 m 2 /s at 25°C, 15 parts by mass of mineral oil having a viscosity of 1.2 ⁇ 10 -5 m 2 /s at 25°C, and 5 parts by mass of magnesium distearate having an average particle diameter of 0.5 ⁇ m.
• Example 1 The 44 dtex polyurethane urea fiber was produced in exactly the same way, except that 2- methyl-tetrahydrofuran was used in place of the 3-methyl-tetrahydrofuran in Comparative Example 1.
• the glass transition point (Tg) was -70°C.
• the urethane group concentration of the polyurethane urea constituting the polyurethane urea fiber was 0.49 mol/kg, and the effective terminal amine concentration was 20 meq/kg.
• Examples 2 to 5 As shown in Table 1, only the concentration of 2-methyl-tetrahydrofuran in the copolyether polyol was changed, and a 44 dtex polyurethane urea fiber was produced using the same method as Example 1.
• Comparative Examples 2 to 5 As shown in Table 1, only the concentration of 3-alkyl-tetrahydrofuran in the copolyether polyol was changed, and a 44 dtex polyurethane urea fiber was produced using the same method as Example 1.
• Example 6 to 10 As shown in Table 2, based on Example 2, only the content of the nitrogen-containing aromatic compound in the polyurethane elastic fiber was changed, and a 44 dtex polyurethane urea fiber was produced using the same method as Example 1. [Comparative Examples 6 to 10] As shown in Table 2, based on Comparative Example 4, only the content of the nitrogen- containing aromatic compound in the polyurethane elastic fiber was changed, and a 44 dtex polyurethane urea fiber was produced using the same method as Example 2.
• Examples 11 to 13 As shown in Table 3, based on Example 7, only the concentration of a secondary hydroxyl group in the copolyether polyol was changed, and a 44 dtex polyurethane urea fiber was produced using the same method as Example 1.
• Examples 14 to 16 As shown in Table 4, based on Example 7, only the number average molecular weight of the copolyether polyol was changed, and a 44 dtex polyurethane urea fiber was produced using the same method as Example1.
• Examples 17 and 18 As shown in Table 4, based on Example 7, only the bio-conversion rate was changed, and a 44 dtex polyurethane urea fiber was produced using the same method as Example 1.
• Example 17 in order to make the raw material 2-MeTHF, which is a raw material of the (CH 2 CH 2 CH 2 CHR 2 -O) structural unit, a component derived from a carbon neutral biomass resource that is suitable for thermal recycling, 2-MeTHF synthesized via D-xylol and furfural derived from hemicellulose was used. Furthermore, in Example 18, THF synthesized via D-xylol and furfural derived from hemicellulose was similarly used as the raw material for the (CH 2 CH 2 CH 2 CH 2 -O) structural unit. As a result, performance was shown that was equal to or better than Example 7 using raw materials of petrochemical origin.
• the content percentage is a value relative to 100 parts by mass of polymer solid content in the spinning dope.
• the dry spun polyurethane elastic fiber (hereinafter referred to as the sample yarn) obtained above was subjected to the following evaluations.
• the stress at 200% elongation was defined as (G+200), and the stress at 300% elongation was defined as (G1).
• the sample length was maintained for 30 seconds at 300% elongation.
• the stress after being maintained for 30 seconds was defined as (G2).
• the sample elongation was recovered, the stress at 200% elongation recovery was defined as (G-200), and the length of the sample when the stress became 0 was defined as (L2).
• This operation of 300% elongation, maintenance, and recovery was repeated, and in a 6th elongation, the sample was elongated until it broke.
• the stress at the time of rupture was defined as (G3), and the sample length at the time of rupture was defined as (L3).
• Rupture strength (cN) (G3) 20 or more: ⁇ , 17 or more and less than 20: ⁇ , 14 or more and less than 17: ⁇ , less than 14: ⁇
• a two-way half tricot having a machine well number of 9/inch and a machine course number of 18/inch composed of 85% by weight of nylon filament (24 dtex, 7 filaments) and 15% by weight of polyurethane elastic fiber (44 dtex) was produced by a conventional knitting method to obtain a raw knitted fabric.
• the obtained raw knitted fabric was preset under conditions of 3% elongation for 60 seconds at 170°C, and 0.1 mL of Agent 1 was applied, followed by an application of 0.1 mL of Agent 2 (at approximately the same time and within 1 minute).
• the fabric was submitted to dry heat treatment (after dry heat treatment for 60 seconds at 175°C, the fabric was extracted once, and after radiating to room temperature, dry heat treatment was then performed for 60 seconds at 180°C). Then, the fabric was subjected to a bending tester with a maximum elongation of 20% alternately in both the vertical and horizontal directions, twice/second.
• a mineral oil-based spinning oil for nylon containing 1% oleic acid was used as Agent 1.
• an aqueous solution of copper acetate (copper concentration of 100 ppm) was used as Agent 2.
• the raw knitted fabric coated with Agent 1 and Agent 2 in this manner was a model reproduction of a slight amount of a mechanical oil (containing a metal) and a spinning oil for nylon during knitting coating a nylon- based stretch raw knitted fabric at a stage before dyeing.
• the amount of Agent 1 coating 0.9 g of the raw knitted fabric was 3.0 mg and the amount of Agent 2 coating 0.9 g of the raw knitted fabric was 3.0 mg.
• the obtained stretch fabric was dyed using a conventional method.
• the degree of damage to the polyurethane tissue in the obtained dyed stretch fabric was observed visually with the naked eye or under magnification, and a determination was made using the following criteria. Note that the determination was performed by five people and that the mode (the determination appearing most frequently) was used.
• UV exposure treatment UV exposure treatment
• B Nitrogen oxide (NOx) exposure treatment
• the sample was subjected to exposure treatment with 10 ppm NO2 gas for 20 hours at a temperature of 40°C and a relative humidity of 60% using a sealed container (Scott tester) with a rotating sample stand.
• This test piece was set in the chuck of an Instron model tensile testing machine (Autograph manufactured by Shimadzu Corporation), and after elongating until the distance between the gauge lines reached 300% at a constant speed of 500 mm/minute under an atmosphere of 25°C, an operation was performed immediately to return to the test piece to the distance between the chuck before elongation at the same speed.
• Residual strain rate (%) ⁇ (D1-D0)/D0 ⁇ 100
• Method for measuring thermal softening point A test piece of 10 mm in length x 10 mm in width was cut out from the film obtained above, the sample was heated from room temperature to 300°C at a speed of 5°C/minute in accordance with JIS K 7196, and the thermal softening point was measured. A TMA/SS6100 (manufactured by SII) was used for the measurement. The higher the thermal softening point, the better the heat resistance of the polyurethane resin. [Table 5]

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