EP4301913A1 - Fil élastique en polyuréthane et son procédé de production - Google Patents

Fil élastique en polyuréthane et son procédé de production

Info

Publication number
EP4301913A1
EP4301913A1 EP22713446.7A EP22713446A EP4301913A1 EP 4301913 A1 EP4301913 A1 EP 4301913A1 EP 22713446 A EP22713446 A EP 22713446A EP 4301913 A1 EP4301913 A1 EP 4301913A1
Authority
EP
European Patent Office
Prior art keywords
group
elastic fiber
polyurethane elastic
polyurethane
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22713446.7A
Other languages
German (de)
English (en)
Inventor
Toshihiro Tanaka
Katsuka SUZUKI
Tatsuaki Kanbayashi
Kazuki NAESHIRO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Opelontex Co Ltd
Original Assignee
Toray Opelontex Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2022017721A external-priority patent/JP2022133242A/ja
Application filed by Toray Opelontex Co Ltd filed Critical Toray Opelontex Co Ltd
Publication of EP4301913A1 publication Critical patent/EP4301913A1/fr
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms

Definitions

  • the present invention relates to a polyurethane elastic fiber with excellent antibacterial properties and excellent yellowing resistance, a polyurethane elastic fiber suitable for obtaining a fabric having antibacterial properties, and a production method therefor.
  • elastic fibers are used in a wide range of applications, including elastic clothing applications such as legwear, innerwear and sportswear, sanitary applications such as disposable diapers and sanitary napkins (as a protective material), and industrial applications.
  • antibacterial products In order to meet growing demand for a more comfortable living environment, so-called "antibacterial products” have become popular in recent years. These products include antibacterial paints, antibacterial films and sheets, antibacterial filaments, antibacterial toiletry products, antibacterial kitchen utensils, antibacterial writing instruments, antibacterial sand, antibacterial tissues, antibacterial fibers, and antibacterial cosmetics.
  • inorganic antibacterial agents are used as antibacterial agents in these products, especially silver antibacterial agents.
  • metal ions constituting inorganic antibacterial agents include silver, mercury, copper, zinc, and tin ions. Silver ions and copper ions are especially used. When these are supported on a material with a porous structure such as glass, zeolite, silica gel, silicate, whiskers, alumina, and ceramics, an excellent antibacterial effect can be realized. Many techniques have been proposed for use on these fibers (Patent Documents 1-3).
  • Patent Document 4 techniques for suppressing discoloration of antibacterial resins containing an added inorganic antibacterial agent have been proposed.
  • Patent Document 4 proposes techniques for suppressing discoloration of antibacterial resins containing an added inorganic antibacterial agent.
  • Patent Document 1 JP H05-339810 A
  • Patent Document 2 JP H06-093565 A
  • Patent Document 3 JP 2017-040007 A
  • Patent Document 4 JP 4485871 B2 [Summary of the Invention]
  • the present invention solves this problem using the following means.
  • a polyurethane elastic fiber whose main component is a polyurethane whose main starting materials are a polymer diol and a diisocyanate, wherein the polyurethane elastic fiber comprises (a) a slowly water-soluble glass containing a Group IB and/or Group 2B element and (b) a nonionic surfactant.
  • a method for producing a polyurethane elastic fiber comprising: mixing (a) a slowly water-soluble glass containing a Group IB and/or Group 2B element with a spinning solution; mixing in a nonionic surfactant in an amount within a range of 0.01% by mass or more and 20% by mass or less relative to the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element; and dry spinning the spinning solution.
  • the present invention is able to obtain a polyurethane elastic fiber with excellent antibacterial properties, discoloration resistance, and elasticity whose main component is a polyurethane whose main starting materials are a polymer diol and a diisocyanate, in which the polyurethane elastic fiber comprises (a) a slowly water-soluble glass containing a Group IB and/or Group 2B element and a nonionic surfactant.
  • a fabric using this polyurethane elastic fiber has excellent antibacterial properties, discoloration resistance, and elasticity.
  • main component means a component constituting more than 50% by mass of the polyurethane elastic fiber.
  • the polyurethane used in the present invention may be any polyurethane as long as it has a structure whose main starting materials are a polymer diol and a diisocyanate.
  • a polymer diol and a diisocyanate as starting materials means the resulting polyurethane polymer has a structure derived from these components.
  • the structure of a polyurethane polymer obtained by using a polymer diol and a diisocyanate as starting materials is specified.
  • An equivalent structure may be formed from different raw materials, and the raw materials themselves are not specified. There are also no particular restrictions on the synthesis method that is used.
  • it may be a polyurethane urea composed of a polymer diol, a diisocyanate, and a low molecular weight diamine serving as a chain extender, or may be a polyurethane urethane composed of a polymer diol, a diisocyanate, and a low molecular weight diol serving as a chain extender. It may also be a polyurethane urea using a compound with a hydroxyl group and an amino group in the molecule as a chain extender. Polyfunctional glycols and isocyanates having trifunctionality or higher may also be used as long as the effects of the present invention are not impaired.
  • a polyurethane whose main starting materials are a polymer diol and a diisocyanate means more than 50% by mass of the isocyanate compounds among the starting materials is a diisocyanate and more that 50% by mass of the components reacting with the isocyanate compounds among the starting materials (polymer diols, low molecular weight diamines, low molecular weight diols, compounds with hydroxyl groups and amino groups in their molecules, polyfunctional glycols, etc.) is a polymer diol.
  • the mass ratios the use of these components as starting materials is assumed regardless of the actual raw materials that are used.
  • a low molecular weight diol means a compound having a molecular weight of less than 500, and diol compounds having a molecular weight of 500 or more are called polymer diols (the same applies to diamine compounds).
  • the polymer diol is preferably a polyether-based diol, a polyester-based diol, or a polycarbonate diol.
  • a polyether diol is preferably used from the standpoint of imparting flexibility and elasticity to the fabric.
  • Preferred examples of polyether diols include polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (PTMG), modified PTMG that is a copolymer of tetrahydrofuran (THF) and 3- methyltetrahydrofuran, modified PTMG that is a copolymer of tetrahydrofuran (THF) and 2- dimethyl tetrahydrofuran, modified PTMG that is a copolymer of THF and 2,3-dimethyl THF, the polyol with side chains on both sides that is disclosed in JP 2615131 B2, and a random copolymer in which THF and ethylene oxide and/or
  • preferred examples include butylene adipate, polycaprolactone diol, polyester diols such as the polyester polyol with a side chain disclosed in JP S61-026612 A, and the polycarbonate diol disclosed in JP H02-289516 A.
  • polymer diols may be used alone, or two or more may be mixed together or copolymerized and then used.
  • the molecular weight of the polymer diol used in the present invention is preferably 1,000 or more and 8,000 or less, and more preferably 1,500 or more and 6,000 or less.
  • a polyol with a molecular weight in this range is used, elastic fibers having excellent elasticity, strength, elastic resilience, and heat resistance can be easily obtained.
  • aromatic diisocyanates used in the present invention are especially suitable for synthesizing polyurethanes with high heat resistance and strength.
  • examples include diphenylmethane diisocyanate (MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate.
  • alicyclic diisocyanates include methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4- diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, and octahydro-l,5-naphthalenediisocyanate.
  • Aliphatic diisocyanates are especially effective for suppressing the yellowing of polyurethane elastic fibers. These diisocyanates may be used alone or in combinations of two or more.
  • the chain extender used in the present invention is preferably at least one of a low molecular weight diamine and a low molecular weight diol.
  • the molecule may also have a hydroxyl group and an amino group such as ethanolamine.
  • low molecular weight diamines include ethylenediamine, 1,2- propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p- xylenediamine, m-xylylenediamine, p,p'-methylenedianiline, 1,3- cyclohexyldiamine, hexahydromethphenylenediamine, 2-methylpentamethylenediamine, and bis (4- aminophenyl) phosphine oxide. These may be used alone or in combinations of two or more. Ethylenediamine is especially preferred.
  • Ethylenediamine can be used to easily obtain a fiber having excellent elasticity, elasticity recovery, and heat resistance.
  • a triamine compound that can form a crosslinked structure, such as diethylenetriamine, may be added to these chain extenders as long as the effects of the present invention are not lost.
  • low molecular weight diols include ethylene glycol, 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, and l-methyl-1,2- ethanediol. These may be used alone or in combinations of two or more. Use of 1,3 propanediol and 1,4 butanediol is especially preferred. When these are used, the diol- extended polyurethane has higher heat resistance and a stronger fiber can be obtained.
  • the number average molecular weight of a polyurethane urea polymer used in the present invention is preferably in the range of 30,000 or more and 150,000 or less.
  • the molecular weight is measured by GPC and converted in terms of polystyrene.
  • end blockers is preferably mixed into a polyurethane elastic fiber of the present invention.
  • Preferred examples of end blockers 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
  • a polyurethane elastic fiber composed of a polyurethane with the basic configuration described above can maintain excellent antibacterial properties by including (a) a slowly water-soluble glass containing a Group IB element and/or a Group 2B element as well as a nonionic surfactant.
  • the slowly water-soluble glass is a silicate glass that is generally water-insoluble, that is, a glass produced by blending a total of 30% by mass or more P2O5 and/or B2O3 with S1O2, which is the main raw material, that slowly dissolves in water.
  • the slowly water-soluble glass used in the present invention only needs to be able to retain (a) a Group IB element and/or Group 2B element.
  • a general slowly water-soluble glass that uses S1O2 as the main raw material it may be composed of P2O5 and/or B2O3, which can be vitrified themselves, as the main raw material, and not contain any S1O2 at all.
  • the Group IB element and/or Group 2B element in the (a) slowly water-soluble glass is preferably added in raw material form as an oxide.
  • oxides of (a) Group IB element and/or Group 2B element include AgO, Ag20, Ag2C>3, CuO, CU2O, ZnO, and AU2O3.
  • the oxidation number of the (a) Group IB element and/or Group 2B element is preferably as low as possible while providing a stable material, and the oxide is more preferably Ag ⁇ 0 or CuO.
  • the oxide of the (a) Group IB element and/or the Group 2B element is blended into a phosphoric acid-based and/or boric acid-based slowly water-soluble glass powder in a total amount of 1% by mass or more on a raw material basis.
  • trace amounts of SrO, BaO, T1O2, ZrC>2, Nb20s, CS2O, Rb20, TeC>2, BeO, GeC>2, B12O3, La2C>3, Y2O3, WO3, M0O3, or Fe2C>3 can be included in the glass solid solution during production of the slowly water-soluble glass.
  • F, Cl, SO3, Sb2C>3, SnC>2, or Ce may be added as a clarifying agent.
  • the amount of (a) slowly water-soluble glass containing a Group IB and/or Group 2B element is preferably in the range of from 0.1% by mass or more and 30% by mass or less relative to the total mass of the polyurethane elastic fiber.
  • the amount of (a) slowly water-soluble glass containing a Group IB and/or Group 2B element is less than 0.1% by mass, it is sometimes difficult to obtain sufficient antibacterial properties when used as a fabric. More preferably, the amount is 0.5% by mass or more. When the amount exceeds 30% by mass, it may cause a deterioration in elastic properties and be unfavorable in terms of cost.
  • the amount is preferably 10% by mass or less, and more preferably 5.0% by mass or less. From the standpoint of antibacterial properties and the balance between physical properties and cost, the range is more preferably 1.0% by mass or more and 5.0% by mass or less.
  • the equivalent of the projected area circle for primary particles is generated by image processing in an interval between two parallel lines in a certain direction that interpose the primary particles in a field magnified by a factor of tens of thousands. Twenty of the diameters are randomly measured, the upper 5% (maximum values) and lower 5% (minimum values) are removed based on a number standard, and the average value of the remaining 90% (values for 18 particles) is calculated.
  • the particle size distribution is preferably obtained by dividing the average primary particle size by the most frequent particle size (mode diameter) from 0.5 to 1.5, and more preferably 0.8 to 1.2.
  • the maximum particle size is distributed within 2.0 times the average primary particle size, and more preferably 1.5 times or less.
  • the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element is preferably distributed uniformly in the polyurethane.
  • Various known surfactants can be used as dispersants to disperse the glass.
  • a nonionic surfactant should be used to uniformly disperse the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element in the polyurethane and obtain polyurethane elastic fibers with excellent spinnability, antibacterial properties, discoloration resistance, and elasticity.
  • use of a nonionic surfactant has a synergistic effect, especially on antibacterial properties.
  • ionic surfactants such as anionic surfactants, cationic surfactants, and anionic-cationic amphoteric surfactants often do not exhibit antibacterial properties after undergoing the required water-based treatment steps for fabrics, such as dyeing.
  • nonionic surfactants examples include polyoxyethylene alkyl ethers, alkyl monoglyceryl ethers, polyoxyethylene alkyl amines, fatty acid sorbitan esters, and fatty acid diethanolamides.
  • the so-called hydrophilic portion (hydrophil) of the surfactant is preferably an ether, and is preferably at least one of an ethylene oxide polymer, a propylene oxide polymer, and an ethylene oxide/propylene oxide copolymer.
  • hydrophobic portion (hydrophob) of the surfactant can be one of the terminally modified structures mentioned above.
  • alkyl groups, phenyl groups, and styrenated phenyl groups are preferred.
  • nonionic surfactants include polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene ethylphenol ether, polyoxyethylene propyl phenol ether, polyoxyethylene styrylated phenyl ether, and polyoxyethylene sorbitol tetraoleate.
  • polyoxyethylene styrenated phenyl ethers such as polyoxyethylene oxypropylene tris styrenated phenyl ether, polyoxyethylene oxypropylene distyrene phenyl ether, polyoxyethylene oxypropylene monostyrene phenyl ether, polyoxyethylene oxypropylene-2,4,6-tris (a,a-dimethylbenzyl) phenyl ether, polyoxyethylene oxypropylene-2,4-bis (a,a-dimethylbenzyl) phenyl ether, polyoxyethylene oxypropylene-2-mono (a,a-dimethylbenzyl) phenyl ether, and polyoxyethylene oxypropylene-4-mono (a,a-dimethylbenzyl) phenyl ether.
  • Most preferred is use of a mixture in which the number of added moles of these styrene groups has a distribution.
  • a quaternary ammonium salt-based antibacterial agent is preferably also used. It is important to keep skin sensitivity at the proper antibacterial level, especially in textile structures for clothing, medical fabrics, and protective materials. Even though the slowly water-soluble glass containing a Group IB and/or Group 2B element is a completely inorganic substance, the organic quaternary ammonium salt-based antibacterial agent is easily distributed on the surface layer of polyurethane elastic fiber. Because elution of quaternary ammonium proceeds more rapidly, it is easy to control the initial antibacterial performance of the quaternary ammonium salt-based antibacterial agent immediately after production or immediately after fabric processing such as dyeing.
  • the required level for antibacterial properties can be maintained even after repeated washing and long-term aging by adjusting, for example, the amount added and the particle size.
  • the antibacterial properties can be designed to remain at the optimum level of the initial state after long-term aging.
  • the antibacterial activity differs depending on the chain length of the alkyl group in the ammonium ion, and the antibacterial activity is preferably strong.
  • a chain type such as an alkyl group, and an alkyl group having a long chain length, that is, an alkyl group having a large number of carbon atoms, is preferably selected.
  • ammonium ions that are especially preferred are didecyldimethyl ammonium ions and oleyltrimethyl ammonium ions.
  • the counter anions that constitute the quaternary ammonium salt should also be taken into consideration.
  • inorganic salts such as chlorides, bromides and iodides
  • organic acid salts such as carboxylates, sulfonates and phosphates. From the standpoint of stability with respect to discoloration and heat resistance and improvement of breaking strength and elongation, carboxylates and sulfonates are preferred, and carboxylates are most preferred.
  • salts with this structure include didecyldimethylammonium carboxylates such as didecyldimethylammonium adipate, didecyldimethylammonium gluconate and didecyldimethylammonium propionate, oleyltrimethylammonium carboxylates such as oleyl trimethylammonium adipate and oleyltrimethylammonium gluconate, and sulfonates such as didecyldimethylammonium trifluoromethylsulfonate, di-n- decyldimethylammonium trifluoromethanesulfonate, di-n-decyldimethylammonium pentafluoroethane sulfonate, n-hexadecyltrimethylammonium trifluoromethanesulfonate, and benzyldimethyl coconut oil alkylammonium pentafluoroethane
  • the amount of quaternary ammonium salt-based antibacterial agent is preferably in a range of from 0.1% by mass or more and 5% by mass or less relative to the total mass of the polyurethane elastic fiber.
  • a polyurethane elastic fiber of the present invention may contain various additives such as stabilizers and pigments.
  • Preferred examples of light stabilizers and antioxidants include hindered phenolic agents such as BHT and Sumilyzer (registered trademark) GA-80 from Sumitomo Chemical Co., Ltd., benzotriazole-based and benzophenone-based agents such as Tinuvin (registered trademark) from Ciba Geigy Co., Ltd., phosphorus-based agents such as Sumilyzer (registered trademark) P-16 from Sumitomo Chemical Co., Ltd., hindered amine agents, pigments such as iron oxide and titanium oxide, minerals such as hydrotalcite compounds, huntite, hydromagnesite, and tourmaline, inorganic materials such as zinc oxide, cerium oxide, magnesium oxide, calcium carbonate, and carbon black, fluorine-based or silicone-based resin powders, metal soaps such as magnesium stearate, disinfectants and deodorizers containing silver, zinc, or compounds of these, lubricants such as silicones and mineral oils, and antistatic agents such as cerium oxide, betaine, and phospho
  • a nitrogen oxide supplement such as HN-150 from Nippon Hydrazine Co., Ltd., a thermal oxidation stabilizer such Sumilyzer (registered trademark) GA-80 from Sumitomo Chemical Co., Ltd., or a light stabilizer such as Sumisorb (registered trademark) 300 #622 from Sumitomo Chemical Co., Ltd. is preferably used.
  • a polymer diol and a diisocyanate are used as the main starting materials, and the polyurethane spinning solution obtained from these that is dry-spun contains (a) a slowly water-soluble glass including a Group IB element and/or Group 2B element and a nonionic surfactant.
  • the (a) slowly water-soluble glass containing a Group IB element and/or a Group 2B element is mixed with the nonionic surfactant.
  • the nonionic surfactant is admixed in a range of 0.01 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the (a) slowly water-soluble glass including a Group IB element and/or Group 2B element.
  • the nonionic surfactant is kneaded beforehand into a fine powder obtained in the step in which the (a) slowly water-soluble glass including a Group IB element and/or Group 2B element is pulverized to coat the fine powder with the nonionic surfactant.
  • a polyurethane solution or polyurethane as the solute in a solution may be prepared using melt polymerization, solution polymerization, or some other method.
  • the solution polymerization method is especially preferred. In the solution polymerization method, not many foreign substances such as gels are produced in the polyurethane, the spinning solution is easy to spin, and a polyurethane elastic fiber with a low degree of fineness is easy to obtain.
  • the solution polymerization method is also advantageous in that a step of making a solution can be omitted.
  • a polyurethane that is especially suitable for the present invention is synthesized using PTMG with a number average molecular weight of 1,500 or more and 6,000 or less as the polymer diol, MDI as the diisocyanate, and at least one type among ethylenediamine, 1,2- propanediamine, 1,3-propanediamine, and hexamethylenediamine as the chain extender.
  • Polyurethane can be obtained by synthesizing the raw materials described above in, for example, dimethylacetamide (DMAc), dimethyl sulfoxide (DMF), dimethyl sulfoxide (DMSO), n-methylpyrrolidinone (NMP), or a solvent whose main components are these.
  • Preferred methods include the so-called one-shot method, in which the raw materials are added to a solvent, dissolved, heated to an appropriate temperature, and reacted to form a polyurethane, and a method in which a polymer diol and diisocyanate are melt-reacted, and the reaction product is dissolved in a solvent and reacted with the chain extender to obtain a polyurethane.
  • adjusting the polyurethane melting point on the high side to a range of 200°C or higher and 260°C or lower is preferred from the standpoint of obtaining excellent heat resistance. This is typically achieved by controlling the types and ratios of polymer diols, MDIs, and diols used.
  • a polyurethane with a high melting point can be obtained by increasing the relative ratio of MDI.
  • a polyurethane with a high melting point can be obtained by reducing the relative ratio of the polymer diol.
  • the polymerization is preferably conducted at a ratio of (moles of MDI)/(moles of polymer diol) > 1.5 in order to raise the melting point on the high side to 200°C or more.
  • one type or a mixture of two or more types of catalysts such as amine catalysts and organometallic catalysts is preferably used.
  • amine catalysts include N,N-dimethylcyclohexylamine, N,N- dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'- tetramethylethylenediamine, N, N, N', N'-tetra methyl- 1,3-propanedia mine, N,N,N',N'- tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N,N,N',N',N'- pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N,N'- dimethylpiperazine, N-methyl-N'-dimethylaminoethyl-piperazine, N-(2-dimethyla mi noethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N,N-dimethylamin
  • organometallic catalysts examples include tin octanoate, dibutyl tin dilaurate, and lead dibutyl octanoate.
  • the concentration of polyurethane urea polymers in the resulting polyurethane polymer solution is preferably in the range of 30% by mass or more and 80% by mass or less.
  • the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element and the nonionic surfactant are added to this polyurethane solution.
  • Any method can be used to add the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element and the nonionic surfactant to the polyurethane solution. Examples include using a static mixer, stirring, using a homomixer, and using a biaxial extruder.
  • the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element is added to the polyurethane elastic fiber in the range of 0.5% by mass or more and 10% by mass or less. Therefore, the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element has to be uniformly dispersed in the polyurethane spinning solution prior to spinning in the range of 0.5% by mass or more and 10% by mass or less.
  • the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element and the nonionic surfactant are added to a polyurethane spinning solution using, for example, N,N- dimethylformamide or N,N-dimethylacetamide, etc. as a solvent, and are then mixed while stirring to uniformly disperse the components.
  • the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element and the nonionic surfactant are dispersed beforehand in the N,N-dimethylformamide or N,N-dimethylacetamide solvent, to obtain a dispersion solution of the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element, and this dispersion solution is mixed into the polyurethane spinning solution.
  • the solvent added to the dispersion solution of the (a) slowly water- soluble glass containing a Group IB and/or Group 2B element is preferably the same solvent used in the polyurethane solution from the standpoint of uniformly adding the dispersion solution to the polyurethane solution.
  • Pigments and chemical agents such as light-resistant agents and antioxidants may be added at the same time the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element is added to the polyurethane solution.
  • the dispersion solution is prepared beforehand by mixing together the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element and the nonionic surfactant and then added to the polyurethane spinning solution.
  • the present invention also preferably contains a quaternary ammonium salt-based antibacterial agent in order to enhance antibacterial properties against various bacteria.
  • the quaternary ammonium salt-based antibacterial agent is added to the polyurethane spinning solution before spinning is performed.
  • the quaternary ammonium salt-based antibacterial agent may be simply mixed into the polyurethane spinning solution or may be mixed into the dispersion solution of the (a) slowly water-soluble glass containing a Group IB and/or Group 2B element and the nonionic surfactant beforehand.
  • the mixing order is mixing the slowly water-soluble glass containing a Group IB and/or Group 2B element and the nonionic surfactant together to create a dispersion solution, mixing the quaternary ammonium salt-based antibacterial agent into the dispersion solution, and then mixing the dispersion solution into the polyurethane spinning solution.
  • the quaternary ammonium salt-based antibacterial agent is included in the spinning solution by simply mixing the quaternary ammonium salt-based antibacterial agent with the spinning solution independent of the dispersion solution obtained beforehand by mixing theslowly water-soluble glass containing a Group IB and/or Group 2B element with the nonionic surfactant.
  • a polyurethane fiber of the present invention can be obtained using, for example, dry spinning, wet spinning, or melt spinning an undiluted spinning solution described above, and then winding the fiber. Dry spinning is especially preferred from the standpoint of stable spinning at all finenesses from thin to thick.
  • the cross-sectional profile of a polyurethane elastic fiber of the present invention may be circular or flat.
  • the spinning conditions are preferably determined based on the intended use for the fiber. From the standpoint of obtaining a polyurethane elastic fiber with the desired permanent strain rate and stress relaxation, take up is preferably conducted at a speed ratio between the godet roller and the winder in the range of 1.10 or more and 1.65 or less.
  • the spinning speed is preferably 250 m/min or more.
  • FE-SEM electrolytic radiation scanning electron microscope
  • the frequency of fiber breakage relative to the solid content of the spinning solution was measured in terms of the number of fiber breakages/t.
  • a 22-dtex polyurethane elastic fiber was stretched by a factor of three, and this was covered at a twist number of 800 T/m with a polyamide-processed fiber (Quup 33 decitex/26 filament from Toray Industries) serving as a sheath fiber to produce S-twisted and Z-twisted single covering yarns (SCY).
  • a polyamide-processed fiber Quup 33 decitex/26 filament from Toray Industries
  • the S-twisted SCY was supplied to yarn feeders 1 and 3 and the Z-twisted SCY was supplied to yarn feeders 2 and 4 of a pantyhose knitting machine (from Lonati, 400 stitches) at a knitting tension of 1.0 g to produce a knitted fabric.
  • the polyurethane elastic fiber content of the knitted fabric was 16%.
  • washing Method 103 40 ml of the JAFET standard detergent (from the Japan Textile Evaluation Technology Council) was dissolved in 30 liters of water at 40°C to produce a liquid washing detergent, and a 1 kg laundry sample was added to this liquid washing detergent.
  • the laundry sample was washed using a process in which a single cycle consisted of washing for five minutes, dewatering, rinsing for two minutes, dewatering, rinsing for two minutes, and dewatering.
  • An antibacterial test was carried out in accordance with the antibacterial test procedure (JIS L1902: 2015, bacterial solution absorption method) specified by the Japan Textile Evaluation Technology Council.
  • the antibacterial activity value was calculated and the antibacterial activity evaluated using X as the viable cell count in an untreated test sample after culturing for 18 hours and Y as the viable cell count in a treated test sample after culturing for 18 hours.
  • the tensile testing was performed three times and the average values were used.
  • PTMG having a molecular weight of 1,800 and MDI were reacted at a molar ratio of 1: 1.58 at 90°C for two hours to obtain an isocyanate-terminated prepolymer, and 35% by mass of the isocyanate-terminated prepolymer was dissolved in DMAc to obtain a prepolymer solution.
  • Ethylenediamine and 1,2-propanediamine serving as chain extenders and diethylamine serving as a chain terminator were mixed together at a mass ratio of 5: 1: 1, and 35% by mass of the mixture was dissolved in DMAc to obtain an amine solution.
  • the prepolymer solution and the amine solution were mixed together while stirring at an isocyanate terminal group to amine terminal group molar ratio of 1: 1.02 to prepare a DMAC solution (35% by mass) of a polyurethane urea polymer.
  • a t-butyldiethanolamine antioxidant with methylene-bis-(4-cyclohexyl isocyanate) (DuPont Metachlor (registered trademark) 2462) was mixed with a condensation polymer of p-cresol and divinylbenzene (DuPont Metachlor (registered trademark) 2390) at a ratio (mass ratio) of 2:1 to prepare an antioxidant DMAc solution (concentration 35% by mass).
  • polymer solution Al 96 parts by mass of the polyurethane urea polymer DMAc solution and 4 parts by mass of the antioxidant solution were mixed together to obtain polymer solution Al.
  • slowly water-soluble silver glass 1 serving as the slowly water-soluble glass containing a Group IB and/or Group 2B element, and a polyoxyethylene alkyl ether (Ionet MO from Sanyo Chemical Industries) serving as the nonionic surfactant were dispersed in DMAc to obtain dispersion solution B1 (35% by mass).
  • polymer solutions Al and B1 were uniformly mixed together at 97% by mass and 2% by mass to prepare spinning solution Dl.
  • a polyurethane elastic fiber was obtained from a composition composed of an antibacterial component and a surfactant component shown in Table 1 using the same method as that of Example 1. The spinnability, NOx yellowing resistance, and elasticity characteristics of the resulting polyurethane fiber were measured. A knitted fabric was created for evaluation purposes, and the antibacterial properties of the knitted fabric were measured. The results of these evaluations are shown in Table 1 and Table 2.
  • a polyurethane elastic fiber was obtained from a composition composed of an antibacterial component, a surfactant component, and a quaternary ammonium salt-based antibacterial agent shown in Table 1 using the same method as that of Example 1. After mixing polymer solution A1 with a dispersion solution containing slowly water-soluble silver glass 1 and the nonionic surfactant, the quaternary ammonium salt-based antibacterial agent was added and dissolved to obtain a spinning solution. The spinnability, NOx yellowing resistance, and elasticity characteristics of the resulting polyurethane fiber were measured. A knitted fabric was created for evaluation purposes, and the antibacterial properties of the knitted fabric were measured. The results of these evaluations are shown in Table 1 and Table 2.
  • Polymer solution A1 was dry-spun in the same manner as in Example 1 to obtain 200 g of wound 22 decitex, double-filament polyurethane yarn. The spinnability, NOx yellowing resistance, and elasticity characteristics of the resulting polyurethane fiber were measured. A knitted fabric was created for evaluation purposes, and the antibacterial properties of the knitted fabric were measured. The results of these evaluations are shown in Table 1 and Table 2.
  • a polyurethane elastic fiber was obtained from a composition composed of an antibacterial component and a surfactant component shown in Table 1 using the same method as that of Example 1. The spinnability, NOx yellowing resistance, and elasticity characteristics of the resulting polyurethane fiber were measured. A knitted fabric was created for evaluation purposes, and the antibacterial properties of the knitted fabric were measured. The results of these evaluations are shown in Table 1 and Table 2.

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

Abstract

L'invention concerne une fibre élastique en polyuréthane ayant d'excellentes propriétés antibactériennes et son procédé de production. L'invention concerne une fibre élastique composée d'un polyuréthane dont les composants principaux sont un diol polymère et un diisocyanate, la fibre élastique en polyuréthane comprenant un verre lentement soluble dans l'eau contenant un élément du groupe 1B et/ou du groupe 2B et un tensioactif non ionique.
EP22713446.7A 2021-03-01 2022-02-25 Fil élastique en polyuréthane et son procédé de production Pending EP4301913A1 (fr)

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JP2022017721A JP2022133242A (ja) 2021-03-01 2022-02-08 ポリウレタン弾性糸およびその製造方法
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JPS6126612A (ja) 1984-07-17 1986-02-05 Kuraray Co Ltd 耐加水分解性の良好なポリウレタンの製法
JP2615131B2 (ja) 1988-05-11 1997-05-28 旭化成工業株式会社 セグメント化ポリウレタンおよびその製造方法
JPH02289516A (ja) 1989-02-28 1990-11-29 Asahi Chem Ind Co Ltd （＋）―プラノプロフェンを含有する医薬組成物
JPH05339810A (ja) 1991-11-07 1993-12-21 Ishizuka Glass Co Ltd 消臭機能を有する繊維
JPH0693565A (ja) 1992-01-09 1994-04-05 Ishizuka Glass Co Ltd 消臭機能を有する繊維
JP2001247333A (ja) * 1999-12-28 2001-09-11 Ishizuka Glass Co Ltd 抗菌性付与用ガラス組成物、抗菌性繊維、抗菌性撚糸及び抗菌性布状物
JP4485871B2 (ja) 2004-07-21 2010-06-23 日清紡ホールディングス株式会社 ポリウレタン弾性体及び弾性繊維
US7772296B2 (en) * 2007-06-08 2010-08-10 Advansource Biomaterials Corporation Antimicrobial polyurethane resins and products made therefrom
WO2016047568A1 (fr) * 2014-09-22 2016-03-31 富士フイルム株式会社 Feuille antibactérienne, revêtement antibactérien, corps stratifié et fluide antibactérien
JP6514604B2 (ja) 2015-08-17 2019-05-15 石塚硝子株式会社 消臭性繊維及び消臭布
KR101913417B1 (ko) * 2017-01-05 2019-01-15 효성티앤씨 주식회사 소취 스판덱스 및 이의 제조방법

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