CN103298985A - Elastic polyurethane thread and manufacturing method thereof - Google Patents

Elastic polyurethane thread and manufacturing method thereof Download PDF

Info

Publication number
CN103298985A
CN103298985A CN2011800610064A CN201180061006A CN103298985A CN 103298985 A CN103298985 A CN 103298985A CN 2011800610064 A CN2011800610064 A CN 2011800610064A CN 201180061006 A CN201180061006 A CN 201180061006A CN 103298985 A CN103298985 A CN 103298985A
Authority
CN
China
Prior art keywords
weight
silk
polyurethane
elastic polyurethane
solution
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.)
Granted
Application number
CN2011800610064A
Other languages
Chinese (zh)
Other versions
CN103298985B (en
Inventor
铃木克哉
上林达昭
田中利宏
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
Application filed by Toray Opelontex Co Ltd filed Critical Toray Opelontex Co Ltd
Publication of CN103298985A publication Critical patent/CN103298985A/en
Application granted granted Critical
Publication of CN103298985B publication Critical patent/CN103298985B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • 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
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Disclosed is an elastic polyurethane thread with excellent antibacterial and deodorant properties and color fastness. The disclosed the elastic thread comprises a polyurethane with polymer diols and diisocyanate as starting materials and contains metal phosphates in a range of 0.5-10 mass%, wherein the emission amount of monoamine compounds with a molecular mass of 120 or less is 100 [mu]g/m2 or greater.

Description

Elastic polyurethane silk and manufacture method thereof
Technical field
The present invention relates to the elastic polyurethane silk of antibiotic property and deodorization excellence and discoloration-resistant excellence, relate to the elastic polyurethane silk and the manufacture method thereof that are suitable for obtaining having the cloth and silk of antibiotic property and deodorization.
Background technology
Elastomer is owing to its excellent expansion performance is widely used in retractility dress material purposes such as socks, underwear, sportswear, sanitary use such as paper nappy and sanitary napkin (use in sanitary products), industry goods, materials and equipments purposes.
In recent years, in requiring the process of more comfortable living environment, so-called " antibiotic property commodity " such as antibiotic property coating, antibiotic property diaphragm, antibiotic property silk thread, antibacterial cosmetic product, antibiotic property kitchen articles, antibiotic property stationery, antibiotic sand, antibiotic dish, anti-bacterial fibre, antibiotic property cosmetics constantly occur on a large scale.In addition, similarly, possess " deodorization products " such as clothing at the deodorization functions of old age flavor etc., beddings and also constantly occur.
As the antiseptic that uses in these products, what see is inorganic series antibacterial agent, particularly silver-series antibacterial agent more.In addition, as deodorant, can exemplify active carbon, contain silver zeolite, zeolite, particulate oxide zinc etc.
Above-mentioned inorganic series antibacterial agent is compared with organic antibacterial agent, has weatherability, chemical-resistant excellence, excellent specific property that acute oral toxicity is low.In addition, to compare heat resistance obviously higher with the organic system antiseptic.Therefore, begin inorganic series antibacterial agent is added in the synthetic resin and in multiple field, use.Yet, carry out moulding in the synthetic resin if inorganic series antibacterial agent is added into, under the effect of the metal that then contains in inorganic antiseptic and under the heat during moulding and the influence to the light of article shaped irradiation, the variable color of moulding product is easy to generate the significantly reduced problem of value of the product.
So, the technology (patent documentation 1) of thermo-color that a lot of inhibition are added with the antibiotic property resin of inorganic series antibacterial agent has been proposed.Yet, by these technology, though confirm that aspect antibiotic, deodorization certain performance is arranged, about yellowing resistance, very big variable color is arranged under the influence of environment and effluxion, solved problem hardly fully.
In addition, as the organic system antiseptic, proposed to contain as the Hinokitiol of natural antibacterial agent and comprised the metal oxide that is selected from least a element among Zn, Si, Cu, Ni, Fe, Al and the Mg and/or the antibacterial and deodouring polyurethane elastomeric fiber (patent documentation 2) of composite metal oxide, confirmed to have certain performance aspect the antibiotic property of elastic polyurethane silk and the deodorization.But, because the antiseptic Hinokitiol can distil under the effect of the heat that affirmation is subjected in dry spinning, so need contain more in advance spinning solution.In addition, because the remaining quantity of Hinokitiol changes according to heat condition of spinning etc., so be difficult to produce the elastic polyurethane silk of guaranteeing to have stable antibiotic property.In addition, expensive as the Hinokitiol of natural antibacterial agent, therefore aspect cost, also have problems.
The purposes (patent documentation 3) of organic system synthetic antibacterial agents etc. has also been proposed.Yet the synthetic antibacterial agents of this organic system does not have effect aspect the deodorization when using separately, existing problems aspect the taking into account of antibiotic property and deodorization.
The prior art document
Patent documentation
Patent documentation 1: No. 4485871 communiques of Japan Patent
Patent documentation 2: TOHKEMY 2002-105757 communique
Patent documentation 3: TOHKEMY 2004-292471 communique.
Summary of the invention
Invent problem to be solved
The elastic polyurethane silk and the manufacture method thereof that the purpose of this invention is to provide antibiotic property and deodorization excellence and discoloration-resistant excellence.
Be used for solving the means of problem
The present invention who is used for addressing the above problem adopts following any technological means.
(1) elastic polyurethane silk, its be by with polymer diol and vulcabond as the elastic yarn that the polyurethane of initiation material constitutes, contain metal phosphate in this elastic yarn, and the emission of the monoamine compound of molecular weight below 120 is 100 μ g/m 2More than.
(2) above-mentioned (1) described elastic polyurethane silk, wherein, the content of described metal phosphate is 0.5～10wt%.
(3) the described elastic polyurethane silk in above-mentioned (1) or (2), wherein, the average primary particle diameter of described metal phosphate is below the 3.0 μ m.
(4) each described elastic polyurethane silk in above-mentioned (1)～(3), wherein, described metal phosphate is to be selected from least a in titanium phosphate, basic zirconium phosphate and the aluminium dihydrogen tripolyphosphate.
(5) each described elastic polyurethane silk in above-mentioned (1)～(4), wherein, the described monoamine compound that distributes is the monobasic secondary amine compound.
(6) each described elastic polyurethane silk in above-mentioned (1)～(5) wherein also contains the quaternary ammonium salt based compound.
(7) above-mentioned (6) described elastic polyurethane silk, wherein, described quaternary ammonium salt based compound has following structure:
[changing 1]
Figure 2011800610064100002DEST_PATH_IMAGE001
Wherein,
R1, R2 are the alkyl of hydrogen or carbon number 1～3, can be the same or different;
R3 is the alkyl of carbon number 10～22;
R4 is the alkyl of carbon number 1～22, can be with R1, R2, R3 is identical also can be different;
X-is acid equilibrium ion.
(8) the described elastic polyurethane silk in above-mentioned (6) or (7), wherein, the content of described quaternary ammonium salt based compound is the scope that 0.1 weight % is above and 5 weight % are following.
(9) manufacture method of elastic polyurethane silk, this method be comprise with polymer diol and vulcabond as the spinning solution of the polyurethane of initiation material in hybrid metal phosphate and the monoamine compound of combined molecular weight below 120 simultaneously, make that the content of this monoamine compound is more than the 0.01 weight % and the scope below the 0.5 weight % with respect to spinning solution, and with this spinning solution dry spinning.
(10) manufacture method of above-mentioned (9) described elastic polyurethane silk wherein, is blended in described metal phosphate and describedly comprises with polymer diol and vulcabond in the spinning solution as the polyurethane of initiation material with the form of dispersion liquid.
(11) manufacture method of above-mentioned (9) or (10) described elastic polyurethane silk, wherein, described metal phosphate is to be selected from least a in titanium phosphate, basic zirconium phosphate and the aluminium dihydrogen tripolyphosphate.
(12) manufacture method of each described elastic polyurethane silk in above-mentioned (9)～(11), wherein, the described monoamine compound of molecular weight below 120 is secondary amine compound.
The effect of invention
According to the present invention, can obtain the elastic polyurethane silk, it is to be the elastic yarn that the polyurethane of polymer diol and vulcabond constitutes by the main composition composition, and this elastic yarn contains metal phosphate, and the emission of the monoamine compound of molecular weight below 120 is 100 μ g/m 2More than, so retractility, deodorization, antibiotic property, discoloration-resistant excellence.Therefore, use retractility, deodorization, antibiotic property, the discoloration-resistant excellence of the cloth and silk of this elastic polyurethane silk.
Description of drawings
Fig. 1 is the schematic diagram of size that each position of packing is shown.
The specific embodiment
Below, the present invention is described in more detail.
At first, the polyurethane that uses among the present invention is described.
The polyurethane that uses among the present invention is so long as get final product with polymer diol and the vulcabond polyurethane as initiation material, can be polyurethane arbitrarily, is not particularly limited.In addition, its synthetic method also is not particularly limited.Namely, for example can be the polyurethane-urea that is made of polymer diol, vulcabond and low molecular weight diamines, perhaps also can be the polyurethane carbamate (polyurethane urethane) that is made of polymer diol, vulcabond and low molecular weight diols.In addition, also can be to use and have hydroxyl and amino compound in the molecule as the polyurethane-urea of cahin extension agent.In the scope that does not hinder effect of the present invention, also preferably use the dihydroxylic alcohols of the above polyfunctionality of 3 degrees of functionality or isocyanates etc.
Polymer diol preferred, polyethers system, polyester are glycol, PCDL etc.And particularly from silk being given the viewpoint of flexibility, percentage elongation, preferably using polyethers is glycol.
Be glycol as polyethers, for example preferably use poly(ethylene oxide), polyethylene glycol, polyethylene glycol derivative, polypropylene glycol, polytetramethylene ether diol (being designated hereinafter simply as PTMG), as the modification PTMG (being designated hereinafter simply as 3M-PTMG) of the copolymer of oxolane (THF) and 3-methyltetrahydrofuran, as disclosed both sides in the modification PTMG of the copolymer of THF and 2,3-dimethyl THF, No. 2615131 communique of Japan Patent etc. have side chain polyalcohol, arrange random copolymer that forms etc. brokenly by THF and oxirane and/or expoxy propane.These polyethers be glycol can one or more mix to use or copolymerization after use.
As the elastic polyurethane silk, from obtaining mar proof and sunproof viewpoint, preferably using in adipic acid Aden ester, polycaprolactone glycol, the Japanese kokai publication sho 61-26612 communique etc. polyester such as disclosed polyester polyol with side chain is disclosed PCDL etc. in glycol, the special fair 2-289516 communique of Japan etc.
This polymer diol both can use separately, also can two or more mixing uses or copolymerization after use.
As the molecular weight of polymer diol, the viewpoint of the percentage elongation when obtaining to make yarn, intensity, heat resistance etc., number-average molecular weight are preferably more than 1000 and below 8000, more preferably more than 1500 and below 6000.By using the polyalcohol of this scope molecular weight, can easily obtain the elastic yarn of percentage elongation, intensity, elastic-restoring force, excellent heat resistance.
Then, as vulcabond, '-diphenylmethane diisocyanate (being designated hereinafter simply as MDI), toluene di-isocyanate(TDI), 1,4-phenylene diisocyanate, XDI, 2, aromatic diisocyanates such as 6-naphthalene diisocyanate are particularly suitable for synthetic heat resistance and the high polyurethane of intensity.Also have, as alicyclic diisocyanate, for example preferred di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) (hereinafter referred to as H12MDI), isophorone diisocyanate, hexahydrotoluene 2,4-vulcabond, hexahydrotoluene 2,6-vulcabond, cyclohexane 1,4-vulcabond, hexahydrobenzene dimethylene diisocyanate, hexahydrotoluene vulcabond, octahydro 1,5-naphthalene diisocyanate etc.Aliphatic diisocyanate can use when suppressing the xanthochromia of elastic polyurethane silk especially effectively.In addition, these vulcabond both may be used alone, used in two or more.
Then, as the cahin extension agent that uses when the synthesis of polyurethane, preferably use at least a in low molecular weight diamines and the low molecular weight diols.Should illustrate, also can be to have hydroxyl and amino compound in the molecule of monoethanolamine and so on.
As preferred low molecular weight diamines, can exemplify for example ethylenediamine, 1,2-propane diamine, 1,3-propane diamine, hexamethylene diamine, p-phenylenediamine (PPD), p dimethylamine, m-xylene diamine, p, p '-methylene dianiline (MDA), 1,3-cyclohexanediamine, six hydrogen m-phenylene diamine (MPD)s, 2-methyl pentamethylene diamine, two (4-aminophenyl) phosphine oxide etc.Preferred wherein one or more of using.Preferred especially ethylenediamine.By using ethylenediamine, can easily obtain the silk of percentage elongation and elastic recovery and excellent heat resistance.Can add triamine compound, for example diethylenetriamines that can form cross-linked structure with the degree of not losing effect in these cahin extension agents.
In addition, as low molecular weight diols, representational is ethylene glycol, 1, ammediol, 1,4-butanediol, two hydroxyl-oxethyl benzene, two hydroxyl ethylene glycol terephthalate, 1-methyl isophthalic acid, 2-ethylene glycol etc.Preferred wherein one or more of using.Preferred especially ethylene glycol, 1, ammediol, 1,4-butanediol.If use these low molecular weight diols, then as the polyurethane of glycol extension, heat resistance further improves, and can obtain the higher silk of intensity.
Among the present invention, from obtaining the viewpoint of the high fiber of durability and intensity, the molecular weight of polyurethane is preferably more than 30000 and 150000 following scopes in number-average molecular weight.Should illustrate that molecular weight is measured by GPC, use polystyrene conversion.
Also preferably mix the end-capping reagent that uses one or more in the polyurethane.As end-capping reagent, monoamines such as preferred dimethylamine, diisopropylamine, ethyl dimethylamine, diethylamine, methyl propylamine, isopropyl methylamine, diisopropylamine, butyl methylamine, isobutyl group methylamine, isopentyl methylamine, dibutyl amine, diamylamine, monohydric alcohols such as ethanol, propyl alcohol, butanols, isopropyl alcohol, allyl alcohol, cyclopentanol, monobasic isocyanates such as phenyl isocyanate etc.Wherein, the monoamine compound emission of the molecular weight from elastic polyurethane silk under the fashionable condition of polyurethane polyureas below 120 reaches 100 μ g/m 2Viewpoint, as this end-capping reagent, preferably use the monoamine of molecular weight below 120.
Among the present invention, contain metal phosphate by making by having in the elastic polyurethane silk that the polyurethane of basic comprising constitutes as mentioned above, can under the situation to the deodorization of acetic acid gas, nonenyl aldehyde gas, isovaleric acid gas that does not influence that the elastic polyurethane silk originally just has, also improve deodorization for ammonia.In addition, contain the monoamine compound of molecular weight below 120 in the elastic polyurethane silk simultaneously by making, make that from the emission of elastic polyurethane silk be 100 μ g/m 2More than, be preferably 100 μ g/m 2More than and 500 μ g/m 2Below, can guarantee to have excellent antibiotic property.
From the viewpoint of deodorization, metal phosphate of the present invention is preferably the acid phosphate of 4 valency metals such as basic zirconium phosphate with layer structure and titanium phosphate and aluminium dihydrogen tripolyphosphate etc.More preferably basic zirconium phosphate.They both can use separately also and can two or morely mix.
The content of metal phosphate is preferably more than the 0.5 weight % and the scope below the 10 weight % with respect to the gross weight of elastic polyurethane silk.If the content of metal phosphate is lower than 0.5 weight %, be difficult to obtain the deodorization of enough ammonias when then making cloth and silk, therefore not preferred.More preferably more than the 1.0 weight %.On the other hand, if content is higher than 10 weight %, then not preferred aspect the deterioration of expansion performance and cost.More preferably below the 7.0 weight %.If consider the balance of the deodorization of ammonia and rerum natura aspect, cost aspect, then be preferably the scope that 1.5 weight % are above and 5.0 weight % are following especially.
From suppressing the viewpoint that spinning solution stops up spinning die, the preferred average primary particle diameter of metal phosphate is below the 3.0 μ m.More preferably below the 1.5 μ m.In addition, from the viewpoint of dispersiveness, under the situation of average primary particle diameter less than 0.05 μ m, the cohesiveness height is difficult in spinning solution equably, and therefore preferred average primary particle diameter is more than the 0.05 μ m.More preferably more than the 0.15 μ m.
On the other hand, reach 100 μ g/m for the emission that makes the monoamine compound of molecular weight below 120 that from the elastic polyurethane silk, distributes 2More than, for example preferably make the spinning solution that comprises polyurethane with more than the 0.01 weight % and the scope below the 0.5 weight % contain the monoamine compound and carry out spinning.When the content of this monoamine compound in the spinning solution is lower than 0.01 weight %, fully do not comprise monoamine in the elastic polyurethane silk that spinning forms, consequently, can't obtain enough antibiotic properties.On the other hand, contain the above monoamine compound of 0.5 weight %, the then quality variation such as xanthochromia of the elastic polyurethane silk of gained in the spinning solution if make.
In addition, even do not add monoamine after polymerization, and the end-capping reagent when being to use the monoamine of molecular weight below 120 as synthesis of polyurethane also can make the emission of this monoamine compound in the elastic polyurethane silk reach 100 μ g/m 2More than.Particularly, when making isocyanate group and amino reaction, preferably in advance with cahin extension agent and the uses of above-mentioned monoamine compound such as diamine compounds.Amino in the cahin extension agent of this moment and the ratio of the amino of this monoamine compound are preferably in the scope of 5:1～25:1.More preferably in the scope of 5:1～20:1.Use amount during as the reaction of the mixture of this cahin extension agent and above-mentioned monoamine compound, the mol ratio of the isocyanate group concentration during reaction and amino terminal radical concentration are preferably in the scope of 1:1.04～1:1.15.By this, compare in the time of can making with conventional polymerization and comprise the more polymer solution of polyamino, can guarantee that the emission of this monoamine in the silk after the spinning is also at 100 μ g/m 2More than.
As the monoamine mixture of molecular weight below 120, can exemplify secondary amine compounds such as diethylamine, dimethylamine, diisopropylamine, ethyl dimethylamine, N methyl pmpyl amine, isopropyl methylamine, N-butyl methylamine, N-methyl isobutyl amine, primary amines such as ethamine, N-propylamine, isopropylamine, N-butylamine, cyclohexylamine.From the viewpoint of the stability of polyurethane spinning solution, preferred secondary amine compound.
In order further to improve antibiotic property, also preferably contain the quaternary ammonium salt based compound in the above-mentioned elastic polyurethane silk.The quaternary ammonium salt based compound is according to the chain length of the alkyl in the ammonium ion and there are differences aspect the antibacterial efficacy, if the chain length of alkyl is long, then antibacterial efficacy becomes higher easily.In addition, if chain length is too short, then volatilization or rotten easily under the effect of the heat when spinning.On the other hand, if the chain length of alkyl is long, then operability is poor.Therefore, preferably select the chain kind, chain length of alkyl etc. to obtain desired characteristic.
From the viewpoint of antibacterial efficacy, particularly preferred ammonium ion is stearyl trimethyl ammonium ion, cetyl trimethyl ammonium ion, didecyldimethyl ammonium ion, oil base trimethyl ammonium ion etc.They have following structure usually, and this structure is supplied with the form of salt such as acylate such as sulfonate, phosphate or chloride, bromide, iodide.Wherein, from the preferred sulfonate of viewpoint of the stability of variable color and heat resistance etc.
[changing 2]
Figure 880612DEST_PATH_IMAGE002
Wherein,
R1, R2 are the alkyl of hydrogen or carbon number 1～3, can be the same or different;
R3 is the alkyl of carbon number 10～22;
R4 is the alkyl of carbon number 1～22, can be with R1, R2, R3 is identical also can be different;
X-is acid equilibrium ion.
As the object lesson of the salt with said structure, didecyl dimethyl three ammonium fluoride mesylates, two positive decyl Dimethyl Ammonium fluoroform sulphonates, two positive decyl Dimethyl Ammonium five fluorine esilates, n-hexadecyl trimethyl ammonium fluoroform sulphonate and benzyl dimethyl cocounut oil alkylammonium five fluorine esilates are arranged.
From embodying antibiotic property, keeping the viewpoint of the balance of variable color and expansion performance, the content of quaternary ammonium salt based compound is preferably more than the 0.1 weight % and the scope below the 5 weight % with respect to elastic polyurethane silk gross weight, more preferably the scope that 0.2 weight % is above and 2 weight % are following.
The elastic polyurethane silk can also contain various stabilizing agents and pigment etc.For example, also preferably at photostabilizer, the hindered phenols such as " Sumilizer " (registration mark) GA-80 that contain BHT and Sumitomo Chemical Company Ltd's system in the antioxidant etc. are reagent, various vapour Ba-Jia Ji company (チ バ ガ イ ギ ー society) system " Tinuvin " benzotriazole such as (registration marks) system, benzophenone is reagent, phosphorus such as " Sumilizer " (registration mark) P-16 of Sumitomo Chemical Company Ltd's system are reagent, various hindered amines are reagent, iron oxide, various pigment such as titanium oxide, zinc oxide, cerium oxide, magnesia, calcium carbonate, inorganic matters such as carbon black, fluorine system or siloxane-based resin powder, metallic soaps such as dolomol, perhaps siloxanes, mineral wet goods lubricant, cerium oxide, various antistatic agents such as betaine and phosphoric acid system etc., in addition, their also preferred and polymer reactions.In addition, particularly in order further to improve the durability to light and various nitrogen oxide etc., the also preferred nitrogen oxide agent for capturing such as HN-150 of Japanese Hydrazine Co., Ltd. system, the thermal oxidation stabilizers such as " Sumilizer " (registration mark) GA-80 of Sumitomo Chemical Company Ltd's system, the light stabilizers such as " Sumisorb " (registration mark) 300 622 of Sumitomo Chemical Company Ltd's system of using for example.
Then, the manufacture method to elastic polyurethane silk of the present invention is elaborated.
Among the present invention, use polymer diol and vulcabond as initiation material, make in the spinning solution of the polyurethane that is obtained by these initiation materials and contain (namely existing) metal phosphate and molecular weight monoamine compound below 120, carry out spinning.From making the viewpoint of polymerization-stableization, preferably make polyurethane solutions in advance, to wherein adding metal phosphate dispersion liquid and the molecular weight monoamine compound below 120.Should illustrate that " spinning solution " of the present invention refers to that finally by the liquid of spinning, on the other hand, polyurethane solutions refers to comprise the solution of polyurethane, also can be the liquid of free position.
The method for making of polyurethane solutions or can be in melt phase polycondensation or the solution polymerization process any as the method for making of the polyurethane of the solute of solution also can be other method.But, more preferably solution polymerization process.Under the situation of solution polymerization process, production of foreign matters such as the gel in the polyurethane are few, and spinning easily obtains to hang down the elastic polyurethane silk of fineness easily.In addition, under the situation of solution polymerization process, obviously have and to save this advantage of operation of making solution.
Polyurethane can use above-mentioned polymer diol, vulcabond, cahin extension agent, can also use above-mentioned end-capping reagent to carry out polymerization as required.As particularly preferred polyurethane, can exemplify and use molecular weight be 1500 or more and 6000 following PTMG as polymer diol, use MDI as vulcabond, use ethylenediamine, 1,2-propane diamine, 1, at least a polyurethane that synthesizes as cahin extension agent in 3-propane diamine, the hexamethylene diamine.
Polyurethane is for example by being to use above-mentioned raw materials to synthesize to obtain in the solvent of principal component at DMAc, DMF, DMSO, NMP etc. or with them.For example, as particularly preferred method, can adopt in above-mentioned solvent and to drop into each raw material and make its dissolving, be heated to that suitable temperature makes its reaction and the so-called one-step method of making polyurethane, perhaps at first make polymer diol and vulcabond frit reaction, then with reactants dissolved in solvent, itself and above-mentioned cahin extension agent reacted and make the method etc. of polyurethane.
Use under the situation of glycol as cahin extension agent, from the viewpoint of the product that obtains excellent heat resistance, preferably the fusing point of the high temperature side of polyurethane is adjusted to more than 200 ℃ in the scope below 260 ℃.As representational method, can realize by kind and the ratio of control polymer diol, MDI, glycol.Under the low situation of the molecular weight of polymer diol, by relatively increasing the ratio of MDI, can obtain the high polyurethane of fusing point of high temperature, similarly, when the molecular weight of glycol hangs down, by relatively reducing the ratio of polymer diol, can obtain the high polyurethane of fusing point of high temperature.
The molecular weight of polymer diol is under the situation more than 1800, the fusing point of high temperature side is reached more than 200 ℃, preferably carries out polymerization with the ratio of (molal quantity of MDI)/(molal quantity of polymer diol)=more than 1.5.
Should illustrate that during this polyurethane synthetic, also preferably one or more mix and use with catalyst such as amine series catalysts or organo-metallic catalysts.
As the amine series catalysts, can exemplify for example N, the N-dimethyl cyclohexyl amine, N, the N-dimethyl benzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N '-tetramethyl-1, the 3-propane diamine, N, N, N ', N '-4-methyl hexamethylene diamine, two-2-dimethylaminoethyl ether, N, N, N ', N ', N '-five methyl diethylentriamine, tetramethyl guanidine, triethylenediamine, N, N '-lupetazin, N-methyl-N '-dimethylaminoethyl piperazine, N-(2-dimethylaminoethyl) morpholine, the 1-methylimidazole, 1, the 2-methylimidazole, N, the N-dimethylaminoethanol, N, N, N '-trimethyl amino ethyl ethanolamine, N-methyl-N '-(2-hydroxyethyl) piperazine, 2,4,6-three (dimethylamino methyl) phenol, N, N-dimethylamino hexanol, triethanolamine etc.
In addition, as organo-metallic catalyst, can exemplify tin octoate, dibutyl tin laurate, dibutyl lead octoate etc.
Among the present invention, preferably add metal phosphate in this polyurethane solutions and the monoamine compound of molecular weight below 120 made spinning solution.Method as add metal phosphate and monoamine compound in polyurethane solutions can adopt arbitrary method.As its representational method, can adopt method, the method for using stirring method, use homomixer of using the static(al) blender, the whole bag of tricks such as method that use biaxial extruder.
Metal phosphate and monoamine compound both can be added into separately respectively in the polyurethane solutions, after also can being pre-mixed it were added in the polyurethane solutions.From embodying the viewpoint to the deodorization of ammonia, be added in the polyurethane solutions after preferably in advance they being mixed and made into dispersion liquid.
In order to improve the deodorization to ammonia, preferably make in the elastic polyurethane silk with more than the 0.5 weight % and the scope below the 10 weight % contain metal phosphate.Therefore, need make metal phosphate with more than the 0.5 weight % of this spinning solution and the scope below the 10 weight % do not have in the polyurethane spinning solution that is dispersed in unevenly before the spinning, preferably to N, dinethylformamide, N, N-dimethylacetylamide etc. is to add above-mentioned metal phosphate in the polyurethane solutions of solvent, stir, mixed processing, it is not had unevenly disperses, thereby obtain spinning solution.Particularly, preferably make metal phosphate be dispersed in N in advance, dinethylformamide, N in the N-dimethylacetylamide equal solvent, make the metal phosphate dispersion liquid, and this dispersion liquid is blended in the polyurethane solutions.Here, from being added into the viewpoint the polyurethane solutions equably, as the solvent of the metal phosphate dispersion liquid that adds, the preferred use solvent identical with polyurethane solutions.In addition, when adding metal phosphate in the polyurethane solutions, can add above-mentioned reagent such as for example photostabilizer, antioxidant etc. and pigment etc. simultaneously.
In addition, can be not among the present invention after the polyurethane polymerization, in comprising the solution of polyurethane, this add monoamine yet, but the end-capping reagent when using the monoamine of molecular weight below 120 as synthesis of polyurethane, thereby make final confession in the spinning solution of spinning, have this monoamine compound.
Among the present invention, metal phosphate and the monoamine of molecular weight below 120 are present in the spinning solution with polyurethane, but in order to improve the antibiotic property to various bacteriums, preferably make in the spinning solution with more than the 0.01 weight % and the scope below the 0.5 weight % contain the monoamine compound of molecular weight below 120.
In addition, the concentration of the polyurethane in the polyurethane spinning solution is usually preferably more than the 30 weight % and the scope below the 80 weight %.
Also have, among the present invention, in order to improve the antibiotic property to various bacteriums, also preferably contain the quaternary ammonium salt based compound.For this reason, make in the preceding polyurethane spinning solution of spinning and contain above-mentioned quaternary ammonium salt based compound, carry out spinning.As making the method that contains the quaternary ammonium salt based compound in the spinning solution, both can mix with polyurethane solutions separately, also can be pre-mixed in above-mentioned metal phosphate dispersion liquid.
By the spinning solution that constitutes as mentioned above being carried out for example dry spinning, wet type spinning or melt spinning and it being batched, can obtain elastic polyurethane silk of the present invention.Wherein, from can with from carefully to the viewpoint of thick any fineness spinning stably, the preferred dry spinning.
The fineness of elastic polyurethane silk of the present invention, cross sectional shape etc. are not particularly limited.For example, the cross sectional shape of silk both can be circular, perhaps also can be for flat.
In addition, also be not particularly limited for the dry spinning mode, the spinning condition that can suitably select to be complementary with desired characteristic and spinning equipment waits to carry out spinning.
For example, the permanent strain rate of elastic polyurethane silk of the present invention and stress relaxation rate are subjected to the influence of the velocity ratio of godet roller and coiling machine especially easily, and therefore preferred application target according to silk suitably determines.That is from the viewpoint of the elastic polyurethane silk that obtains to have desired permanent strain rate and stress relaxation rate, be that scope more than 1.10 and below 1.65 is batched in the velocity ratio of godet roller and coiling machine preferably.
In addition, from the viewpoint of the intensity of the elastic polyurethane silk that improves gained, spinning speed was preferably more than 250m/ minute.
Embodiment
The present invention will be described in more detail with embodiment.
[intensity of elastic polyurethane silk, stress relaxation rate, permanent strain rate, percentage elongation]
The intensity of elastic polyurethane silk, stress relaxation rate, permanent strain rate, percentage elongation are measured by with Instron 4502 type cupping machines the sample silk being carried out tension test.
Their definition as described below.
That is, the sample of 5cm (L1) is stretched 300% with 50cm/ minute draw speed, repeat 5 times.The stress note of this 5th is made (G1).Then, keep 30 seconds of this stretching of 300%.Make (G2) with keeping the stress note after 30 seconds.Then, make extension recovery, the length note that stress is reached 0 o'clock sample silk is made (L2).Then, in the time of the 6th time, the sample silk is stretched until fracture.Stress note when this is ruptured is made (G3), and the length note of the sample silk during with fracture is made (L3).
Below, above-mentioned characteristic is known by following formula.
Intensity [cN]=(G3)
Stress relaxation rate [%]=100 * ((G1)-(G2))/(G1)
Permanent strain rate [%]=100 * ((L2)-(L1))/(L1)
Percentage elongation [%]=100 * ((L3)-(L1))/(L1)
In addition, tension test is carried out 3 times, tries to achieve according to mean value.
[deodorization, the antibiotic property evaluation manufacturing of knitted fabric]
The elastic polyurethane silk of 22dtex is stretched 3 times, covers polyamide processing silk (trade mark Kyuupu, the (East レ of Dongli Ltd.) system, 33 dtexs, 26 monofilament as the sheath silk with the twisting count of 800T/m thereon), make that S twists with the fingers and single covering filament (SCY) of Z sth. made by twisting.
Then, twist with the fingers SCY for above-mentioned S with knitting tension 1.0g to silk mouthful 1,3 confessions that supply of pantyhose knitting machine (several 400 of Luo Nadi company (ロ Na テ ィ society) system, pin), twist with the fingers SCY to 2,4 confessions to above-mentioned Z, be made into knitted fabric.The containing ratio of the elastic polyurethane silk in the knitted fabric is 16%.
Then, the dyeing of enforcement knitted fabric as described below processing obtains the pantyhose knitted fabric.
(1) default: as to use vacuum drier, 90 ℃ * 10 minutes
(2) dyeing: use dyestuff " Lanaset " (registration mark) the Black B of Ciba Co., Ltd. (チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ) system of 2.0owf%, handled 60 minutes down at 90 ℃, dye black.PH during dyeing adjusts and carries out with acetic acid and ammonium sulfate.
(3) carry out soft treatment at last, carry out fine finishining by setting operation (use pantyhose boarding machine, setting: 115 ℃ * 10 seconds, drying: 120 ℃ * 30 seconds).
[washing methods]
The washing methods handbook of working out with the new functional evaluation appraisal meeting of fibre is benchmark (subordinate list 1 of JIS L0217:1995, washing methods 103).Namely, the family expenses electric washing machine of regulation in the subordinate list 1 of use JIS L0217:1995, the washing methods 103, cleaning solution is made in dissolving 40 milliliters of JAFET standard wash agent (the new functional evaluation of fibre appraisal meeting system) in 3 liters 40 ℃ water, adds 1kg as the washings of sample in this cleaning solution.Washed 5 minutes, dehydration, rinsing 2 minutes, dehydration, rinsing 2 minutes, dehydration, is washed as 1 time with above-mentioned operation.
[deodorization]
Deodorizing test is benchmark with deodorizing processing fiber goods Valuation Standard (enactor: estimation of fibres technical protocol meeting goods authentication department of civic organization, formulation day: put down into 14 years (2002) September 1), the deodorization evaluation of carrying out the foul smell composition by instrument test as described below.In addition, by civic organization's estimation of fibres technical protocol can work out, the criterion of acceptability that is evaluated as " deodorizing effect is arranged " for the slip of each the foul smell composition in this Instrumental Analysis test is shown in table 1.
(detector tube method)
1. (10cm * 10cm) puts into sampler bag (Tedlar bag) with sample.
2. inject the test gas of the ormal weight shown in the table 1, with the survival gas concentration (ppm) of detector tube (Gastech company (ガ ス テ ッ Network society) system) mensuration after 2 hours of composition correspondence.In addition, the gas filling rate is 3L, and diluent gas is dry air or nitrogen.
[table 1]
Gas Initial concentration (ppm) Criterion of acceptability Specification
Ammonia 100 More than 70% JAFET
Acetic acid 50 More than 80% JAFET
Nonenyl aldehyde 14 More than 75% JAFET
3. do not use sample to carry out same evaluation, as blank test.
4. in estimating, according to the slip that following formula is calculated survival gas concentration, note is made the deodorizing rate.
[several 1]
Figure 2011800610064100002DEST_PATH_IMAGE004
In addition, measured value is tried to achieve according to the mean value of n=3.
[antibiotic property]
Antibacterial tests with civic organization's estimation of fibres technical protocol can appointment antibiotic property test procedure (JIS L1902:2008, bacterium liquid absorption process) be that benchmark is implemented.The viable count (individual) of cultivation after 18 hours of no processing sample is made as X, the viable count (individual) of cultivation after 18 hours of testing fabric is made as Y, calculate the bacteriostatic activity value by following formula, estimate antibacterial efficacy.In addition, measured value is tried to achieve according to the mean value of n=3.
[several 2]
Bacteriostatic activity value=LogX-LogY
In addition, according to civic organization's estimation of fibres technical protocol meeting, the bacteriostatic activity value of staphylococcus aureus is 2.2 when above, thinks " to produce effect " at antibiosis.
[emission of monoamine compound]
Preliminary treatment:
After batching the elastic polyurethane silk, under the condition of 35 ℃ * 65%RH, preserved 14 days.Then, (produce J-4 processed of Japanese society, 340mm * 240mm * 0.04mm), inject behind the pure air airtightly rapidly, preservation is 100 hours under 23 ℃ room temperature the elastic polyurethane silk to be put into bag with bayonet.
Analyze:
From the treated bag with bayonet of putting into the elastic polyurethane silk gas is all captured to trap tube.The organic principle that captures is heated disengaging from trap tube, import GC/MS and analyze.Condition determination is shown in table 2.
[table 2]
Quantitatively use the calibration curve of toluene, undertaken by absolute calibration curve method according to total ion absolute area.Should illustrate that measure by following formula from the emission of per unit area of test, measured value is 2 points of sample determination to same level, tries to achieve according to the mean value of n=2.
[several 3]
Emission (μ g/m 2Exposed area (the cm of)=become component (μ g)/silk part 2) * 10
Exposed area (the cm of silk part 2)=((A/2) 2* 3.14-(B/2) 2* 3.14) * 2+ ((C+D)/2) * A * 3.14
Here, A, B, C, D such as Fig. 1 define.Should illustrate, among Fig. 1, (a) be the vertical view of packing, (b) be the front view of packing.
[NOx yellowing resistance]
10g elastic polyurethane silk is batched in corrosion resistant plate, make the sample card.Use Scott tester (Scott tester), make this sample in making air, contain the NO of normal concentration (7ppm) 2Gas and gas in expose 50 hours.Before and after this exposes processing, use color management device (Color Master) (D25 DP-9000 type signal processor (Signal Processor)) to measure " b " color, estimate the xanthochromia degree according to poor " the △ b " that handle front and back.In addition, measured value is tried to achieve according to the mean value of n=3.
[average primary particle diameter]
Take with the inorganic particulate of Hitachi Ltd.'s field emission scanning electron microscope processed (FE-SEM) S-800, analyze and try to achieve with image processing software Image-Pro Version4.0.In addition, measure the projected area equivalent circle diameter, for each sample, according on average trying to achieve of the number of n=20.
[content of metal phosphate]
Analyze the elastic polyurethane silk by the raw yarn absorption photometry, measure the concentration of metal phosphate.Mensuration is carried out at the metal in the metal phosphate (Al, Zr, Ti).In addition, measured value is on average tried to achieve according to n=3's, obtains the content of metal phosphate by following formula.
[several 4]
Figure 515172DEST_PATH_IMAGE007
。
[content of quaternary ammonium salt]
Weighing 1g sample (polyurethane silk) is added in the 100ml methyl alcohol, the extraction quaternary ammonium salt.For extract, carry out quantitatively according to ready-made titer by liquid chromatography.Analysis condition is as follows.In addition, measure on average trying to achieve according to n=2.
Post: LiChrospher 100 RP-18 (5 μ m), internal diameter 4.6mm, long 150mm, column temperature: 35 ℃
Detect: UV210nm
Phase flows: methanol mixed solution (60/40 capacity %), flow velocity: 1ml/ minute, injection rate: 2 μ l.
[embodiment 1]
Make the PTMG of molecular weight 1800 and MDI with the mol ratio of 1:1.58 90 ℃ of reactions 2 hours down, make the prepolymer of isocyanates end after, be dissolved in DMAc, make it reach 35 weight %, be modulated into pre-polymer solution.In addition, will be as the ethylenediamine, 1 of cahin extension agent, the 2-propane diamine, mix with the ratio of the amino terminal radical concentration of 10:2:1 as the diethylamine of chain terminating agent (end-capping reagent), be dissolved in DMAc, make it reach 35 weight %, be modulated into amine aqueous solution.Be that the condition of 1:1.02 is mixed while stirring with pre-polymer solution and amine aqueous solution with the mol ratio of isocyanates end group and amine end group, be modulated into the DMAC solution (concentration 35 weight %) of polyurethaneurea polymer.Then, to mix with 2 to 1 (weight ratios) by the polyurethane solutions (E.I.Du Pont Company's system " Methacrol " (registration mark) 2462) that generates as the tert-butyl group diethanol amine of antioxidant and the reaction of di-2-ethylhexylphosphine oxide (4-cyclohexyl isocyanate) and the condensation polymer (E.I.Du Pont Company's system " Methacrol " (registration mark) 2390) of paracresol and divinylbenzene, be modulated into antioxidant DMAc solution (concentration 35 weight %).DMAc solution 96 weight portions and antioxidant DMAc solution 4 weight portions of above-mentioned polyurethaneurea polymer are mixed, make polymer solution A1.
Then, be that deodorant " ケ ス モ Application " (registration mark) NS-10 (average primary particle diameter 0.9 μ m) is scattered in DMAc with homomixer with the synthetic society in East Asia basic zirconium phosphate, make basic zirconium phosphate dispersion liquid B1 (35 weight %).
Then, diethylamine (molecular weight 73.14) is modulated into 35 weight % in DMAc, makes monoamine solution C 1.
Polymer solution A1, B1, C1 are mixed equably with 96.9 weight %, 3 weight %, 0.1 weight %, make spinning solution D1.Be to carry out dry spinning with 720m/ minute speed under 1.3 the condition with its velocity ratio at godet roller and coiling machine, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 3 weight %.
For the elastic polyurethane silk of gained, make to estimate and use knitted fabric, measure deodorization and antibiotic property.Emission, the NOx yellowing resistance of the monoamine compound of result and elastic polyurethane silk itself are shown in table 3,4,5 in the lump.
[embodiment 2]
Polymer solution A1, B1, C1 are mixed equably with 97.98 weight %, 2 weight %, 0.02 weight %, make spinning solution D2.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 3]
Synthetic titanium phosphate (average primary particle diameter 1.1 μ m) is scattered in DMAc with homomixer, makes titanium phosphate dispersion liquid B2 (35 weight %) and replace basic zirconium phosphate dispersion liquid B1.
Polymer solution A1, B2, C1 are mixed equably with 96.98 weight %, 3 weight %, 0.02 weight %, make spinning solution D3.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, titanium phosphate is the 200g curled hair body of the polyurethane silk of 3 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 4]
Ethyl dimethylamine (molecular weight 89.14) is modulated into 35 weight % in DMAc, makes monoamine solution C 2 (35 weight %) and replace monoamine solution C 1.
Polymer solution A1, B1, C2 are mixed equably with 94.88 weight %, 5 weight %, 0.12 weight %, make spinning solution D4.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 5 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 5]
Diisopropylamine (molecular weight 101.19) is modulated into 35 weight % in DMAc, makes monoamine solution C 3 (35 weight %) and replace monoamine solution C 1.
Polymer solution A1, B1, C3 are mixed equably with 99.35 weight %, 0.5 weight %, 0.15 weight %, make spinning solution D5.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 0.5 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 6]
Isopropyl methylamine (molecular weight 73.14) is modulated into 35 weight % in DMAc, makes monoamine solution C 4 (35 weight %) and replace monoamine solution C 1.
Polymer solution A1, B1, C4 are mixed equably with 89.5 weight %, 10.0 weight %, 0.5 weight %, make spinning solution D6.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 10 weight %.But, the broken string of the obstruction of mouthful mould has taken place to be considered in spinning process, spinnability is not good.
Various evaluation results are shown in table 3,4,5.
[embodiment 7]
N-butylamine (molecular weight 73.14) is modulated into 35 weight % in DMAc, makes monoamine solution C 5 (35 weight %) and replace monoamine solution C 1.
Polymer solution A1, B1, C5 are mixed equably with 95.9 weight %, 4.0 weight %, 0.1 weight %, make spinning solution D7.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 4 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 8]
Polymer solution A1, B2, C1 are mixed equably with 92.9 weight %, 7.0 weight %, 0.1 weight %, make spinning solution D8.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, titanium phosphate is the 200g curled hair body of the polyurethane silk of 7 weight %.
Various evaluation results are shown in table 3,4.
[embodiment 9]
Synthetic separately basic zirconium phosphate (average primary particle diameter 3.5 μ m) is scattered in DMAc with homomixer, makes basic zirconium phosphate dispersion liquid B3 (35 weight %) and replace basic zirconium phosphate dispersion liquid B1.
Polymer solution A1, B3, C1 are mixed equably with 97.4 weight %, 2.5 weight %, 0.1 weight %, make spinning solution D9.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, titanium phosphate is the 50g curled hair body of the polyurethane silk of 2.5 weight %.But, the broken string of the obstruction of mouthful mould has taken place to be considered in a large number in spinning process, spinnability is poor.
Various evaluation results are shown in table 3,4,5.
[embodiment 10]
Polymer solution A1, B1, C1 are mixed equably with 93.9 weight %, 6 weight %, 0.01 weight %, make spinning solution D10.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 6 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 11]
The DMAC solution (35 weight %) of the polyurethane urethane polymer that modulation constitutes by PTMG, the MDI of molecular weight 2100, ethylene glycol with as the 1-butanols of end-capping reagent.Then, to mix with 2 to 1 (weight ratios) by the polyurethane solutions (E.I.Du Pont Company's system " Methacrol " (registration mark) 2462) that generates as the tert-butyl group diethanol amine of antioxidant and the reaction of di-2-ethylhexylphosphine oxide (4-cyclohexyl isocyanate) and the condensation polymer (E.I.Du Pont Company's system " Methacrol " (registration mark) 2390) of paracresol and divinylbenzene, be modulated into antioxidant DMAc solution (concentration 35 weight %).DMAc solution 96 weight portions and antioxidant DMAc solution 4 weight portions of above-mentioned polyether polyols with reduced unsaturation are mixed, make polymer solution A2.
Quaternary ammonium salt based compound processed " BARQUAT " (registration mark) MS-100 of Long Sha Japanese firm (ロ Application ザ ジ ャ パ Application (strain) society) (benzyl dimethyl four decyl ammonium chlorides) is modulated into 35 weight % in DMAc, makes antimicrobial C6.
Polymer solution A2, B1, C1, C6 are mixed equably with 96.8 weight %, 2.5 weight %, 0.2 weight %, 0.5 weight %, make spinning solution D11.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2.5 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 12]
The aluminium dihydrogen tripolyphosphate that Chemical Co., Ltd of kingdom (テ イ カ (strain) society) is made is that deodorant " K-FRESH " (registration mark) #100P (average primary particle diameter 1.0 μ m) is scattered in DMAc with homomixer, makes aluminium dihydrogen tripolyphosphate dispersion liquid B4 (35 weight %) and replaces basic zirconium phosphate dispersion liquid B1.
Polymer solution A1, B4, C1 are mixed equably with 94.8 weight %, 5 weight %, 0.2 weight %, make spinning solution D12.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, aluminium dihydrogen tripolyphosphate is the 200g curled hair body of the polyurethane silk of 5 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 13]
Polymer solution A2, B1, C1 are mixed equably with 96.9 weight %, 3 weight %, 0.1 weight %, make spinning solution D13.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 3 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 14]
With the PTMG of molecular weight 1800 and the MDI mixed in molar ratio with 1:1.58,90 ℃ of reactions 2 hours down, make the prepolymer of isocyanates end after, be dissolved in DMAc, make it reach 35 weight %, be modulated into pre-polymer solution.In addition, will be as the ethylenediamine of cahin extension agent, mix with the ratio of the amino terminal radical concentration of 14:1 as the diethylamine of chain terminating agent, be dissolved in DMAc, make it reach 35 weight %, be modulated into amine aqueous solution.
Be that the condition of 1:1.06 is mixed while stirring with pre-polymer solution and amine aqueous solution with the mol ratio of isocyanates end group and amine end group, be modulated into the DMAC solution (35 weight %) of polyurethaneurea polymer.Then, to mix with 2 to 1 (weight ratios) by the polyurethane solutions (E.I.Du Pont Company's system " Methacrol " (registration mark) 2462) that generates as the tert-butyl group diethanol amine of antioxidant and the reaction of di-2-ethylhexylphosphine oxide (4-cyclohexyl isocyanate) and the condensation polymer (E.I.Du Pont Company's system " Methacrol " (registration mark) 2390) of paracresol and divinylbenzene, be modulated into antioxidant DMAc solution (concentration 35 weight %), DMAc solution 96 weight portions and antioxidant DMAc solution 4 weight portions of above-mentioned polyether polyols with reduced unsaturation are mixed, make polymer solution A3.
Polymer solution A3, B1 are mixed equably with 97 weight %, 3 weight %, make spinning solution D14.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 3 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 15]
EQ-01D is modulated into 35 weight % in DMAc with day oiling Co., Ltd.'s quaternary ammonium salt based compound processed " Nissan Cation " (registration mark), makes antimicrobial C7.
Polymer solution A1, B1, C1, C7 are mixed equably with 96.8 weight %, 2.5 weight %, 0.2 weight %, 0.5 weight %, make spinning solution D15.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2.5 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 16]
Sanyo Chemical Industries Co., Ltd. quaternary ammonium salt based compound processed " Neojaami DFS " is modulated into 35 weight % in DMAc, makes solution C 8 (35 weight %).
Polymer solution A3, B1, C8 are mixed equably with 96.5 weight %, 2.5 weight %, 1 weight %, make spinning solution D16.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2.5 weight %.
Various evaluation results are shown in table 3,4,5.
[embodiment 17]
Polymer solution A3, B1, C8 are mixed equably with 97.4 weight %, 2.5 weight %, 0.1 weight %, make spinning solution D17.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2.5 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 1]
Polymer solution A1 is carried out dry spinning similarly to Example 1, obtain the 200g curled hair body of the polyurethane silk of 22 dtexs, 2 monofilament.
Various evaluation results are shown in table 3,4,5.
[comparative example 2]
Polymer solution A1, B1 are mixed equably with 97.5 weight %, 2.5 weight %, make spinning solution D18.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2.5 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 3]
Polymer solution A1, C2 are mixed equably with 99.8 weight %, 0.2 weight %, make spinning solution D19.It is carried out dry spinning similarly to Example 1, obtain the 200g curled hair body of the polyurethane silk of 22 dtexs, 2 monofilament.
Various evaluation results are shown in table 3,4,5.
[comparative example 4]
Will product river fuel Co., Ltd. (シ Na ネ Application ゼ オ ミ ッ Network (strain) society) system contain silver zeolite " Zeomikku " (registration mark) SW-10N (average primary particle diameter 1.0 μ m) and be scattered in DMAc with homomixer, make Zeolite dispersion B3 (35 weight %) and replace basic zirconium phosphate dispersion liquid B1.
Polymer solution A1, B3 are mixed equably with 96 weight %, 4 weight %, make spinning solution D20.With its dry spinning similarly to Example 1, the content that obtain 22 dtexs, 2 monofilament, contains silver zeolite is the 200g curled hair body of the polyurethane silk of 4 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 5]
Diamylamine (molecular weight 157.3) is modulated into 35 weight % in DMAc, makes monoamine solution C 9 (35 weight %) and replace monoamine solution C 1.
Polymer solution A1, B1, C9 are mixed equably with 97.9 weight %, 2.0 weight %, 0.1 weight %, make spinning solution D21.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 6]
With the (East ソ ー of TOSOH Co., Ltd (strain) society) high silica zeolites HSZ-980HOA processed (average primary particle diameter 2.0 μ m) is scattered in DMAc with homomixer, and make Zeolite dispersion B5 (35 weight %) and replace basic zirconium phosphate dispersion liquid B1.
Polymer solution A1, B5, C1 are mixed equably with 96.8 weight %, 3 weight %, 0.2 weight %, make spinning solution D22.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, zeolite is the 200g curled hair body of the polyurethane silk of 3 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 7]
(average primary particle diameter 0.04 μ m) is scattered in DMAc with homomixer with Sakai KCC ultra-fine particles of zinc oxide processed " FINEX "-25, makes zinc oxide fluid dispersion B6 (35 weight %) and replaces basic zirconium phosphate dispersion liquid B1.
Polymer solution A1, B6, C1 are mixed equably with 96.9 weight %, 3 weight %, 0.1 weight %, make spinning solution D23.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, zinc oxide is the 200g curled hair body of the polyurethane silk of 3 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 8]
The natural antibacterial agent Hinokitiol is modulated into 35 weight % in DMAc, makes solution C 10 (35 weight %) and replace monoamine solution C 1.
Polymer solution A1, B6, C10 are mixed equably with 96.9 weight %, 3 weight %, 0.1 weight %, make spinning solution D24.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, zinc oxide is the 200g curled hair body of the polyurethane silk of 3 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 9]
Polymer solution A1, C8 are mixed equably with 99 weight %, 1 weight %, make spinning solution D25.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, zinc oxide is the 200g curled hair body of the polyurethane silk of 3 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 10]
Toagosei Co., Ltd's silver-containing antibacterial agent processed " NOVARON " (registration mark) AGT330 (average primary particle diameter 0.5 μ m) is scattered in DMAc with homomixer, makes inorganic series antibacterial agent dispersion liquid C11 (35 weight %) and replace monoamine solution C 1.Polymer solution A1, B1, B6, C11 are mixed equably with 96.5 weight %, 1.5 weight %, 1.0 weight %, 1.0 weight %, make spinning solution D26.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 1.5 weight %.
Various evaluation results are shown in table 3,4,5.
[comparative example 11]
Polymer solution A2, B1 are mixed equably with 97.5 weight %, 2.5 weight %, make spinning solution D27.With its dry spinning similarly to Example 1, the content that obtains 22 dtexs, 2 monofilament, basic zirconium phosphate is the 200g curled hair body of the polyurethane silk of 2.5 weight %.
Various evaluation results are shown in table 3,4,5.
[table 3]
[table 4]
Figure 346600DEST_PATH_IMAGE009
[table 5]
Figure DEST_PATH_IMAGE010
Industrial applicability
By the present invention, can obtain the elastic polyurethane silk of retractility, deodorization, antibiotic property, discoloration-resistant excellence, therefore by using this elastic polyurethane silk, can obtain the cloth and silk of retractility, deodorization, antibiotic property, discoloration-resistant excellence.
The explanation of symbol
The external diameter of A packing
The external diameter of B paper tube
The outermost silk volume of C width
The silk volume width of D innermost layer

Claims (12)

1. elastic polyurethane silk, its be by with polymer diol and vulcabond as the elastic yarn that the polyurethane of initiation material constitutes, contain metal phosphate in this elastic yarn, and the emission of the monoamine compound of molecular weight below 120 is 100 μ g/m 2More than.
2. elastic polyurethane silk as claimed in claim 1, wherein, the content of described metal phosphate is 0.5～10wt%.
3. elastic polyurethane silk as claimed in claim 1 or 2, wherein, the average primary particle diameter of described metal phosphate is below the 3.0 μ m.
4. as each described elastic polyurethane silk in the claim 1～3, wherein, described metal phosphate is to be selected from least a in titanium phosphate, basic zirconium phosphate and the aluminium dihydrogen tripolyphosphate.
5. as each described elastic polyurethane silk in the claim 1～4, wherein, the described monoamine compound that distributes is the monobasic secondary amine compound.
6. as each described elastic polyurethane silk in the claim 1～5, wherein also contain the quaternary ammonium salt based compound.
7. elastic polyurethane silk as claimed in claim 6, wherein, described quaternary ammonium salt based compound has following structure:
[changing 1]
Wherein,
R1, R2 are the alkyl of hydrogen or carbon number 1～3, can be the same or different;
R3 is the alkyl of carbon number 10～22;
R4 is the alkyl of carbon number 1～22, can be with R1, R2, R3 is identical also can be different;
X-is acid equilibrium ion.
8. as claim 6 or 7 described elastic polyurethane silks, wherein, the content of described quaternary ammonium salt based compound is the scope that 0.1 weight % is above and 5 weight % are following.
9. the manufacture method of elastic polyurethane silk, this method be comprise with polymer diol and vulcabond as the spinning solution of the polyurethane of initiation material in hybrid metal phosphate and the monoamine compound of combined molecular weight below 120 simultaneously, make that the content of this monoamine compound is more than the 0.01 weight % and the scope below the 0.5 weight % with respect to spinning solution, and with this spinning solution dry spinning.
10. the manufacture method of elastic polyurethane silk as claimed in claim 9 wherein, is blended in described metal phosphate and describedly comprises with polymer diol and vulcabond in the spinning solution as the polyurethane of initiation material with the form of dispersion liquid.
11. as the manufacture method of claim 9 or 10 described elastic polyurethane silks, wherein, described metal phosphate is to be selected from least a in titanium phosphate, basic zirconium phosphate and the aluminium dihydrogen tripolyphosphate.
12. as the manufacture method of each described elastic polyurethane silk in the claim 9～11, wherein, the described monoamine compound of molecular weight below 120 is secondary amine compound.
CN201180061006.4A 2010-10-19 2011-10-12 Elastic polyurethane thread and manufacturing method thereof Expired - Fee Related CN103298985B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010234355 2010-10-19
JP2010-234355 2010-10-19
PCT/JP2011/073398 WO2012053401A1 (en) 2010-10-19 2011-10-12 Elastic polyurethane thread and manufacturing method thereof

Publications (2)

Publication Number Publication Date
CN103298985A true CN103298985A (en) 2013-09-11
CN103298985B CN103298985B (en) 2015-05-06

Family

ID=45975118

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180061006.4A Expired - Fee Related CN103298985B (en) 2010-10-19 2011-10-12 Elastic polyurethane thread and manufacturing method thereof

Country Status (10)

Country Link
US (2) US20140148537A1 (en)
EP (1) EP2631338A4 (en)
JP (1) JP5870928B2 (en)
KR (1) KR101851419B1 (en)
CN (1) CN103298985B (en)
BR (1) BR112013009233A2 (en)
HK (1) HK1189248A1 (en)
MX (1) MX2013004238A (en)
TW (1) TWI553176B (en)
WO (1) WO2012053401A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106687631A (en) * 2014-05-29 2017-05-17 东丽奥培隆特士株式会社 Deodorant fabric
CN110291236A (en) * 2017-01-05 2019-09-27 晓星天禧(株) Deodorization spandex and preparation method thereof
CN110923946A (en) * 2019-11-20 2020-03-27 苏州市雄林新材料科技有限公司 Nano antibacterial breathable TPU (thermoplastic polyurethane) film and preparation method thereof
CN111334879A (en) * 2020-04-28 2020-06-26 连云港杜钟新奥神氨纶有限公司 Preparation method and application of polyhexamethylene biguanide intercalated α -zirconium phosphate and antibacterial spandex

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5413360B2 (en) * 2010-12-14 2014-02-12 東レ・オペロンテックス株式会社 Polyurethane elastic yarn
JP6516121B2 (en) * 2013-07-19 2019-05-22 東レ・オペロンテックス株式会社 Polyurethane elastic yarn and method for producing the same
JP6453026B2 (en) * 2014-10-09 2019-01-16 リケンテクノス株式会社 Method for producing thermoplastic resin composition film
EP3491179B1 (en) * 2016-07-29 2020-12-02 The LYCRA Company UK Limited Silicone oil elimination from spandex polymer spinning solutions
CN106283265B (en) * 2016-09-07 2018-06-26 浙江华峰氨纶股份有限公司 A kind of preparation method of the microcosmic finely dispersed fire-retardant spandex of basic zirconium phosphate synergistic
JP6718783B2 (en) * 2016-09-30 2020-07-08 Ｋｂセーレン株式会社 Polyurethane elastic functional nonwoven
EP4328251A1 (en) * 2021-08-23 2024-02-28 Lg Chem, Ltd. Elastic and antibacterial polyurethane, preparation method therefor, and product comprising same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07166425A (en) * 1993-11-24 1995-06-27 Asahi Chem Ind Co Ltd Polyurethane elastic fiber
CN1646741A (en) * 2002-04-22 2005-07-27 东洋纺织株式会社 Elastic fiber and use thereof
JP2006028453A (en) * 2004-07-21 2006-02-02 Nisshinbo Ind Inc Polyurethane elastomer and elastic fiber
WO2009101995A1 (en) * 2008-02-15 2009-08-20 Opelontex Co., Ltd. Deodorizing material
CN101760000A (en) * 2009-12-10 2010-06-30 鲁东大学 Antibacterial nano-silver composite polyurethane material and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58156074A (en) * 1982-03-10 1983-09-16 三菱レイヨン株式会社 Sterilizable fiber molded article
JPS6126612A (en) 1984-07-17 1986-02-05 Kuraray Co Ltd Preparation of polyurethane having improved resistance to hydrolysis
US4875901A (en) * 1986-10-14 1989-10-24 Minnesota Mining And Manufacturing Company Treating fibrous polyamide articles
US4822373A (en) * 1988-03-11 1989-04-18 Minnesota Mining And Manufacturing Company Process for providing polyamide materials with stain resistance with sulfonated novolak resin and polymethacrylic acd
JP2615131B2 (en) 1988-05-11 1997-05-28 旭化成工業株式会社 Segmented polyurethane and method for producing the same
JPH02289516A (en) 1989-02-28 1990-11-29 Asahi Chem Ind Co Ltd (+)-pranoprofen-containing drug composition
US5310828A (en) * 1989-04-20 1994-05-10 Peach State Labs, Inc. Superior stain resistant compositions
US5516337A (en) * 1992-09-02 1996-05-14 Minnesota Mining And Manufacturing Company Chemical system for providing fibrous materials with stain resistance
JP2842564B2 (en) * 1993-12-20 1999-01-06 東邦レーヨン株式会社 Antibacterial viscose rayon and method for producing the same
US5962130A (en) * 1995-01-03 1999-10-05 Dupont-Toray Co., Ltd. Durable polyurethane fiber and method for the manufacture thereof
DE4446339C1 (en) * 1994-12-23 1996-05-02 Bayer Faser Gmbh Reducing viscosity of polyurethane spinning solns.
DE69610232T2 (en) * 1995-02-15 2001-03-01 Kuraray Co Deodorising fibers and process for their manufacture
JP3637503B2 (en) * 1995-08-18 2005-04-13 オペロンテックス株式会社 Polyurethane fiber, clothing and clothing secondary materials
JP3051709B2 (en) * 1997-09-30 2000-06-12 憲司 中村 Antimicrobial cellulose fiber and method for producing the same
JP4439707B2 (en) 2000-09-27 2010-03-24 旭化成せんい株式会社 Method for producing polyurethane elastic fiber
US6403682B1 (en) * 2001-06-28 2002-06-11 E. I. Du Pont De Nemours And Company Spandex containing quaternary amine additives
JP2004292471A (en) 2003-03-25 2004-10-21 Nisshinbo Ind Inc Polyurethane elastomer and elastic fiber
JP2005097820A (en) * 2003-08-27 2005-04-14 Kanebo Ltd Deodorizing fiber
CN100487187C (en) * 2004-05-19 2009-05-13 三洋化成工业株式会社 Oiling agent for fiber treatment
CN100344822C (en) * 2004-10-19 2007-10-24 东华大学 Polycomponent fiber product composite nano antibacterial agent, its preparing method and use
EP2163665A4 (en) * 2007-06-22 2012-11-28 Opelontex Co Ltd Elastic polyurethane yarn and process for production thereof
JP4235244B1 (en) * 2008-02-15 2009-03-11 長谷虎紡績株式会社 Stretch fabric

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07166425A (en) * 1993-11-24 1995-06-27 Asahi Chem Ind Co Ltd Polyurethane elastic fiber
CN1646741A (en) * 2002-04-22 2005-07-27 东洋纺织株式会社 Elastic fiber and use thereof
JP2006028453A (en) * 2004-07-21 2006-02-02 Nisshinbo Ind Inc Polyurethane elastomer and elastic fiber
WO2009101995A1 (en) * 2008-02-15 2009-08-20 Opelontex Co., Ltd. Deodorizing material
CN101760000A (en) * 2009-12-10 2010-06-30 鲁东大学 Antibacterial nano-silver composite polyurethane material and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106687631A (en) * 2014-05-29 2017-05-17 东丽奥培隆特士株式会社 Deodorant fabric
TWI716351B (en) * 2014-05-29 2021-01-21 日商東麗奧培隆特士股份有限公司 Deodorant fabric
CN110291236A (en) * 2017-01-05 2019-09-27 晓星天禧(株) Deodorization spandex and preparation method thereof
CN110291236B (en) * 2017-01-05 2022-02-25 晓星天禧(株) Deodorization spandex and preparation method thereof
CN110923946A (en) * 2019-11-20 2020-03-27 苏州市雄林新材料科技有限公司 Nano antibacterial breathable TPU (thermoplastic polyurethane) film and preparation method thereof
CN110923946B (en) * 2019-11-20 2022-08-23 苏州市雄林新材料科技有限公司 Nano antibacterial breathable TPU (thermoplastic polyurethane) film and preparation method thereof
CN111334879A (en) * 2020-04-28 2020-06-26 连云港杜钟新奥神氨纶有限公司 Preparation method and application of polyhexamethylene biguanide intercalated α -zirconium phosphate and antibacterial spandex

Also Published As

Publication number Publication date
KR20130122622A (en) 2013-11-07
WO2012053401A1 (en) 2012-04-26
BR112013009233A2 (en) 2016-07-26
JPWO2012053401A1 (en) 2014-02-24
US20140148537A1 (en) 2014-05-29
TW201221713A (en) 2012-06-01
CN103298985B (en) 2015-05-06
JP5870928B2 (en) 2016-03-01
TWI553176B (en) 2016-10-11
US20140033451A1 (en) 2014-02-06
MX2013004238A (en) 2013-08-01
EP2631338A4 (en) 2014-06-11
EP2631338A1 (en) 2013-08-28
KR101851419B1 (en) 2018-05-31
HK1189248A1 (en) 2014-05-30

Similar Documents

Publication Publication Date Title
CN103298985B (en) Elastic polyurethane thread and manufacturing method thereof
JP6133254B2 (en) 2 component spandex
US8691201B2 (en) Deodorant material
JP5413360B2 (en) Polyurethane elastic yarn
US10040892B2 (en) Polyurethane elastic yarn and production method thereof
US9404199B2 (en) Polyurethane elastic yarn and method for producing same
CN101809209A (en) Elastic polyurethane yarn and process for production thereof
JP6031331B2 (en) Polyurethane elastic fiber and method for producing the same
JP6855652B2 (en) Fiber structure
JP3826378B2 (en) Polyurethane yarn and method for producing the same
JP3826377B2 (en) Polyurethane yarn and method for producing the same
TW201627555A (en) Fiber structure and production method for same
US20040019146A1 (en) Elastomeric polyurethane fiber with high heat-set efficiency
JP4406761B2 (en) Polyurethane yarn and method for producing the same
WO2017116983A1 (en) Polyurethane fiber structure
JP2002363823A (en) Hygroscopic polyurethane elastic fiber and method for producing the same
JP2009144276A (en) Polyurethane yarn and method for producing the same
WO2002050349A1 (en) Elastomeric polyurethane fiber with high heat-set efficiency
WO2022084941A1 (en) Polyurethane urea elastic fiber and production method therefor
WO2022185171A1 (en) Polyurethane elastic thread and production method therefor
CN117280086A (en) Polyurethane elastic thread and method for producing the same
JP2002363822A (en) Hygroscopic polyurethane elastic fiber and method for producing the same
JP2022069010A (en) Polyurethane elastic fiber and production method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1189248

Country of ref document: HK

C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1189248

Country of ref document: HK

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150506

Termination date: 20201012

CF01 Termination of patent right due to non-payment of annual fee