CN1213178C - Polyurethane spandex and its manufacturing method, cottons and silks and swimwear - Google Patents
Polyurethane spandex and its manufacturing method, cottons and silks and swimwear Download PDFInfo
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- CN1213178C CN1213178C CNB021198225A CN02119822A CN1213178C CN 1213178 C CN1213178 C CN 1213178C CN B021198225 A CNB021198225 A CN B021198225A CN 02119822 A CN02119822 A CN 02119822A CN 1213178 C CN1213178 C CN 1213178C
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- 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
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Abstract
The present invention is related to polyurethane elastic fiber which is characterized by consisting from polyurethane urea and polyurethane and preparation thereof. The polyurethane elastic fiber of present invention can be used for the usage of swimming suit by way of such excellent anti-chlorine brittle function and thermoset property.
Description
Technical field
The present invention relates to polyurethane elastomeric fiber and manufacture method thereof, cloth and silk and swimsuit.
More detailed saying relates to be suitable for the good polyurethane elastomeric fiber of chlorine resistance of the swimsuit that uses in swimming pool etc.
Technical background
Polyurethane elastomeric fiber has the caoutchouc elasticity of height, because engineering properties such as tensile stress, recovery, thermal property are good, so be widely used in stocking, underwear, sportswear etc.
Yet the clothing product of use polyurethane elastomeric fiber soaks in chlorine bleach for a long time, when washing repeatedly, has the problem of polyurethane elastomeric fiber spring function reduction.
That is, when the swimsuit that uses polyurethane elastomeric fiber soaked in chlorine water repeatedly in the sterilization of water-based pond isoreactivity cl concn 0.5-3ppm, the spring function of polyurethane elastomeric fiber was significantly impaired, produces silk and breaks.
In order to improve the chlorine resistance of polyurethane elastomeric fiber, be polyurethane elastomeric fiber though disclose the polyester that uses the aliphatic poly esterdiol to make raw material, chlorine resistance is insufficient.And, owing to the biologically active of aliphatic polyester is very high, invade the shortcoming that polyester is a polyurethane elastomeric fiber easily so have bacterium, also there is the problem of reduction of swimsuit spring function and easy generation fracture of wire in use or the preservation.The polyethers that uses the minimum PTMEG of biologically active to make raw material is a polyurethane elastomeric fiber, though be subjected to the danger of bacterium initiation embrittlement very little, is the more inferior problem of polyurethane elastomeric fiber but still there is chlorine resistance than polyester.
Polyethers is that polyurethane elastomeric fiber lacks hot residual deformation properties, for this reason, contains the various cloth and the silk of polyurethane elastomeric fiber, all has the problem of hot residual deformation.
That is, because polyurethane elastomeric fiber has very low hot residual deformation efficient, so the silk made from polyurethane elastomeric fiber for hot residual deformation, needs long-time and high-temperature.In the cloth that contains nylon fiber and polyurethane elastomeric fiber, when hot residual deformation temperature is very high, there is the problem that causes the fiber inhomogeneities.This silk fracture strength is little, and is difficult to silk manufacturing is processed into cloth, when wearing the clothing product of being made by this silk, worries the clothing product breakage.This worry is when silk with the little polyurethane elastomeric fiber of fiber number of particularly using in women's socks and swimsuit, particularly remarkable.
Summary of the invention
Purpose of the present invention is exactly in view of above-mentioned the problems of the prior art, and a kind of polyurethane elastomeric fiber and stable method of making this polyurethane elastomeric fiber that swimsuit uses that be suitable for good chlorine resistance and hot residual deformation properties is provided.
The present invention adopts following solution for solving above-mentioned problem.
Promptly, polyurethane elastomeric fiber of the present invention, it is characterized in that: it is the elastomer that is formed with the mixture of the polyurethane of making through the glycol chains elongation by polyurethane-urea, and wherein the content of polyurethane is 3 weight %～90 weight %, and the weight ratio of polyurethane and polyurethane-urea is 1/4～4/1.
For solving above-mentioned problem, the manufacture method of polyurethane elastomeric fiber of the present invention adopts following solution.
Promptly, the manufacture method of polyurethane elastomeric fiber of the present invention, it is characterized in that: to by polyurethane-urea with through glycol chains elongation and the polyurethane of making constitutes and polyurethane content is 3 weight %～90 weight %, and the weight ratio of polyurethane and polyurethane-urea is that 1/4～4/1 polymeric blends is that the solution of solute carries out spinning.
The specific embodiment
Below the present invention is described in detail.Polyurethane elastomeric fiber of the present invention is formed by polyurethane-urea and polyurethane.
Polyurethane-urea among the present invention, the main composition composition is polyalcohol, vulcabond and diamines preferably.
The polyalcohol that uses in the polyurethane-urea, preferably polyethers is that glycol, polyester are glycol, PCDL etc.
When polyurethane elastomeric fiber of the present invention is used in particular for swimsuit, from preventing that bacterium from causing the embrittlement aspect and considering, as polyalcohol, for example preferably use copolymer sex change PTMG (following note is made 3M-PTMG), the THF and 2 of polyethylene glycol, polypropylene glycol, polytetramethylene ether diol (following note is made PTMG), THF and 3-MeTHF, the copolymer sex change PTMG of 3-dimethyl THF, No. 2615131 disclosed polyethers such as polyalcohol that has side chain in both sides such as communique of Japan Patent are glycol.These polyethers are that glycol can a kind or be no less than 2 kinds of mixing, or combined polymerization is used.
As polyurethane elastomeric fiber, when especially needing mar proof and light resistance, preferably use butylene adipate, polycaprolactone glycol, spy to open that polyester such as disclosed polyester polyol with side chain is disclosed PCDL etc. in fair 2-289516 communique of two pure and mild spies etc. in clear 61-26612 communique etc.
Such polyalcohol can use separately, also can be no less than 2 kinds mix or combined polymerization after use.Consider the number-average molecular weight of the polyalcohol that uses in the polyurethane-urea of the present invention, 1000～8000 scope that good is, more preferably 1800～6000 scope from the polyurethane elastomeric fiber that obtains percentage elongation, intensity, elastic-restoring force, excellent heat resistance.
As the vulcabond that uses in the polyurethane-urea of the present invention, the sex change body of aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, aromatic-aliphatic vulcabond, these vulcabond (carbodiimides sex change body, ammonia ester sex change body, urine diketone sex change body etc.) and be no less than 2 kinds mixture etc. in them preferably.
Concrete example as above-mentioned aromatic diisocyanate, preferably 1, the 3-phenylene vulcabond, 1, the 4-phenylene vulcabond, 2,4-benzal vulcabond, 2,6-benzal vulcabond, 2,4 '-methyl diphenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate (following note is made MD1), 4,4 '-two isocyanic acid diphenyl, 3,3 '-dimethyl-4,4 '-two isocyanic acid diphenyl, 3,3 '-dimethyl-4,4 '-two isocyanic acid diphenyl methanes, 1, the 5-naphthalene diisocyanate, 1,4 '-vulcabond benzene, benzene diformazan vulcabond, 2,6-naphthalene diisocyanate etc.
Concrete example as above-mentioned aliphatic diisocyanate, preferably ethylidene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ten dimethylene diisocyanates, 2,2,4-trimethyl hexamethylene diisocyanate, lysinediisocyanate, 2,6-two isocyanic acid methylhexanoic acid esters, two (2-ethyl isocyanate) carbonic acid ester, 2-ethyl isocyanate-2,6-two isocyanic acid hexanol esters etc.
Concrete example as above-mentioned alicyclic diisocyanate, dicyclohexyl methyl hydride-4 preferably, 4 '-vulcabond, cyclohexylene vulcabond, methyl cyclohexylene vulcabond, two (2-ethyl isocyanate)-4-cyclohexylene-1,2-dicarboxylic ester, 2,5-norborneol vulcabond, 2,6-norborneol vulcabond, (following note is made H to di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate)
12MDI), hexahydrotoluene 2,4-vulcabond, hexahydrotoluene 2,6-vulcabond, cyclohexane 1,4-vulcabond, hexahydrobenzene diformazan vulcabond, hexahydro benzal vulcabond, octahydroization 1,5-naphthalene diisocyanate etc.
As the concrete example of above-mentioned aromatic-aliphatic vulcabond, preferably between benzene diformazan vulcabond, terephthaldehyde's vulcabond, α, α, α ', α '-durol diformazan vulcabond etc.
In these, in various uses, from improving the intensity of end article, obtains the consideration of good heat resistance and intensity, good is aromatic diisocyanate, be more preferably MDI.
Consider from suppressing the flavescence of polyurethane silk, preferably aliphatic diisocyanate.
Equally, these vulcabond can use separately, also can 2 kinds or greater than 2 kinds and use.
The chain lengthening agent of using in the polyurethane-urea of the present invention, preferably low molecular weight diamines etc.As the low molecular weight diamines, ethylenediamine, 1 is for example arranged, 2-propane diamine, 1,3-propane diamine, hexamethylene diamine, 1,3-cyclohexyl diamines, six hydrogen m-phenylene diamine (MPD)s, 2 methyl pentamethylenediamine, two (4-aminophenyl) phosphine oxide etc.Preferably from these low molecular weight diamines, select a kind or be no less than 2 kinds of uses.From percentage elongation and elastic recovery, and then from obtaining excellent heat resistance consideration, preferably ethylenediamine.
As the chain lengthening agent, preferably use to have hydroxyl and amino in the molecule of monoethanolamine and so on.
Preferably use the triamine compound that can form cross-linked structure in these chain lengthening agent, for example, the Diethylenetriamine of the fruit of not losing efficacy.
Polyurethane among the present invention, preferably main constituent is polyalcohol, vulcabond and glycol.
The polyalcohol that uses in the polyurethane, vulcabond, can be with last polyurethane-urea in use the same, but also can be with polyurethane-urea in use different.
Wherein, as polyalcohol, preferably number-average molecular weight is 2500～5000 polytetramethylene ether diol.
Among the present invention, the chain lengthening agent of using in the polyurethane, preferably low-molecular-weight diol.As low-molecular-weight diol, ethylene glycol, 1 preferably for example, ammediol, 1,4-butanediol, dihydroxy ethoxy benzene, dihydroxy ethylidene terephthalate etc.
Can from these low-molecular-weight diols, select a kind or be no less than 2 kinds of uses.
Polyurethane elastomeric fiber of the present invention is formed by above-mentioned polyurethane-urea and above-mentioned polyurethane.
The polyurethane elastomeric fiber that forms by polyurethane-urea only, anti-chlorine embrittlement performance is insufficient, and hot residual deformation is inferior.
The polyurethane elastomeric fiber that forms by polyurethane only, recovery is inferior, and it is unstable that spinning easily becomes, and particularly during heavy denier, generation can not get the problem of the elastomer of even fiber number.
Among the present invention, consider from obtaining the viewpoint that anti-chlorine water, hot residual deformation, mechanical residual deformation, intensity, percentage elongation, stress relax good especially polyurethane elastomeric fiber, polyurethane to contain measured be the scope of 3 weight %～97 weight %, the scope of 3 weight %～90 weight % more preferably.
Particularly consider that from can be stably the elastomer of even fiber number being carried out the spinning aspect that good is 3 weight %～50 weight %, more preferably 10 weight %～40 weight %.
The content of polyurethane is preferably suitably determined according to the purposes of polyurethane elastomeric fiber.
The fiber number of polyurethane elastomeric fiber of the present invention, section configuration etc. do not have particular determination.For example, section configuration can be circular, also can be flat.
Polyurethane elastomeric fiber of the present invention preferably contains various stabilizing agents and pigment etc.For example, as photostabilizer, antioxidant etc., containing with the hindered phenol headed by " ス ミ ラ ィ ザ-" GA-80 of so-called BHT and Sumitomo Chemical (strain) system etc. is reagent, チ バ ガ ィ ギ-society's system benzotriazole such as " チ ヌ PVC Application " system, benzophenone is a reagent, the phosphorus such as " ス ミ ラ ィ ザ-" P-16 of Sumitomo Chemical (strain) system are reagent, various hindered amines are reagent, titanium oxide, zinc oxide, inorganic pigments such as carbon black, fluorine resin powder or silicon-type resin powder, metallic soaps such as dolomol, argentiferous, the bactericide of zinc and their compound etc., deodorant, polysiloxanes, mineral wet goods lubricant, barium sulfate, cerium oxide, various antistatic agents such as betaine and phosphoric acid system etc., in addition, also be preferred with polymer reaction.
Particularly sterilization is considered with the durability aspect of chlorine water, light and various nitrogen oxides etc., for example preferably used oxide, composite oxides, the hydroxide of the metal that zinc oxide, magnesia, aluminium oxide etc. select from Mg, Zn, Al from further raising; Select in the group by oxide, composite oxides and the hydroxide of the metal of from Mg, Zn, Al, selecting 2 kinds or greater than 2 kinds of solid solution that constitute, and hydrotalcite-based compound; Mg
2Ca (CO
3)
4The anti-chlorine degradation of (Off Application ィ ト) and hydromagnesite mineral intermixtures such as (water magnesium ore deposits) etc., for example, the nitrogen oxide replenishers such as HN-150, for example of Japan's ヒ De ラ ジ Application (strain) system, the thermal oxidation stabilizers such as " ス ミ ラ ィ ザ-" GA-80 of Sumitomo Chemical (strain) system, for example, the light stabilizers such as " ス ミ ソ-Block " 300#622 of Sumitomo Chemical (strain) system, or the like.
Particularly, when polyurethane elastomeric fiber of the present invention is used for the swimsuit purposes, more preferably use anti-chlorine degradation.
Among the present invention,, preferably use from following 1 as this anti-chlorine degradation)～3) at least a kind metallic compound selecting:
1) oxide of the metal of from Mg, Zn, Al, selecting, composite oxides, hydroxide any,
2) in the oxide of the metal of from Mg, Zn, Al, selecting, composite oxides and the hydroxide, by 2 kinds that select or be no less than 2 kinds of solid solution that constitute,
3) hydrotalcite-based compound.
That is, only preferably use from 1) select at least the group a kind, only from 2) select at least the group a kind, only from 3) select at least the group a kind, respectively from 1) and 2) select at least the group a kind, respectively from 1) and 3) select at least the group a kind, respectively from 2) and 3) select at least organizing a kind, respectively from 1), 2) and 3) select a kind organizing at least.
As this anti-chlorine degradation, preferably for example magnesia, magnesium hydroxide, zinc oxide, zinc hydroxide, aluminium oxide, aluminium hydroxide, contain divalent metal M (M represent from Zn and Mg, select at least a kind) and aluminium, the divalent metal with respect to the mol ratio of aluminium be 1～5 composite oxides, MgO and ZnO composite oxides, use 2ZnOZnAl
2O
4, 3ZnOZnAl
2O
4, 4ZnOZnAl
2O
4, 5ZnOZnAl
2O
4The expression composite oxides, with Mg
6Al
2(OH)
16CO
34H
2O and Mg
4.5Al
2(OH)
13CO
33.5H
2O is hydrotalcite-based compound, MgO/ZnO solid solution, ZnO/AlO solid solution, MgO/ZnO/AlO solid solution, the Mg of representative
2Ca (CO
3)
4(Off Application ィ ト) and Mg
4(CO
3)
4Mg (OH)
34H
2The mixture of O (hydromagnesite) etc.Preferably zinc oxide, hydromagnesite compounds, MgO/ZnO solid solution and Mg
2Ca (CO
3)
4Mixture with hydromagnesite.
In order to make anti-chlorine degradation effects abundant, the rerum natura to fiber does not make a very bad impression, and with respect to fiber quality, the addition of anti-chlorine degradation is preferably 0.1 weight %～10 weight %, more preferably adds 1 weight %～5 weight %.
The anti-chlorine degradation that uses among the present invention considers that from the stability of spinning preferably average grain diameter is not more than the fine powder of 1 μ m.
In order to improve the anti-dispersiveness of chlorine degradation in silk, make purposes such as spinning stabilisation, for example, preferably using aliphatic acid, fatty acid ester, polyalcohol is that organic matter, silane such as organic matter are that coupling agent, titanate are that coupling agent or their mixture carry out surface treatment.
The formation cloth and silk of preferably natural fabric, chemical fibre, synthetic fiber, the semisynthetic fibre of polyurethane elastomeric fiber of the present invention and other being weaved together after the dyeing fine finishining, is made, and is made into goods such as swimsuit.In order to weave the knitwear that constitute by polyurethane elastomeric fiber and other fibers, can adopt various deinterleaving methods.This knitwear can be through compiling, and also can be weft knittings, when being used for the swimsuit purposes, from its function, preferably through compiling.
Can use tricot warp knitting machine to weave, also can use the Raschel looms braiding.Any volumes such as woollen yarn knitting tissue can adopt and half compile, anti-half compile, two sley bar satin is compiled, two sley bar warp plain stitch volumes are amassed.
Say that with regard to liquor style the most handy other natural fabrics in knitwear surface, chemical fibre, synthetic fiber, semisynthetic fibre constitute.
Among the present invention, after the use usual way dyeing processing, can be made into swimsuit by making.
Swimsuit of the present invention, except adaptability, liquor style well, the deterioration that is caused by chlorine waters such as swimming pools is very little, has improved durability.
Below the manufacture method of polyurethane elastomeric fiber of the present invention is described.
Among the present invention, the solution of making solute with polyurethane-urea and polyurethane is preferably modulated in beginning.
Among the present invention,, can adopt any method as the polyurethane-urea of the solute of solution and the manufacture method of polyurethane.
That is, can be any of melt phase polycondensation or solution polymerization process.Yet, be more preferably solution polymerization process.During solution polymerization process, polyurethane-urea and polyurethane seldom produce foreign matters such as gel, obtain the polyurethane elastomeric fiber of low-titer easily.Solution is laborsaving from forming in addition, the production efficiency aspect considers that it also is preferred adopting solution polymerization process certainly.
As the polyurethane-urea that uses among the present invention, can use polyalcohol, MDI, ethylenediamine, 1 from molecular weight 1000～8000,2-propane diamine, 1,3-propane diamine, hexamethylene diamine, 1, at least a kind of diamines selecting in 3-cyclohexyl diamines and the 2 methyl pentamethylenediamine, synthesize, and the high temperature side fusing point is preferably 250 ℃～300 ℃.
Synthesizing of polyurethane-urea, for example the best way is, at first makes polyalcohol and MDI carry out frit reaction, is in the solvent of principal component with reactants dissolved at DMAc, DMF, DMSO, NMP etc. or with them subsequently, with above-mentioned diamine reactant, form polyurethane urea solutions again.
The high temperature side fusing point of polyurethane-urea is adjusted to 250～300 ℃, can reaches by the kind and the ratio of control polyalcohol, MDI, diamines.When the molecular weight of polyalcohol is very high, relatively improve the ratio of MDI, can obtain the very high polyurethane-urea of high temperature fusing point.The molecular weight of polyalcohol is 1000 or greater than 1000 o'clock, reach 250 ℃ or from the high temperature side fusing point that makes polyurethane-urea, be not less than 1.3 as being preferably based on the NCO base of vulcabond with based on the addition ratio of the molal quantity ratio of hydroxyl groups ((based on the molal quantity of the NCO base of vulcabond)/(based on the molal quantity of hydroxyl groups)) greater than 250 ℃ of considerations.
When synthesizing this polyurethane-urea, preferably mix a kind of use or be no less than 2 kinds amine series catalysts and organo-metallic catalyst.As the amine series catalysts, N is for example arranged, the N-dimethyl cyclohexyl amine, N, the N-dimethyl benzyl amine, triethylamine, N-methylmorpholine, N, 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-dimethylamino ether, N, N, N ', N ', N '-pentamethyl Diethylenetriamine, tetramethyl guanidine, triethylenediamine, N, N '-lupetazin, N-methyl-N '-dimethylaminoethyl piperazine, N-(2-dimethylaminoethyl) morpholine, the 1-methylimidazole, 1, the 2-methylimidazole, N, N-dimethylamino ethanol, N, N, N '-triethyl group aminoethyl ethanolamine, N-methyl-N '-(2-ethoxy) croak piperazine, 2,4,6-three (dimethylaminoethyl) phenol, N, N-dimethylamino hexanol, triethanolamine etc.
As organo-metallic catalyst, preferably tin octoate, dibutyl tin laurate, lead octoate dibutyl ester etc.
Among the present invention, the concentration of polyurethane urea solutions is preferably the scope of 30 weight %～80 weight % usually.
As the polyurethane that uses among the present invention, use the polyalcohol, MDI of molecular weight 1000～8000, from ethylene glycol, 1, ammediol and 1, at least a kind the glycol of selecting in the 4-butanediol and synthesizing, and, as based on the molal quantity of the NCO base of vulcabond with based on the addition ratio of the ratio of the molal quantity of hydroxyl groups, be preferably and be not less than 1.3.
Being more preferably and using number-average molecular weight is 2500～5000 polytetramethylene ether diol, as being 3.0～4.5 based on the molal quantity of the NCO base of vulcabond with based on the addition ratio of the ratio of the molal quantity of hydroxyl groups.
The synthetic of this polyurethane preferably adopted following method, for example, various raw materials are put into DMAc, DMF, DMSO, NMP etc. and is in the solvent of principal component with them, make it dissolving, be heated to proper temperature, make it reaction, obtain a so-called Completion Techniques of polyurethane solutions; After at first making polyalcohol and MDI frit reaction, reactants dissolved in above-mentioned solvent, again with above-mentioned glycol reaction, is obtained the method for polyurethane solutions.
When synthetic this polyurethane, preferably with a kind or be no less than 2 kinds amine series catalysts and organo-metallic catalyst mixes and uses.As the amine series catalysts, N is for example arranged, the N-dimethyl cyclohexyl amine, N, the N-dimethyl benzyl amine, triethylamine, N-methylmorpholine, N, 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-dimethylamino ether, N, N, N ', N ', N '-pentamethyl Diethylenetriamine, tetramethyl guanidine, triethylenediamine, N, N '-lupetazin, N-methyl-N '-dimethylaminoethyl-croak piperazine, N-(2-dimethylaminoethyl) morpholine, the 1-methylimidazole, 1, the 2-methylimidazole, N, N-dimethylamino ethanol, N, N, N '-triethyl group aminoethyl ethanolamine, N-methyl-N '-(2-ethoxy) croak piperazine, 2,4,6-three (dimethylaminoethyl) phenol, N, N-dimethylamino hexanol, triethanolamine etc.
As organo-metallic catalyst, preferably tin octoate, dibutyl tin laurate, lead octoate dibutyl ester etc.
Among the present invention, the concentration of polyurethane solutions is preferably 30 weight %～80 weight % usually, and is preferably the same with the concentration of polyurethane urea solutions.
Among the present invention, can adopt the method for in polyurethane urea solutions, adding polyurethane solutions, also can adopt the method for in polyurethane solutions, adding polyurethane urea solutions.
Among the present invention, consider, preferably adopt the method in the many solution of the solution amount of adding to that amount is few from solution is evenly mixed mutually.
Among the present invention, preferably contain the polyurethane of 3 weight %～97 weight %, more preferably contain 3 weight %～50 weight %, most preferably contain 10 weight %～40 weight %.
At this moment, preferably polyurethane solutions is added in the polyurethane urea solutions.
As the method that polyurethane solutions is added in polyurethane urea solutions, can adopt any means, preferably the method for being undertaken by static mixer, utilize to stir the method for carrying out etc.
At this, reagent such as polyurethane solutions that is added and anti-chlorine degradation, spinning photostabilizer, antioxidant and pigment etc. are added to simultaneously.
Among the present invention, to being that the solution of solute carries out spinning with polyurethane-urea and polyurethane, as preferably dry spinning or wet type spinning of spinning process.
Dry spinning does not have particular determination, can adopt any means.
The residual deformation of polyurethane elastomeric fiber of the present invention and stress relax, and are easy to be subjected to the influence of the velocity ratio of deflector roll and up-coiler, so preferably suitably determine according to purposes.
Among the present invention, the velocity ratio of deflector roll and up-coiler is that 1.15～1.65 to reel be desirable.Particularly when making the polyurethane elastomeric fiber that high residual deformation and low stress relax, above-mentioned velocity ratio is taken as 1.15～1.40 and reel better, be taken as 1.15～1.35 and reel best.
On the other hand, when making the polyurethane elastomeric fiber of low residual deformation and heavily stressed mitigation, above-mentioned velocity ratio is taken as 1.25～1.65 and reel better, is taken as 1.35～1.65 and reel best.
The intensity of the polyurethane elastomeric fiber when making from improving considers that spinning speed is preferably and is not less than 450m/ minute.
Embodiment
Below illustrate in greater detail the present invention with embodiment.
Assay method to the intensity among the present invention, stress mitigation, residual deformation, percentage elongation, anti-chlorine embrittlement ability, hot residual deformation during beginning describes.
[intensity, stress mitigation, residual deformation, percentage elongation]
Intensity, stress mitigation, residual deformation, percentage elongation can use the cupping machine of omnipotent accurate cupping machine 4502 types, by the test portion silk is carried out stretching test measurement.
These can define according to following.With the test portion of 5cm (L1), be stretched to 300% length with 50cm/ minute draw speed, 5 times repeatedly, the stress of this moment is designated as (G1).
Tensile elongation with 300% kept for 30 seconds, and the stress of maintenance after 30 seconds is designated as (G2).Tensile elongation is replied, and the length that stress becomes 0 test portion silk is designated as (L2).Further, be stretched to the fracture of test portion silk at the 6th time.Stress during this fracture is designated as (G3), and the length of test portion silk is designated as (L3) during with fracture.
Below, utilize following formula to obtain above-mentioned characteristic.
Intensity=(G3)
Stress relaxes=100 * ((G1)-(G2))/(G1)
Residual deformation=100 * ((L2)-(L1))/(L1)
Percentage elongation=100 * ((L3)-(L1))/(L1)
[anti-chlorine embrittlement ability]
The elastic polyurethane silk:
Inferior sodium chlorite liquid is diluted with ion exchange water, forming effective chlorine density is 3ppm and then urea concentration 3ppm, to join with the chlorine water that phosphate buffer is adjusted to pH7.2 in the thermostat of adjustment to 28 ℃, apply 5g weight for the test portion silk, be impregnated in the thermostat, estimate the time that disconnects up to the test portion silk.
Knitwear:
The knitwear of cross directional stretch 50% are impregnated in the chlorine water thermostat identical with above-mentioned elastic polyurethane silk, estimate the time that disconnects up to the elastic polyurethane silk that can see knitwear.
[hot residual deformation]
(length=L5) elongate 100% (length=2 * (L5)) under this length, was handled 1 minute down at 180 ℃ with the test portion silk under free state.And then under this length, under room temperature, placed 1 day.Remove the extended state of test portion silk, measure its length (L6).
Hot residual deformation=100 * ((L6)-(L5))/(L5)
[embodiment 1]
The tetramethylene ether glycol of molecular weight 1800 and MDI are packed in the container, making the CR value is 1.58,90 ℃ of reactions down, with the reactants dissolved that obtains at N, in the N-dimethylacetylamide (DMAc), then in the solution that has dissolved above-mentioned reactant, add the DMAc solution that contains ethylenediamine and diethylamine, obtain that solid constituent is the polyurethane urea solutions (solution A 1) of 35 weight % in the polymer.
In addition, the tetramethylene ether glycol of molecular weight 2900 and MDI are packed in the container, making the CR value is 3.5,90 ℃ of reactions down, then be dissolved among the DMAc, then in the solution that has dissolved above-mentioned reactant, add the DMAc solution that contains ethylene glycol, butanols, obtain that solid constituent is the polyurethane solutions (solution B 1) of 35 weight % in the polymer.
Then,, add the solution B 1 of 450g, stirred 2 hours, make solution C 1 with respect to the solution A 1 of 1800g.Then in solution C 1, add zinc oxide (this Chuang of micronized zinc oxide, chemistry (strain) system), make the zinc oxide that contains 3 weight % in the polyurethane elastomeric fiber, stirred again 2 hours, make solution D 1.The velocity ratio of deflector roll and up-coiler is taken as 1.20,, solution D 1 is carried out dry spinning, polyurethane elastomeric fiber (44 dtexs, 4) is reeled with 540m/ minute speed.
In spinning, there are not troubles such as fracture of wire fully, spinning stably.The polyurethane elastomeric fiber that obtains contains the polyurethane of 19 weight %, has good anti-chlorine embrittlement performance, and has good hot residual deformation.The result is shown in table 1 in the lump.
[embodiment 2]
Add 970g solution B 1 with respect to 1800g solution A 1, stirred 2 hours, make solution C 2.Then in solution C 2, add zinc oxide (this Chuang of micronized zinc oxide, chemistry (strain) system), make the zinc oxide that contains 3 weight % in the polyurethane elastomeric fiber, stirred again 2 hours, make solution D 2.The velocity ratio of deflector roll and up-coiler is taken as 1.20, solution D 2 is carried out dry spinning, polyurethane elastomeric fiber (44 dtexs, 4) is reeled with 540m/ minute speed.
Troubles such as fracture of wire do not appear in spinning fully, spinning stably.The polyurethane elastomeric fiber that obtains contains the polyurethane of 34 weight %, has extraordinary anti-chlorine embrittlement performance, and has extremely good hot residual deformation.The result is shown in table 1 in the lump.
[embodiment 3]
The tetramethylene ether glycol of molecular weight 2100 and MDI are packed in the container, making the CR value is 2.1,90 ℃ of reactions down, then be dissolved among the DMAc, then add the DMAc solution that contains ethylene glycol, butanols in above-mentioned solution, the solid constituent that obtains in the polymer is the polyurethane solutions (solution B 2) of 35 weight %.
Then,, add the solution B 2 of 1200g, stirred 2 hours, make solution C 3 with respect to the solution A 1 of 1800g.Then in solution C 3, add zinc oxide (this Chuang of micronized zinc oxide, chemistry (strain) system), make the zinc oxide that contains 3 weight % in the polyurethane elastomeric fiber, stirred again 2 hours, make solution D 3.The velocity ratio of deflector roll and up-coiler is taken as 1.20, solution D 3 is carried out dry spinning, polyurethane elastomeric fiber (44 dtexs, 4) is reeled with 540m/ minute speed.
Troubles such as fracture of wire do not appear in spinning fully, spinning stably.The polyurethane elastomeric fiber that obtains contains the polyurethane of 39 weight %, has good anti-chlorine embrittlement performance, and has extremely good hot residual deformation.The result is shown in table 1 in the lump.
[embodiment 4]
Add the solution B 1 of 1200g with respect to the solution A 1 of 800g, stirred 2 hours, make solution C 4.Then in solution C 4, add zinc oxide (this Chuang of micronized zinc oxide, chemistry (strain) system), make the zinc oxide that contains 3 weight % in the polyurethane elastomeric fiber, stirred again 2 hours, make solution D 4.The velocity ratio of deflector roll and up-coiler is taken as 1.20, solution D 4 is carried out dry spinning, polyurethane elastomeric fiber (44 dtexs, 4) is reeled with 540m/ minute speed.
Though the spinning quite stable just produced about 1 time fracture of wire in average 24 hours.The polyurethane elastomeric fiber that obtains contains the polyurethane of 58 weight %, has extremely good anti-chlorine embrittlement performance, and has extremely good hot residual deformation.The result is shown in table 1 in the lump.
[embodiment 5]
Add the solution B 1 of 1600g with respect to the solution A 1 of 400g, stirred 2 hours, make solution C 5.Then in solution C 5, add zinc oxide (this Chuang of micronized zinc oxide, chemistry (strain) system), make the zinc oxide that contains 3 weight % in the polyurethane elastomeric fiber, stirred again 2 hours, make solution D 5.The velocity ratio of deflector roll and up-coiler is taken as 1.20, solution D 5 is carried out dry spinning, polyurethane elastomeric fiber (44 dtexs, 4) is reeled with 540m/ minute speed.
The spinning quite stable, but produced about 1 time fracture of wire in average 24 hours.The polyurethane elastomeric fiber that obtains contains the polyurethane of 78 weight %, has the extremely good degradation property of anti-chlorine, and has extremely good hot residual deformation, and the result is shown in table 1 in the lump.
[embodiment 6]
Except using hydrotalcite (Mg
6Al
2(OH)
16CO
34H
2O) powder replaces outside the zinc oxide, and other are the same with embodiment 2, obtain the elastic polyurethane silk.The polyurethane elastomeric fiber that obtains has extremely good anti-chlorine embrittlement performance, and has extremely good hot residual deformation.The result is shown in table 1 in the lump.
[embodiment 7]
Except using the MgO/ZnO solid-solution powder to replace the zinc oxide, other are the same with embodiment 2, obtain the elastic polyurethane silk.The polyurethane elastomeric fiber that obtains has extremely good anti-chlorine embrittlement performance, and has extremely good hot residual deformation.The result is shown in table 1 in the lump.
[embodiment 8]
Except using Mg
2Ca (CO
3)
450: 50 mixture of (Off Application ィ ト) and hydromagnesite (Britain Microfine Minerals Ltd. system) replaces outside the zinc oxide, and other are the same with embodiment 2, obtain the elastic polyurethane silk.The polyurethane elastomeric fiber that obtains has extremely good anti-chlorine embrittlement performance, and has extremely good hot residual deformation, and the result is shown in table 1 in the lump.
[embodiment 9]
Embodiment 2 polyurethane elastomeric fibers and the polyhexamethylene adipamide that obtain are carried out melt spinning, with the polyamide fiber that obtains (50 DENIER/17 thread), the tricot of the 2 kind modes of making through compiling, this tricot is dyeed after the fine finishining, make and be made into swimsuit.
The anti-chlorine embrittlement ability of tricot of dyeing has 122 hours premium properties, and liquor style is also fine.
The swimsuit that obtains is worn in the actual swimming pool tests, the result is up to seeing that the elastic polyurethane silk produces fracture of wire, is 113 hours (wearing 4 times mean value), and durability is good.
[comparative example 1]
Solution A 1 with respect to 1800g adds zinc oxide (this Chuang of micronized zinc oxide chemistry (strain) system), make the zinc oxide that contains 3 weight % in the polyurethane elastomeric fiber, stirred 2 hours, make solution E 1, the speed of deflector roll and up-coiler is taken as 1.20, solution E 1 is carried out dry spinning, polyurethane elastomeric fiber (44 dtexs, 4) is reeled with 540m/ minute speed.The polyurethane elastomeric fiber that obtains is not contain polyurethane, and anti-chlorine embrittlement performance is low, and hot residual deformation is also low, and the result is shown in table 1 in the lump.
[comparative example 2]
Solution B 1 with respect to 1800g adds zinc oxide (this Chuang of micronized zinc oxide, chemistry (strain) system), makes the zinc oxide that contains 3 weight % in the polyurethane elastomeric fiber, stirs 2 hours, makes solution E 2.The velocity ratio of deflector roll and up-coiler is taken as 1.20, solution E 2 is carried out dry spinning, polyurethane elastomeric fiber (44 dtexs, 4) is reeled with 540m/ minute speed.With solution E 2 spinning, spinnability is very poor, and fracture of wire is given birth in not stopping pregnancy.
The polyurethane elastomeric fiber that obtains is not contain polyurethane-urea, though anti-chlorine embrittlement performance height, hot residual deformation is low simultaneously, recovery very poor (stress mitigation and residual deformation are big), and the result is shown in table 1 in the lump.
[comparative example 3]
Use the polyurethane elastomeric fiber of comparative example 1, with embodiment 9 the same tricot and the swimsuits made.The anti-chlorine embrittlement ability of the tricot after the dyeing is very short, has only 86 hours, and the dress of swimsuit in the time of 79 hours, just can see that the elastic polyurethane silk produces fracture of wire with test.
Table 1
| A | B | A/B (weight ratio) | Metallic compound | Intensity (cN) | Stress relaxes (%) | Residual deformation (%) | Percentage elongation (%) | Anti-chlorine embrittlement ability (time) | Hot residual deformation (%) | |
| Embodiment 1 | A1 | B1 | 4/1 | Zinc oxide | 42 | 29 | 21 | 455 | 133 | 61 |
| Embodiment 2 | A1 | B1 | 180/97 | Zinc oxide | 47 | 30 | 20 | 458 | 138 | 65 |
| Embodiment 3 | A1 | B2 | 3/2 | Zinc oxide | 41 | 30 | 22 | 461 | 126 | 70 |
| Embodiment 4 | A1 | B1 | 2/3 | Zinc oxide | 44 | 30 | 23 | 470 | 140 | 71 |
| Embodiment 5 | A1 | B1 | 1/4 | Zinc oxide | 41 | 31 | 24 | 465 | 157 | 71 |
| Embodiment 6 | A1 | B1 | 180/97 | Hydrotalcite | 45 | 30 | 21 | 455 | 134 | 66 |
| Embodiment 7 | A1 | B1 | 180/97 | MgO/Zn O | 44 | 31 | 22 | 460 | 135 | 65 |
| Embodiment 8 | A1 | B1 | 180/97 | Mg 2Ca( CO 3) 4/ hydromagnesite | 46 | 30 | 20 | 451 | 130 | 63 |
| Comparative example 1 | A1 | - | ∞ | Zinc oxide | 41 | 28 | 21 | 479 | 117 | 55 |
| Comparative example 2 | - | B1 | 0 | Zinc oxide | 38 | 33 | 30 | 472 | 173 | 75 |
A: polyurethane urea solutions B: polyurethane solutions
The invention effect
A kind of have good anti-chlorine embrittlement performance and hot residual deformation properties can be provided according to the present invention, be suitable for the polyurethane elastomeric fiber of swimsuit purposes.
The polyurethane elastomeric fiber of the application of the invention can provide garment fitting, liquor style good and knit goods and swimsuit deteriorated little, that durability is good that the chlorine water such as swimming pool causes.
Claims (16)
1, a kind of polyurethane elastomeric fiber, it is characterized in that: it is the elastomer that is formed with the mixture of the polyurethane of making through the glycol chains elongation by polyurethane-urea, wherein the content of polyurethane is 3 weight %～90 weight %, and the weight ratio of polyurethane and polyurethane-urea is 1/4～4/1.
2, the polyurethane elastomeric fiber of putting down in writing according to claim 1, it is characterized in that: polyurethane is that 1000～8000 polyalcohol and methyl diphenylene diisocyanate polymerization obtain by glycol, molecular weight, and above-mentioned polyalcohol is copolymer and oxolane and 2 that are selected from polytetramethylene ether diol, oxolane and 3-methyltetrahydrofuran, in the copolymer of 3-dimethyl-tetrahydrofuran a kind or more than.
3, according to the polyurethane elastomeric fiber of claim 1 record, it is characterized in that: in the polyurethane, as being 1.3 or greater than 1.3 based on the molal quantity of the NCO base of vulcabond with based on the addition ratio of the ratio of the molal quantity of hydroxyl groups.
4, the polyurethane elastomeric fiber of putting down in writing according to claim 1, it is characterized in that: polyurethane is by from ethylene glycol, 1, ammediol, 1, at least a glycol of selecting in the 4-butanediol, molecular weight are that 2500～5000 polytetramethylene ether diol and methyl diphenylene diisocyanate are synthetic, as being 3.0～4.5 based on the molal quantity of the NCO base of vulcabond with based on the addition ratio of the ratio of the molal quantity of hydroxyl groups.
5, according to the polyurethane elastomeric fiber of claim 1 record, it is characterized in that: contain from following 1)～3) at least a kind metallic compound selecting, wherein,
1) any of the oxide of the metal of from Mg, Zn, Al, selecting, composite oxides, hydroxide;
2) in the oxide of the metal of from Mg, Zn, Al, selecting, composite oxides and the hydroxide, by 2 kinds that select or greater than 2 kinds of solid solution that constitute;
3) hydrotalcite-based compound.
6, according to the polyurethane elastomeric fiber of claim 5 record, it is characterized in that: the above-mentioned metallic compound that contains 0.1 weight %～10 weight %.
7, according to the polyurethane elastomeric fiber of claim 1 record, it is characterized in that: contain Mg
2Ca (CO
3)
4Mixture with hydromagnesite.
8, according to the polyurethane elastomeric fiber of claim 7 record, it is characterized in that: the said mixture that contains 0.1 weight %～10 weight %.
9, a kind of cloth and silk is characterized in that: the polyurethane elastomeric fiber that contains claim 1 record.
10, a kind of swimsuit is characterized in that: it is to be made of the cloth and silk that claim 9 is put down in writing.
11, a kind of manufacture method of polyurethane elastomeric fiber, it is characterized in that: to by polyurethane-urea with through glycol chains elongation and the polyurethane of making constitutes and the content of polyurethane is 3 weight %～90 weight %, and the weight ratio of polyurethane and polyurethane-urea is that 1/4～4/1 polymeric blends is that the solution of solute carries out spinning.
12, according to the manufacture method of the polyurethane elastomeric fiber of claim 11 record, it is characterized in that: polyurethane solutions is added in the polyurethane urea solutions, then carry out spinning.
13, according to the manufacture method of the polyurethane elastomeric fiber of claim 11 record, it is characterized in that: spinning process is the dry spinning method.
14, according to the manufacture method of the polyurethane elastomeric fiber of claim 11 record, it is characterized in that: as polyurethane, use is 1000～8000 the polyalcohol and the polyurethane of methyl diphenylene diisocyanate polymerization by glycol, molecular weight, wherein above-mentioned polyalcohol is copolymer and oxolane and 2 that are selected from polytetramethylene ether diol, oxolane and 3-methyltetrahydrofuran, in the copolymer of 3-dimethyl-tetrahydrofuran a kind or more than.
15, according to the manufacture method of polyurethane elastomeric fibers of claim 11 or 14 records, it is characterized in that: in the polyurethane, as being 1.3 or greater than 1.3 based on the molal quantity of the NCO base of vulcabond with based on the addition ratio of the ratio of the molal quantity of hydroxyl groups.
16, according to the manufacture method of the polyurethane elastomeric fiber of claim 11 record, it is characterized in that: polyurethane is by being selected from ethylene glycol, 1, ammediol, 1, at least a kind of glycol of 4-butanediol, molecular weight are that 2500～5000 polytetramethylene ether diol and methyl diphenylene diisocyanate are synthetic, as being 3.0～4.5 based on the molal quantity of the NCO base of vulcabond with based on the addition ratio of the ratio of the molal quantity of hydroxyl groups.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP71881/2001 | 2001-03-14 | ||
| JP2001071881 | 2001-03-14 |
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| CN1213178C true CN1213178C (en) | 2005-08-03 |
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| CNB021198225A Expired - Fee Related CN1213178C (en) | 2001-03-14 | 2002-03-14 | Polyurethane spandex and its manufacturing method, cottons and silks and swimwear |
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|---|---|
| KR (1) | KR100866054B1 (en) |
| CN (1) | CN1213178C (en) |
| TW (1) | TWI238206B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101484620B (en) * | 2006-07-04 | 2011-05-18 | 旭化成纤维株式会社 | Polyurethane urea elastic fiber |
| KR100780395B1 (en) * | 2006-09-04 | 2007-11-29 | 태광산업주식회사 | Chlorine resistant polyurethaneurea elastic fiber and preparation of thereof |
| KR101262775B1 (en) | 2006-12-29 | 2013-05-09 | 주식회사 효성 | A polyurethaneurea fibers with stabilization of inorganic materials |
| KR100870533B1 (en) * | 2007-06-28 | 2008-11-26 | 주식회사 효성 | Spandex fibers containing a heat-treated mineral mixture of huntite- hydromagnesite |
| KR20090005802A (en) * | 2007-07-10 | 2009-01-14 | 주식회사 효성 | Spandex fibers containing hydromagnesite |
| KR101166807B1 (en) | 2008-10-28 | 2012-07-26 | 태광산업주식회사 | High heat and chlorine resistant polyurethaneurea elastic fiber and preparation of thereof |
| CN102534856B (en) * | 2010-12-10 | 2014-08-13 | 烟台泰和新材料股份有限公司 | Preparation method of spandex spinning stock solution by PCL dry method |
| JP5688601B2 (en) * | 2011-06-23 | 2015-03-25 | 東レ・オペロンテックス株式会社 | Polyurethane yarn and fabric and swimsuit using the same |
| KR101453649B1 (en) * | 2013-01-25 | 2014-10-22 | 주식회사 효성 | Polyurethaneurea elastic fiber and manufacturing method of the same |
| CN104726960A (en) * | 2013-12-20 | 2015-06-24 | 浙江华峰氨纶股份有限公司 | Polyurethane elastic fiber with improved heat-setting performance, and preparation method thereof |
| US20180305842A1 (en) * | 2015-06-30 | 2018-10-25 | Invista North America S.A R.L. | Polyurethane fiber including copolymer polyol |
| CN105603583B (en) * | 2015-12-30 | 2017-10-24 | 浙江华峰氨纶股份有限公司 | A kind of spandex with endurance and fusible characteristic and preparation method thereof |
| KR101766269B1 (en) * | 2016-03-25 | 2017-08-08 | 태광산업주식회사 | Polyurethaneurea elastic fiber |
| KR101943894B1 (en) * | 2017-11-23 | 2019-01-30 | 태광산업주식회사 | Preparation Method of Black Polyurethaneurea Fiber |
| CN108277553A (en) * | 2017-12-21 | 2018-07-13 | 苏州浩洋聚氨酯科技有限公司 | A kind of modified form polyurethane elastomeric fiber |
| CN108277551A (en) * | 2017-12-21 | 2018-07-13 | 苏州浩洋聚氨酯科技有限公司 | A kind of polyurethane composite fibre |
| CN108277554A (en) * | 2017-12-21 | 2018-07-13 | 苏州浩洋聚氨酯科技有限公司 | A kind of new polyurethane fiber |
| CN108277552A (en) * | 2017-12-21 | 2018-07-13 | 苏州浩洋聚氨酯科技有限公司 | A kind of polyurethane elastomeric fiber based on butanediol |
| WO2020153375A1 (en) * | 2019-01-22 | 2020-07-30 | 旭化成株式会社 | Polyurethane elastic fiber and fabric containing same |
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| US4916199A (en) * | 1988-07-14 | 1990-04-10 | The B. F. Goodrich Company | Polyurethanes made from blends of polypropyleneoxide polyol and organic-silicone block copolymer based polyol intermediates |
| US6353049B1 (en) * | 1997-02-13 | 2002-03-05 | Asahi Kasei Kabushiki Kaisha | Elastic polyurethane fiber and process for producing the same |
| KR100200422B1 (en) * | 1997-02-17 | 1999-06-15 | 한형수 | The manufacture method of a high density polyurethane-urea system high molecule solution |
| JP4017232B2 (en) * | 1998-02-05 | 2007-12-05 | Ｂａｓｆジャパン株式会社 | Polyurethane resin composition for extrusion molding |
| JP3883278B2 (en) * | 1998-02-13 | 2007-02-21 | 旭化成せんい株式会社 | Method for producing polyurethane elastic fiber and its water-wearing elastic fabric |
| JP3968736B2 (en) * | 1998-08-20 | 2007-08-29 | オペロンテックス株式会社 | Polyurethane yarn and process for producing the same |
| JP2001055628A (en) * | 1999-08-10 | 2001-02-27 | Okada Engineering:Kk | Production of polyurethane fiber |
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2002
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| KR100866054B1 (en) | 2008-10-30 |
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