CN1058813A - Elastic core and sheath type bicomponent filament yarn and contain the fabric construction of this bicomponent filament yarn - Google Patents
Elastic core and sheath type bicomponent filament yarn and contain the fabric construction of this bicomponent filament yarn Download PDFInfo
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- CN1058813A CN1058813A CN 91103483 CN91103483A CN1058813A CN 1058813 A CN1058813 A CN 1058813A CN 91103483 CN91103483 CN 91103483 CN 91103483 A CN91103483 A CN 91103483A CN 1058813 A CN1058813 A CN 1058813A
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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Abstract
A kind of elastic core and sheath type bicomponent filament yarn, it is by thermoplasticity inelastic body skin component, as polyamide, copolyesters and polyolefin, and cross-linked polyurethane, preferably form based on the cross-linked polyurethane core component of allophanate cross-bond, the crosslink density (Y micromoles per gram) of its SMIS/skin conjugate ratio (X) and polyurethane satisfies following inequality simultaneously:
3≤X≤100 '; Y 〉=0 and Y 〉=-8.7X+52
Excellent workability when long filament incohesion of the present invention and elastic stretching recovery, heat resistance and knitting or braiding can provide quality high fabric construction, high tensility for example, the support type stockings that outward appearance and sense of touch are good.
Description
The present invention relates to the elastic core and sheath type bicomponent filament yarn, it is made up of fine thermoplasticity inelastic body skin component of one-tenth such as polyurethane core component, and relates to the fabric construction that contains this bicomponent filament yarn.
Up to the present, the polyurethane elastomer long filament has been applied to every field, and its use has brought particular performances.Yet these polyurethane elastomer long filaments are different from common synthetic fiber filament, because its intrinsic adhesivity.Therefore adhere to each other each other, not only need excessive tension force for pulling out by the yarn volume, and when the long filament unwinding of reeling tension force generation great changes.
In addition, because the polyurethane elastomer long filament be with elongating once little tensile stress, and coefficient of friction is big, the poor processability of this long filament is difficult to processing, therefore in post-processing step, even under the strict process control condition, thing followed problem is a filament breakage, and is knitting unequal.One of measure that overcomes above-mentioned difficulties is to use oil agent, and (for example, a kind of oil agent of Japanese patent publication 40-5557 and 46-16312 disclosure mainly contains the dimethyl silscone that mixes with metallic soap, monoamine etc.
Yet, it is believed that by oil agent to reach to a certain degree improvement, but be restricted and be unfavorable.That is to say, suppose in spinning and under the situation of reeling on the take up roll, if the adhesivity of long filament reduces, owing to remove spider web, long filament package densified or the like, operating winding can not carry out for a long time continuously, along with reduce (for example 100 millimeters or littler) of the increase (for example 500 meters/minute or bigger) of winding speed in reeling and yarn coil diameter, this trend becomes obviously.
Otherwise, if long filament is become sticky, can carry out long operating winding, but because the unwinding difficulty will produce a series of trouble at post-processing step.
Therefore, there is the promising problem that this difficulty must distinguishingly adopt recoil step or similar step that overcomes.That is to say, there is the same good alternative situation of operability with other synthetic fiber, for example adhere to by in spinning process, eliminating mutually fully, also will allowing reels carries out for a long time, in addition, the situation that long filament is reached in the easy processing of post-processing step is only utilized to oil and must not be expected to reach by accurate control.
As another measure of eliminating these difficulties, once the someone recommends the core-sheath bicomponent filament yarn so far, the elastic filament of forming by concentric polyurethane core and the compound monofilament of polyurethane skin (the Japanese patent publication 61-14 of inventor application for example for example, 245), with the elastic filament of forming by polyurethane core and the compound monofilament of polyolefin skin (for example Japanese patent publication 61-194,221).
The concentric bicomponent filament yarn of above-mentioned elastic polyurethane-polyurethane-type, because skin is made of polyurethane, with regard to its intrinsic adhesivity, in the high-speed winding ability of spinning step, in the machinability of post-processing step, with regard to the aspects such as sense of touch performance of its product of making, all have weak point, this in addition long filament is difficult to and the polyester filament blending.
Under the situation of polyurethane core and polyolefin skin bicomponent filament yarn, there is the defective of poor heat resistance, if attempt to improve heat resistance by the hardness that increases the polyurethane core component, then the elastic stretching of bicomponent filament yarn recovers to reduce.In addition, because core/skin conjugate ratio is very little, skin greatly influences and has reduced the character of long filament.Therefore such long filament comes into operation, and mainly is the viscosity of utilizing it.
In addition, people have known that also the fabric construction that is made of the elastic polyurethane long filament has undesirable tactile properties (as feel or sense of touch), but that the dyeability difference is reaching COLOR FASTNESS is poor.Because production technology is accompanied by exceedingly difficult situation, so almost there is not the independent fabric construction that constitutes by the polyurethane elastomer long filament on the market.
In order to strengthen the polyurethane elastomer yarn, promote its processed, for many purposes, recommended and used to comprise the bag core FANCY YARNS that is wound with the nylon coating cotton thread around polyurethane core yarn and this heart yarn line.But compare with the polyurethane bare wire, because the coating cotton thread of having reeled, the fiber number of bag core FANCY YARNS increases, with the thick and poor transparency of knitwear of such yarn braiding.In addition, making this yarn needs encapsulation steps, has brought the extremely low different problem of productive rate.
Especially stockings, importantly therefore tensile property and particularly to the adaptability of leg, except above-mentioned bag core FANCY YARNS, recommends to use the potential crimping property bicomponent filament yarn.For example, the crimp yarn of forming by the eccentric polyurethane core of having saved encapsulation steps and polycaprolactam skin bicomponent filament yarn, (Japanese patent publication 55-27,175), and all be known by comprising the elastic filament (Japanese patent publication 1-118,619) that eccentric cross-linked polyurethane elastomer composite silk forms.
On the other hand, there are shortcoming in eccentric polyurethane core and polycaprolactam skin bicomponent filament yarn, and the result is that it need stretch and bounce back treatment step improving its curling restoring force, and have very low stretching restore modulus when it curls.And must give great concern to the inhomogeneities of curling.In addition, there are some problems in the stockings that are made of such yarn, poor transparency for example, and knitting quality is poor, and outward appearance is undesirable or the like when being through on the leg.
In addition, the polyurethane elastomer yarn is at most 10% more 100 ℃ hot water shrinkage.Method as increasing this value has hot-stretch or cold stretch technology.When the polyurethane elastomer yarn carried out hot-stretch, for example, at 120 ℃ of stretching 2-3 doubly, the hot water percentage of contraction was generally 20-30.But before carrying out such hot water shrinkage's measurement, the polyurethane elastomer yarn that is stretched at room temperature shrinks earlier naturally.In addition, different with other synthetic fiber, the polyurethane elastomer yarn almost can not formalize, and therefore is difficult to process.That is to say that in put procedure, even do not heat, yarn also produces nature and shrinks, and therefore has the size problem of unstable.
As the method for improving draftability, Japanese patent publication 55-9,093 has proposed a kind of method, promptly when conjugate spinning that inelastic body is compound with the polyether polyols with reduced unsaturation that contains the unreacting isocyanate base, the amount of the unreacting isocyanate base that mixes is every gram polymer 1-45 microequivalent, but being the content of isocyanate group in the polyurethane, the difficulty of this method must be controlled in the above-mentioned scope till spinning, and owing to use fusing point to be 200-235 ℃, the polyurethane that hard segment increases greatly, it is poor that the elastic stretching of gained bicomponent filament yarn recovers.
The inventor carries out the result of lucubrate at top problem, thereby has finished the present invention.
First purpose of the present invention provides a kind of new elastic composite long filament, and it has excellent elasticity tensility, and owing to there is not adhesivity, machinability improves in spinning and coiling step and post-processing step.
But second purpose of the present invention provides a kind of polyurethane filament that has excellent dyeability and present high shrinkage by hot water treatment.
The 3rd purpose of the present invention provides a kind of fabric construction of novelty, women's hosiery particularly, it has the new capability that is different from the conventional fabrics structure that comprises the naked yarn of polyurethane fully, for example You Yi elastic elongation, heat resistance, sense of touch when wearing and transparency.
That is to say, in order to achieve the above object, according to long filament of the present invention is a kind of flexible core-sheath bicomponent filament yarn, it is characterized in that this bicomponent filament yarn is characterised in that the crosslink density Y(micromoles per gram of core/skin conjugate ratio X and polyurethane by becoming fine thermoplasticity inelastic body skin component and polyurethane core component to form) satisfy following inequality simultaneously:
3≤X≤100
Y 〉=0 reaches
Y≥-8.7X+52
Consider in the spinning process and the balance of melt polyurethane viscosity that the best spinning temperature of preferred above-mentioned inelastic body is up to 238 ℃.
First embodiment of the present invention, the inelastic body in the aforementioned long filament are the polyamide that has one of following characteristics at least: the fusing point of using differential scanning calorimetry (DSC) (DSC) mensuration is in 80 ° of-220 ℃ of scopes; The solution of one gram polymer in 100 milliliter of 98% sulfuric acid is no more than 2.3 at most in the relative viscosity of 25 ℃ of mensuration.
Second embodiment of the present invention, the inelastic body in the aforementioned long filament are to comprise the copolyesters of polyethylene terephthalate as key component and 12-50 mole % isophthalic acid ester comonomer.
The 3rd embodiment of the present invention, inelastic body in the described long filament is a kind of copolyesters, it is by the dicarboxylic acid component of containing 60-88 mole % terephthalic acid (TPA) and 12-40 mole % M-phthalic acid and contains that 75-90% mole % ethylene glycol and 10-25 mole % are at least a to be selected from the copolyesters that following diol component makes, these glycol are diethylene glycols, triethylene glycol, neopentyl glycol and butanediol.
The 4th embodiment of the present invention, the inelastic body in the described long filament is to be selected from polyethylene, polypropylene, the polyolefin of polystyrene and polybutene, the crosslink density Y of polyurethane is at least 6 micromoles per gram, preferably is at least 10 micromoles per gram.
The preferred polyurethane core component of the present invention comprises the polyurethane with multi isocyanate crosslinking, and its crosslink density Y is at least 6 micromoles per gram, preferably is at least 10 micromoles per gram.
Such cross-linked polyurethane preferably has the structure based on the allophanate cross-linked structure.
Most preferred long filament of the present invention is that its shape of cross section is that core component and skin component have common center of gravity basically.
In addition, the present invention includes the fabric construction that contains above-mentioned flexible core-sheath bicomponent filament yarn.
Promptly, according to the present invention, this fabric construction comprises with by becoming fine pad plastic inelasticity body skin component and polyurethane core component to consist of the elastic core and sheath type bicomponent filament yarn of feature, it is characterized in that the core/skin conjugate ratio X and the crosslink density Y(micromoles per gram of polyurethane) satisfy following inequality simultaneously:
3≤X≤100
Y 〉=0 He
Y≥-8.7X+52
The such fabric construction of the present invention is preferentially obtaining enforcement aspect women's hosiery, wherein inelastic body is a polyamide.
In such women's hosiery, most preferred polyamide is a PA-12.
In conjunction with the accompanying drawings, by reading following these detailed description of preferred embodiments, above-mentioned purpose with other of the present invention, it is more apparent that characteristic and advantage will become, wherein:
Fig. 1 is the vertical section sketch of the spinnerets that adopts in making long filament of the present invention, two parts that molten components stream meets in spinnerets of having drawn especially.
At first, in first embodiment of the present invention, as the exemplary of the polyamide that is used to into fine thermoplasticity inelastic body skin component, for example, above mentioned have nylon-6 and a modification of nylon-66.In addition, homopolyamide is as nylon-8, nylon-9, nylon-10, nylon-11, PA-12 or analog, copolyamide, as nylon-6/66, nylon-6/12 or analog, three polyamide, as nylon-6/12/10 or analog, also have many copolyamides and their mixture, also can both preferentially be used.Wherein, PA-12 particularly preferably is used for women's hosiery.
In spinning, consider and melt polyurethane viscosity between balance, the best spinning temperature of these inelastic bodies preferably is no more than 238 ℃, this also is the upper limit of the best spinning temperature of polyurethane.For the measurement of best spinning temperature, can adopt relative viscosity or melting temperature.Example in, for nylon-6, preferably select for use those relative viscosity maximums to be no more than 2.3 nylon-6, this with 1 restrain nylon samples in 100 milliliter of 98% concentrated sulfuric acid solution 25 ℃ of mensuration.In addition, the melting temperature that records with differential scanning calorimetry (DSC) (DSC) is that 80-220 ℃ nylon also is preferred, for example, and modification of nylon-66, nylon-8, nylon-9, nylon-10, nylon-11, PA-12, their copolymer, their mixed polymer or analog.If melting temperature surpasses 220 ℃, the melt stability of core component polyurethane and heat resistance reduce, in the composite spinning process, and the melt viscosity imbalance of core component and skin component, it is low that the stretching of gained fiber recovers modulus, is worthless therefore.It also is worthless that melting temperature is lower than 80 ℃, but because this moment inelastic body the fibre forming property difference and be clamminess.
Secondly, in second embodiment of the present invention, the polyester that is used for the skin component is to comprise the copolyesters of polyethylene terephthalate as major constituent and the acid constituents of 12-50 mole % M-phthalic acid.If in the acid constituents, the content of M-phthalic acid surpasses 50 moles of %, and polymer beads is inter-adhesive, forms bridge joint in the dry run, or spun filament can cause that therefore, this is worthless such as adhesion or similar trouble.Otherwise if M-phthalic acid content is lower than 12 moles of %, best spinning temperature will be elevated to such degree, and consequently the melt viscosity of this melt viscosity and core component almost can not balance in spinning.Therefore also be worthless.So this scope is preferred between 15 moles of % and 45 moles of %.
Particularly in order to improve the hot water shrinkage of long filament, the 3rd embodiment of the present invention is preferred, it comprises that the copolyesters that makes with dicarboxylic acid component and diol component is as the skin component, dicarboxylic acid component wherein contains 60-88 mole % terephthalic acid (TPA) and 12-40 mole % M-phthalic acid diol component contains 75-90 mole % ethylene glycol and 10-25 mole % is selected from diethylene glycol, triethylene glycol, at least a glycol in neopentyl glycol and the butanediol.If the glycol above except that ethylene glycol is less than 10 moles of %, be difficult to reduce and shrink initial temperature, therefore almost can not obtain preferable effect.On the other hand, will be reduced to big like this degree, so that can cause that probably nature shrinks if the amount of such glycol, shrinks initial temperature greater than 25 moles of %.If M-phthalic acid as the amount of dicarboxylic acids less than 12 moles of %, thermal contraction can not reach the improvement of expection, and the amount of M-phthalic acid also is worthless above 40 moles of %, because polymer beads trends towards being clamminess or assembling under this situation, therefore biting particle because of the screw rod of extruder in spinning process produces difficulty.
Be used for copolyesters of the present invention, its glass transition temperature be preferably between 55 ℃ and 80 ℃ scope in.If be lower than 55 ℃, shrink initial temperature and will be reduced to big like this degree, so that can cause that probably nature shrinks.In addition, if surpass 80 ℃, shrink initial temperature and will raise too much, so that fall flat.
In the 4th embodiment of the present invention, the skin component is by at least a polyethylene that is selected from, polystyrene, and the polyolefin of polypropylene and polybutene is formed.Among this embodiment, the crosslink density Y of core component polyurethane is at least 6 micromoles per gram, preferably is at least 10 micromoles per gram.Because the non-constant of this skin component hot property, if crosslink density Y is lower than 6 micromoles per gram, then this bicomponent filament yarn will present low heat resistant, and elastic stretching recovers poor.
According to the present invention, for the core component of long filament, become fine thermoplasticity inelastic body can with known polymer modifiers, as matting agent (for example titanium dioxide), antioxidant, electricity is led agent, fungicide, dyestuff, pigment or analog mix.
According to the present invention, for the core component of bicomponent filament yarn, polyurethane has no particular limits, but as long as it has fibre forming property.Yet thermoplastic polyurethane and crosslinked polyamine fat are preferred.Thermoplasticity polyamine fat is the polymer of melting spinning, and its available high molecular weight diol and organic diisocyanate and chain extender reaction make.
High molecular weight diol is to have terminal hydroxy group and molecular weight is the glycols of 500-5000, and for example, such as polytetramethylene glycol, polypropylene glycol or similar ether alcohol how are such as poly-adipic acid hexylene glycol ester.Poly adipate succinic acid ester, PCDL, polycaprolactone glycol or similar ester polyol.These can use separately or be used in combination.
As chain extender, that mentions has a 1.4-butanediol, ethylene glycol, and propylene glycol, two hydroxyl-oxethyl benzene or analog, its molecular weight is no more than 500 at most.Wherein, 1.4-butanediol and two hydroxyl-oxethyl benzene are particularly preferred.
As organic diisocyanate, that mentions has a methylene phenylene diisocyanate (TDI), 4.4 '-methyl diphenylene diisocyanate (MDI), non-yellowing vulcabond, as 1.6-hexyl diisocyanate etc., and their mixture.Wherein, particularly preferably be MDI.
The polyurethane of Shore hardness in the 60-98 scope is preferred.Do not wish the problem that takes place if this hardness less than 60, will produce, stretch and recover and stability of spinning process is reduced to cause the gained bicomponent filament yarn to present low elasticity.In addition, if this hardness surpasses 98, polyurethane itself has so low elastic stretching and recovers, if so that do not rely on coiled structure, the stretching that just can not obtain the long filament expected recovers, and will cause unfavorable problem, consequently the best melt spinning condition for the polyurethane of this hardness is limited in the very narrow scope.The preferable range of this hardness is between 65 and 95.
Such polyurethane can with known polymer modifier, as dyestuff, pigment, the UV stabilizing agent, the UV absorbent, fungicide or analog mix.
Further improve at needs under the situation of compatibility or the like of heat resistance, elastic stretching recovery, core component and skin component of bicomponent filament yarn, in core component, can arrange the cross-linked polyurethane that makes by top polyurethane and polyisocyanates reaction.About cross-linking method, can use the inventor at Japanese patent publication 58-46, the method described in 573, promptly molten thermoplastic polyurethane mixes with polyisocyanates, thus it is crosslinked to finish allophanate in spinning process or after the spinning.
A kind of compound that polyisocyanates is made up of polyol component and isocyanate component contains 2 at least in its molecule, preferably 2-3 isocyanate group (NCO yl).As polyol component, the glycol of average hydroxy functionality 2-3 and the mixture of triol, or synthetic many alcohol of degree of functionality 2-3 are applicable to that above mentioned molecular weight is the glycols that 300-4000 is used for synthesis of polyurethane.In addition, as isocyanate component, can use the aforementioned vulcabond that is used for synthesis of polyurethane, the tripolymer of organic diisocyanate, the product of trimethylolpropane and organic diisocyanate, degree of functionality is isocyanates (for example isocyanates of carbodiimides modification) of 2-3 or the like, and their mixture.
The reaction of above-mentioned two components can be undertaken by any known method, yet, be preferably under the excessive situation of the content of isocyanate group and react, promptly the content of isocyanate group is 3-22%(weight in the product).Much less, this amount depends on the physical property (as heat resistance, elastic stretching recovers or similar performance) of purpose product and the polyalcohol that uses.
The feeding quantity of this polyisocyanates is preferably in the 6-40%(weight of the polyurethane/polyisocyanate mixtures weight that is used for core component) in the scope.This feeding quantity depends on the kind of the content and the used carbimide of NCO base.If feeding quantity surpasses 40%(weight) because mixing is inhomogeneous, the spinning operation instability, the long filament mechanical performance that perhaps makes is unsatisfactory, and therefore, this is worthless.Otherwise, if feeding quantity is less than 6%(weight) therefore gained long filament heat resistance deficiency, also is worthless.The scope of being more preferably is a 10-30%(weight).
Therefore, the main cross-linked structure that forms the allophanate cross-bond in the polyurethane core component, the cross-linked structure that is mainly formed by the biuret bonding is worthless simultaneously, but because it makes the spinnability extreme difference that becomes.That is to say that owing to form the speed of the speed of biuret cross linkage greater than the allophanate cross linkage, in spinning process, system viscosity will be increased to the degree to cause stable spinning operation almost can not carry out.
Explained later core/skin conjugate ratio.
Be generally 3-100 as cross section than core/skin conjugate ratio X, 5-90 is better, and 10-80 is better, and 20-70 is best.If core/skin ratio is less than 3, the elastic recovery at high temperature of this long filament stretches and recovers and the heat resistance variation.In addition, if this ratio surpasses 100, skin ruptures easily, or and form monofilament easily, be exposed to monofilament surface to cause core component, but spinnability and photostability will be had a strong impact on like this.
In the present invention, in order to provide performance satisfied bicomponent filament yarn, not only above mentioned conjugate ratio is important, and the crosslink density Y(micromoles per gram of polyurethane core component) also be key factor.Core/skin conjugate ratio X and crosslink density Y must satisfy following inequality simultaneously:
Y 〉=0 He
Y≥-8.7×X+52
That is, when crosslink density is low, must increase according to top second inequality conjugate ratio, otherwise, when crosslink density is high, the applicable expanded range of conjugate ratio.The long filament that does not satisfy top second inequality and constitute is worthless, because the performance of bicomponent filament yarn recovers poor as elastic stretching.Particularly require stable on heating long filament, it is desirable that crosslink density is at least 6 micromoles per gram, is more preferably to be at least 10 micromoles per gram.
Among the present invention, the crosslink density of polyurethane in the core component that this method was measured under crosslink density was meant and uses:
Under the situation of nylon skin component, remove nylon, preparation polyurethane core sample with solvent (as formic acid or similar solvent).In the skin component is under the situation of other polymer, selects appropriate solvent to remove peeling.Then, at 23 ℃, the such polyurethane of 1 gram was dissolved in the dimethyl sulphoxide solution that contains the 200 micromoles per gram n-butylamines of having an appointment after 24 hours, and the n-butylamine of staying in the reaction system carries out back titration (making indicator with bromjophenol blue) with hydrochloric acid/methanol solution of 1/100～1/50N.Crosslink density Y(μ moles per gram) calculate with following equation:
Y=((V
O-V
S) * f-HCl * N-HCl)/(1000 * example weight) * 10
6
In the formula:
W
1: the weight of solvent of sample dissolution (gram),
W
2: the solution weight after the sample dissolution (gram),
V
O: the titer (milliliter) that blank test is required,
V
s: the titer (milliliter) that sample dissolution is required,
F-HCl: titer () and
N-HCl: conventional soln concentration (N).
According to method recited above, the crosslink density of core component is too high may not to be dissolved.Yet self-evident, as long as in having the limit of good spinnability, such system is applicatory.
For the conjugation shape, consider that from stability of spinning process and yarn uniformity the shape of cross section of long filament preferably wherein core component and skin component has common center of gravity basically.And according to the present invention, the shape of cross section of bicomponent filament yarn can be garden garden shape an or non-shape.Wherein, the garden shape is particularly preferred with one heart.
Because core is wrapped fully, and has common basically center of gravity with the skin component, even the viscosity of core component and skin component is some imbalance each other, bicomponent filament yarn of the present invention still has extraordinary spinnability, this is a notable feature of the present invention, and this is to can't see in the eccentric type bicomponent filament yarn.
Below, explain the method for preparing bicomponent filament yarn of the present invention.
During beginning, the thermoplastic polyurethane particle is joined in the extruder with feed hopper, and heating and melting.Suitable melt temperature is between 190 ℃ and 230 ℃.
On the other hand, polyisocyanates is fusion under 100 ℃ or lower temperature in gravitation tank, and deaeration in advance.If melt temperature is too high, the easy sex change of polyisocyanates.Therefore, in the scope of possibility fusion, it is desirable to adopt lower temperature.Generally, be suitable for adopting temperature between room temperature and 100 ℃.
The most handy fusion conjugate spinning device that melt extrudes thermoplastic polyurethane equipment that is equipped with of conjugate spinning carries out, and the polyisocyanates blender is arranged in the extrusion equipment, and the skin component polymer melt extrudes machine and comprises the spinneret of core-sheath conjugate spinning spinnerets.Can use known equipment as the polyisocyanates blender with measuring pump metering fusion polyisocyanates, if desired, available filter filtering molten thing, then at the extruder mouth of pipe at core and the skin component place that meets, it is mixed in the fusion polyurethane.Perhaps, can use and have the mixing arrangement that rotates hydrid component and make the polyisocyanates blender.Yet, be more preferably and use the mixing arrangement that has the static mixing parts.Can use known static mixer to make such mixing arrangement.Though the shape and the number of static mixing parts depend on service condition, an important condition is before entering the spinnerets of conjugate spinning thermoplastic polyurethane and polyisocyanates can be mixed fully.20-90 parts generally are provided.The core component polyurethane that mixes with polyisocyanates measures with measuring pump, and imports spinning head.The spinning head preferred design becomes to make as far as possible the parking space of mixture to reduce.If desired, with the wire netting in the filter course that is contained in the spinneret, bead or similar thing are removed impurity, then this mixture are imported the spinnerets of core-sheath conjugate spinning, and with skin component, the i.e. fine thermoplasticity inelastic body of the one-tenth of fusion conjugation in another extruder.Like this, the fused mass of conjugation is from the spinnerets spinning, and is air quenched, oils, and reels on take up roll then, and winding speed is generally 400-1,500 meters/minute.
Particularly in order to improve core/skin conjugate ratio X, for example bring up to 15 or bigger, the meet structure preferred design of part of spinnerets SMIS and skin component becomes as shown in Figure 1.That is, in Fig. 1, the horizontal channel of skin B component constitutes a little depth D, for example 2.0 millimeters, can further be reduced to the 0.05-1.0 millimeter near the vertical transport pipe of core component A.In this embodiment, the distance H between the upper end of the lower end of top vertical transport pipe 1 and following vertical transport pipe 2 is less than depth D.
Immediately the bicomponent filament yarn that obtains behind spinning and the coiling, promptly first growing filament, its physical property such as tensile strength, heat resistance etc. are very poor sometimes.But after at room temperature placing about 2 hours to 7 days, physical property is obviously improved, and the compatibility of elastic stretching recovery at high temperature and core component and skin component also improves.And, after the spinning, heat-treat with suitable method, can promote yarn property, the improvement of the compatibility of hot property and core and skin.
The character of this nascent bicomponent filament yarn and hot property in time or heat treatment and changing, this is owing to not finishing the single step reaction of going forward side by side as yet and cause as the thermoplastic polyurethane of spinning material with the reaction between the polyisocyanates that it mixes.This reaction generates side chain or crosslinked polyether polyols with reduced unsaturation by allophanate and polyisocyanic acid ester linkage, and think that this is (to be the amino in the polymer of base as polyamide by the active group in polyisocyanates and the used inelastic body, amide groups or carbonyl) between reaction, the compatibility of itself and polyisocyanates is improved causes.
According to the present invention, this long filament can be used as spun filament or drawn yarn.Bicomponent filament yarn for example of the present invention, the skin component that they comprise are with the copolyesters of diethylene glycol as diol component, if this bicomponent filament yarn is placed on one side, the 1.2-5.0 of hot-stretch or its former length of cold stretch times then, then the hot water shrinkage of this long filament will increase.Under this situation, determine draw ratio and heating-up temperature according to required hot water shrinkage.But generally speaking, these numerical value are high more, and the shrinkage factor of gained long filament is high more.
As above institute this because the skin component is into fine thermoplasticity inelastic body, and core component is a polyurethane, therefore bicomponent filament yarn of the present invention has better elastic and stretches and restore.That is, though the time must not expect that inelastic body skin component has elasticity in beginning, the long filament of making core component and having a particularly conjugated shape according to use polyurethane of the present invention shockingly presents the better elastic tensile property.This elastic stretching performance do not cause by coiled structure, but caused by the elasticity of long filament itself, and this long filament also has the performance of excellence like this, and its permanent deformation is little when 100% elongation.
In addition, in core component, mix polyisocyanates, because the further reaction in these compositional range not only improved elastic stretching and recovered and heat resistance, and the compatibility of core component and skin component also improves.
According to the present invention, the further feature and advantage of this long filament are as follows:
Long filament of the present invention does not definitely have adhesivity, because core component is encapsulated in the inelastic body skin component fully.Therefore, at post-processing step, this long filament is easy to from reel (as bobbin, on its direction of principal axis) unwinding, and this is that the conventional polyurethanes yarn can not be finished.
When spinning and coiling step oil, can use cheap emulsion finish.And long filament of the present invention can be wound on the little paper cop of bobbin or diameter with at a high speed (as 1000 meters/minute).
Owing to adopted melt spinning method, long filament of the present invention has superiority aspect the suitability for industrialized production progress.
Long filament of the present invention all is good in mildew resistance and at operability (as knitting, the weaving etc.) aspect of post-processing step.
According to the present invention, but the long filament that comprises polyamide or copolyamide skin component has excellent dyeability.
According to bicomponent filament yarn of the present invention, because they have various excellent characteristic recited above, therefore can be used for making various fabric constructions, as women's stockings, swimsuit, socks, lining cloth or similar thing.Particularly compare with common stockings, stockings transparency according to the present invention is good, good appearance, and have desirable sense of touch etc.
The stockings relevant with the present invention comprise the stockings of crossing knee of all kinds, long the longest stockings and the lady's company trousers stockings that partly combine of stockings part and slacks to the thigh root, they are to carry out knitting separately with bicomponent filament yarn of the present invention, perhaps with common nylon yarn, false twisted yarn, bag core FANCY YARNS that contains the polyurethane core long filament etc. combines, by mixing knitting or blend spinning obtains.
More specifically explain the present invention below.
Embodiment 1-5
Polyurethane:
With molecular weight is 2,010 pcl-diol acid lactone, P, and P '-methyl diphenylene diisocyanate and 1.4-butanediol (making chain extender), the synthetic hardness of method is 85 thermoplastic polyurethane routinely.
Polyisocyanates:
Molecular weight be 950 and degree of functionality be 2 pcl-diol acid lactone and P, P '-methyl diphenylene diisocyanate reacts with a kind of like this method, the content that makes the NCO base is 7.0%(weight), obtain polyisocyanates thus.
Polyamide:
The use fusing point is nylon-6/66 copolymers (trade mark is called 5013B, is made by Ube Industrial Co., Ltd) of 199 ℃.
Top thermoplastic polyurethane fusion in extruder, top polyisocyanates is mixed in the polyurethane stream of fusion with various charging rate, with the static mixer that 35 hydrid components are housed (making) these polymer are filled then with sending out and mix mutually by Kenics.On the other hand, top nylon fusion in another extruder.Above-mentioned two kinds of fused mass measure respectively, and it is imported spinnerets carry out conjugate spinning, and it is 0.5 millimeter spinneret orifice that this spinnerets has 8 diameters.
Change core/skin conjugate ratio, spin the monofilament (embodiment 2-5 and comparative example 1-2) at 40 dawn with 600 meters/minute spinning speeds.In addition, except not mixing the polyisocyanates, spin similar long filament (embodiment 1) with identical method.
The character of the long filament that core/skin conjugate ratio is different with crosslink density is listed in table 1.
In the table 1, elastic stretching recovers with following equation calculating, when long filament at room temperature stretches 100% the time twice of replication:
Elastic stretching recovers (%)=(convergent force when stretching for the second time 50% elongation)/(tension force when stretching for the second time 50% elongation) * 100
Top numerical value is big more, and it is good more that elastic stretching recovers.
As seen from Table 1, it is poor that the very crisp and elastic stretching of the little long filament (comparative example 1) to 2 of core/skin conjugate ratio recovers, and that conjugate ratio is these two performances of long filament of 10 embodiment 1 is all fine.Do not satisfy inequality Y 〉=-the long filament elastic stretching of the comparative example 2 of 8.7X+52 recover and other performance all poor, and these performances of the long filament of embodiment 2 are improved greatly.Find from embodiment 3-5 that in addition by increasing core/skin conjugate ratio, the character of long filament and elastic stretching recover all to improve.
Use four threads feeding apparatus knitting machines, connect the trousers stockings with the long filament braiding of embodiment 1-4, with common stockings relatively, these stockings have excellent transparency and good knitting quality, tensility etc.
Embodiment 6
Carrying out spinning by embodiment 1 identical method, has been the stiffness changing of polyurethane core component, and core/skin conjugate ratio is 15, and the crosslink density of core component is 14 micromoles per gram.
The results are shown in table 2.
Table 2
| Hardness | Spinnability | Elastic stretching recovers |
| 55 70 80 90 95 100 | △～X 0 0 0 0 △～X | △～X 0 0 0 ○～△ X |
As seen from Table 2, the hardness of polyurethane is too high or too low all to be worthless, because it has reduced spinnability and elastic stretching recovers.
Embodiment 7
In order to spin the bicomponent filament yarn that comprises polyurethane, this polyurethane is made core and the coaxial conjugation of polyamide sheath, with aforementioned thermoplastic polyurethane and polyamide fusion and metering respectively, imports spinnerets then.Carry out conjugate spinning with 600 meters/minute spinning speeds, the shape of cross section core/skin conjugate ratio that obtained for 20 dawn is 20 the compound monofilament of a concentric core/integumentary pattern (long filament-A).
Perhaps, thermoplastic polyurethane is fusion in extruder, and polyisocyanates is incorporated in importing the way of spinnerets carries out conjugate spinning in the polyurethane.With the static mixer that has 35 hydrid components (making) fused mass that merges is fully mixed, prepare the compound monofilament (long filament-B) at 20 dawn then by the identical method of spinning filament yarn-A by Kenics.The crosslink density of the polyurethane of long filament-B is 29 micromoles per gram.
Prepare following four kinds of long filaments as a comparative example:
Long filament-C: with the monofilament at 20 dawn that prepare the used thermoplastic polyurethane spinning of long filament-A;
Long filament-D:20/6 dawn multifilament spins a mao nylon yarn, and it is the high false twist yarn of bulkiness;
The eccentric core-sheath bicomponent filament yarn that long filament-E:20/2 dawn curls, the polyurethane core that it comprised is identical with the composition of the thermoplastic polyurethane of embodiment 1, and hardness is 95, and this polyurethane and relative viscosity are 2.1 nylon-6 skin conjugation; With
Long filament-F: the single bag core FANCY YARNS that comprises long filament-C is made core, is wound with the compound wool yarn line that spins of 13/3 dawn that makes in S-or the false twisting of Z-direction on every side.
Use 4-threads feeding apparatus seamless stockings knitting machine, weave 6 kinds of stockings with these long filaments with 600 rev/mins knitting speed.4 all threads feeding apparatus are all supplied with identical yarn, just wrap core FANCY YARNS (long filament-F) alternately supply with 4 threads feeding apparatus with compound flat filament of 13/3 dawn.
To six kinds of long filaments obtaining like this with the stockings of their braidings, carry out physical property test, and wear by 30 people and to see test.
The results are shown in table 3.
Table 3
| Certified variety | Embodiment 7 | Comparative example 3 | ||||
| Long filament-A | Long filament-B | Long filament-C | Long filament-D | Long filament-E | Long filament-F | |
| The physical property elastic stretching recovers transparency (%) | 63 96 | 67 96 | 63 96 | 40 85 | 50 92 | 65 87 |
| Wearing test: the knitting quality transparency of sense of touch adaptability support sense (extruding force) | ○ ◎ ◎ ○ ○ | ○ ◎ ◎ ○ ◎ | X △ ◎ ○ ◎ | ○ △ △ △ △ | ○ △ ○ ○ ○ | ○ △ △ ◎ ◎ |
In the table 3, the physical property of stockings is described as follows:
Elastic stretching recovers:
The lower leg portion of stockings carries out 100% stretching on the direction vertical with its length, repeat 5 times, and during with last the stretching, the ratio of the shrinkage stress the when tensile stress during 80% elongation is extended with 80% represents that elastic stretching recovers, and calculates with following equation:
Elastic stretching recovers (%)=(shrinkage stress during 80% elongation)/(tensile stress during 80% elongation) * 100
This value is big more, and adaptability is big more.
Transparency:
The stockings of 10 centimeters stretch 100% respectively at vertical and horizontal before 20 watts of incandescent lamp with placing, and detect light transmission by the stockings knitwear in fabric back 10 centimeters.Light intensity is 100 when supposing that fabric is removed, and transparency is represented with the percentage that luminous intensity reduces.
According to the present invention, use the elastic stretching recovery (adaptability and support sense) and long filament-C(polyurethane filament of the stockings of long filament-A and long filament-B) on same level, and the defective sense of touch of polyurethane filament is improved, and therefore stockings of the present invention have extraordinary dress property.
Spin mao stockings of nylon yarn braiding with long filament-D and lack the suitable sense that produces by the recovery that stretches, and opaque.The curling lack of homogeneity of stockings with the eccentric core-skin bicomponent filament yarn braiding of long filament-E.In addition, poor with the stockings fibre structure of long filament-F bag core FANCY YARNS braiding, and lack the transparency.Therefore, not that long filament of the present invention is all distinguished defectiveness, so that high-quality stockings can not be provided.
Stoped the light transmission because long filament-E curls and long filament-F is bulk.Otherwise,, therefore can provide the stockings of the high grade of transparency because long filament-A and long filament-B are straight.In addition, when stockings were stretched, long filament of the present invention provided high-tension and excellent suitable sense, and this is not to be given by the spring stress that curls, but utilized the tensile stress of long filament itself.
From the wearing test result as seen,, in each certified variety, obtained excellent achievement, and kept the feature of polyurethane filament according to stockings of the present invention.And, we can say except stockings of the present invention do not have a kind of stockings to have extremely good quality and performance like this.
Embodiment 8
The identical method of long filament-B with preparation embodiment 7 is carried out conjugate spinning, and the fusing point that only is to use DSC to record is 178 ℃ a PA-12 (trade (brand) name: L1600 is made by Daicel-Huells).The long filament that obtains is called long filament-G.
With the garden shape knitting machine of single threads feeding apparatus, be made into socks with long filament-B of embodiment 7 and long filament-C and long filament-G.The performance of the socks after research washing and the dyeing.The results are shown in Table 4.
Table 4
| Certified variety | Invention | Relatively |
| Long filament-B long filament-G | Long filament-C | |
| Slickness (°) | 19 14 | 28 |
Slickness in the table 4 is measured as follows:
One aluminium skeleton is inserted in the knitting socks, and horizontal positioned is that 25 millimeters plate is placed on the socks then with heavy 23 gram diameters, and the aluminium skeleton tilts gradually, and the angle that tilts when plate begins to slide is represented the slickness of this socks fabric.
The more little slickness of this angle is good more.
As seen from Table 4, make the socks that the long filament-G of skin component is made into PA-12 and present good slickness.In order to test, performance is very good when wearing with the woven stockings of long filament-G.
Embodiment 9-13
Thermoplastic polyurethane:
Using 14.6 moles is 1,950 polyhexamethylene adipate ester, 50.5 moles of P, P '-methyl diphenylene diisocyanate and 34.9 moles of the 1.4-butanediols of making chain extender, method synthesis of polyurethane routinely.Resulting polymers is 2.11 25 ℃ of relative viscosities of measuring in/100 milliliters of dimethyl formamide solutions of 1 gram.
Polyisocyanates:
23.9 the molal quantity average molecular weight is 1,250 polycaprolactone glycol and 4.2 molal quantity average molecular weights is polycaprolactonetriol and 71.9 moles of P of 1,250, P '-methyl diphenylene diisocyanate reaction obtains a kind of compound of thickness.The NCO group content of this compound is a 6.6%(weight).
Copolyesters:
The dihydroxy ethyl terephthalate is fully mixed with the dihydroxy ethyl isophthalic acid ester, in autoclave (270 ℃ of internal temperatures), vacuumize under the stirring and carry out polycondensation reaction, obtain isophthalic acid ester combined polymerization ratio and be respectively 10,20,30,50 and the 60%(mole) five kinds of copolyesters.These copolyesters granulations.
With the fusion in extruder of top thermoplastic polyurethane.Top polyisocyanates is mixed in the polyurethane stream of fusion, with the static mixer that 35 hydrid components are housed (making) these polymer are fully mixed between mutually then by Kenics.
On the other hand, top copolyesters fusion in another extruder.The aperture that top two kinds of fused mass were measured and imported 8 spinneret orifices respectively is that 0.5 millimeter spinnerets carries out concentric conjugate spinning.
In the 10-70 scope, change core/skin conjugate ratio, with 600 meters/minute spinning speeds spin the monofilament at 40 dawn.In the spinning step, make oil agent with 15% emulsion (to polyester).
In dry and conjugate spinning step, the operability of above-mentioned polyester is listed in table 5.
Table 5
| Polymer number | The isophthalic acid ester combined polymerization is than (mole %) | Particle drying condition (60 ℃, vacuum 24 hours) | The spinning ability |
| 1 2 3 4 5 | 10 20 30 50 60 | Owing to adhesivity, particle forms bridge joint carefully | No good spinnability screw rod carefully can not be clamp-oned particle |
When isophthalic acid ester combined polymerization ratio is the 10%(mole) time, need the rising spinning temperature, so the heat endurance of polyurethane reduces to such an extent that consequently can not carry out conjugate spinning too much.Otherwise, when this ratio is the 60%(mole) time, because its adhesivity makes particle aggregation and form bridge joint in dry run, and the screw rod that can not be extruded machine is clamp-oned, and therefore can not carry out spinning.
Thermoplastic polyurethane above using replaces copolyesters to make the skin component, carries out conjugate spinning with top identical method.In this case, the long filament that uses dimethyl silscone and 5% or 0.2% amino modified silicone to mix mutually as oil agent (comparative example 4 or 5) comparative example 4 does not have adhesivity.
The physical property of these bicomponent filament yarns is listed in the table 6.
Certified variety in the table 6 is measured as follows:
The unwinding coefficient:
Be wound on bicomponent filament yarn on the bobbin with 50 meters/minute speed unwinding, and be wound on the take up roll, the unwinding coefficient is represented with the bobbin and the ratio of the superficial velocity of the yarn package of take up roll, just can not carry out unwinding when bicomponent filament yarn is bonded at the bobbin surface.
Reel the duration:
The spinning and the duration of reeling are meant this section period, at this moment between in, being spun into compound silk and being wound on external diameter with 600 meters/minute winding speed is on 83 millimeters the paper web, does not produce spider web or long filament package fracture.
Heat resistance:
The bicomponent filament yarn of 12.5 milligrams/dawn of loading weight is during with the heating of 70 ℃/minute heating rate, and this bicomponent filament yarn extends 50% o'clock temperature, is used for representing heat resistance.
High pressure dyeing:
Bicomponent filament yarn in the table 5 is made into socks with single threads feeding apparatus garden shape knitting machine, and dyeed 60 minutes at 130 ℃ with the blue dyes of concentration 2%OWF.Reduce at 70 ℃ then and washed 20 minutes.In addition, with the used identical bath dyeing preparation standard polyester textile of the socks of catching face, measure the aberration between above-mentioned socks and the standard fabric.Aberration (△ E) be 1.5 or littler usefulness zero represent that aberration is 12 or represents with XX greatlyyer.
As seen from Table 6, unwinding is good and coiling is poor for polyurethane-polyurethane-type bicomponent filament yarn (comparative example 4), and on the contrary, coiling character improves if long filament is clamminess (as comparative example 5), and unwinding character variation.The long filament high pressure dyeing of also finding comparative example is poor.
In addition, find that coiling character of unwinding character in an embodiment of the present invention and high pressure dyeing are all fine.Find also from embodiment 9 and 10 heat resistance depends on whether there is cross-bond the core component to a great extent.In addition, find from embodiment 11-13 also that if core/skin conjugate ratio increases, promptly the ratio of skin component reduces, then physical property and polyurethane-polyurethane-type bicomponent filament yarn is approaching.
Embodiment 14
The long filament sample of embodiment 10 and comparative example 5 is embedded in ground next month in spring, then, wash with water and drying after, measure the strength retention of this sample, the results are shown in table 7.Long filament strength retention of the present invention as seen from Table 7 is very excellent.
Table 7
| Tested number | Intensity keeps (%) |
| Embodiment 10 | 88.9 |
| Comparative example 5 | 23.2 |
Embodiment 15-17
Copolyesters:
By 85 moles of % terephthalic acid (TPA)s, 15 moles of % M-phthalic acids, 85 moles of % ethylene glycol and 15 moles of % diethylene glycols, method synthesizing polyester routinely.The glass transition temperature of this polyester is 64 ℃.
The fusion in extruder of the thermoplastic polyurethane of embodiment 9 is incorporated into embodiment 10 used isocyanates in the polyurethane stream of this fusion, with the static mixer (Kenics manufacturing) that 35 parts are housed these polyester is fully mixed each other then.On the other hand, with the fusion in another extruder of top copolyesters, and to import the aperture have 8 spinneret orifices be that 0.5 millimeter spinnerets carries out concentric conjugate spinning.In the 2-20 scope, change core/skin conjugate ratio, spin the monofilament at 40 dawn with 600 meters/minute spinning speeds.In the spinning stage, make oil agent with 15% aqueous emulsion.In addition, do not mix the long filament of polyisocyanates with above-mentioned identical method spinning.
The character of these long filaments is listed in the table 8.
Table 8
| Routine number | Example 15 | Comparative example 6 | Example 16 | Comparative example 7 | Example 17 |
| Crosslink density (micromoles per gram) core of skin component core component/skin conjugate ratio tensile strength (gram/dawn) extension at break (%) heat resistance (℃) elastic stretching recovery (%) | Copolyesters 0 15 0.88 302 117 29 | ← ← 5 0.32 114 100 0 | ← 28 7 0.89 388 168 23 | ← ← 2 0.61 207 138 5 | ← 30 20 1.13 420 163 56 |
As seen from Table 8, comparative example 6 and 7 long filament do not satisfy inequality Y 〉=-8.7X+52, its elastic stretching recovers and poor heat resistance.In addition, also find to increase core/skin conjugate ratio from embodiment 16 and 17 and can improve the elastic stretching recovery.
The long filament tensile strength of being made up of separately this skin component was 0.60 gram/dawn, extension at break be 0% and elastic stretching revert to 0%, therefore, the long filament that comprises this polymer provided by the invention has excellent tensility, this point is very surprising.
Embodiment 18
The long filament of embodiment 16 and comparative example 42 times 90 ℃ of its former length that stretch.Then, there is the long filament of 1.0 milligrams/dawn initial load in 100 ℃ of hot water, to soak 30 minutes with additional.Air drying.Measured length L(millimeter then).Calculate percent thermal shrinkage with following equation:
Percent thermal shrinkage (%)=(L
1-L)/(L
1) * 100
L in the formula
1Be the length before soaking in hot water, establishing former length is L
0, L under the situation of shrinking naturally then
0＞L
1The nature shrinkage factor is calculated with following formula:
Nature shrinkage factor (%)=(L
O-L
1)/(L
O) * 100
Table 9
| Pilot project | The long filament of example 16 | The long filament of comparative example 4 |
| Nature shrinkage factor (%) hot water shrinkage (%) | 0.2 50.3 | 30.5 26.7 |
As seen from Table 9, the low and hot water shrinkage's height of long filament of the present invention nature shrinkage factor, polyurethane-polyurethane-type bicomponent filament yarn can not formalize by stretching.
That does not use the long filament of embodiment 16 and 17, stretches at 120 ℃, changes draw ratio and measures percent thermal shrinkage.The results are shown in table 10.The natural shrinkage factor of these long filaments is 0.8% or lower.
Table 10 percent thermal shrinkage (%)
| Sample filaments | Core/skin conjugate ratio | Draw ratio | |
| X2 | X3 | ||
| Example 16 | 7 | 51.4 | 60.2 |
| Example 17 | 20 | 41.0 | 45.4 |
Increase with the increase of skin component ratio or the increase of draw ratio by the visible percent thermal shrinkage of table 10.
Embodiment 19-21
Carry out conjugate spinning by embodiment 16 same methods, only being to use fusing point is that 100 ℃ low density polyethylene (LDPE) (trade (brand) name: PE356, Tosoh company make) is made the skin component, and the physical property of gained long filament sees Table 11.
Table 11
| Routine number | Example 19 | Comparative example 8 | Comparative example 9 | Example 20 | Example 21 |
| Crosslink density (micromoles per gram) tensile strength (gram/dawn) extension at break (%) elastic stretching of skin component core/skin conjugate ratio core component recovers (%) 190 ℃ of recoveries (%) | Polyethylene 4 38 1.81 496 64 3 | ← 6 8 0.69 515 23 X ＊ | ← 3 20 0.77 520 15 -13 | ← 12 ← 1.53 511 69 13 | ← ← 36 1.62 508 74 26 |
Annotate:
*X: because dissolving can not be measured
Determination of physical appearance in the table 11 is as follows:
190 ℃ of recoveries
To at room temperature extend the heat treatment 1 minute in 190 ℃ of hot air dryers of 30% bicomponent filament yarn, and then turn back to room temperature.190 ℃ of recoveries are exactly the recovery of length after getting back to room temperature, calculate with following formula:
190 ℃ of recoveries (%)=(length during elongation-setting length)/(length-original length during elongation) * 100
As seen from Table 11, comparative example 8 crosslink density Y are not more than the long filament of 10 micromoles per gram, or comparative example 9 do not satisfy inequality Y 〉=-long filament of 8.7X+52, its elastic stretching recovers and poor heat resistance.In addition, from embodiment 20 with 21 visible elastic stretchings recover and heat resistance improves with the increase of crosslink density, can see also that from embodiment 19 and 21 the two character improves with the increase of core/skin conjugate ratio.
The long filament tensile strength of being made up of this this component was 0.12 gram/dawn separately, and fusing point is 100 ℃, and the result is that the present invention has improved tensile strength and heat resistance greatly, and this is surprising.
Embodiment 22
Carry out alkali-proof research with the long filament of embodiment 20 and the polyurethane of comparative example 5-polyurethane bicomponent filament yarn.
Use contains 10%(weight) the aqueous solution of NaOH make alkaline aqueous solution, the long filament that will be under the tension force condition soaks in this solution, and handles 60 minutes at 80 ℃ or 100 ℃.Then, measure strength retention, the results are shown in Table 12.
Table 12
| The long filament sample | Example 20 | Comparative example 5 | |
| Temperature | 180℃ 100℃ | 102.3 93.9 | 66.5 34.2 |
The polyurethane of comparative example 5-polyurethane bicomponent filament yarn becomes fragile in the time of 100 ℃ significantly as seen from Table 12, and long filament alkali resistance of the present invention is very good.
Claims (12)
1, a kind of elastic core and sheath type bicomponent filament yarn, it is by becoming fine thermoplasticity inelastic body skin component and polyurethane core component to form, and the crosslink density (Y) (micromoles per gram) of its SMIS/skin conjugate ratio (X) and polyurethane satisfies following inequality simultaneously:
3≤X≤100，
Y 〉=0 He
Y≥-8.7X+52
2, according to the long filament of claim 1, the best spinning temperature of wherein said inelastic body is the highest to be no more than 238 ℃.
3, according to the long filament of claim 1, wherein said inelastic body is the polyamide that has one of following feature at least: in the scope of melting temperature between 80 ℃ and 220 ℃ that records with differential scanning calorimetry (DSC); In 100 milliliter of 98% sulfuric acid solution, be no more than 2.3 with 1 gram polymer 25 ℃ of relative viscosity maximums that record.
4, according to the long filament of claim 1, wherein said inelastic body is a kind of copolyesters that contains polyethylene terephthalate as major constituent and 12-50 mole % isophthalic acid ester comonomer.
5, according to the long filament of claim 1, wherein said inelastic body is a kind of copolyesters, it is by the dicarboxylic acid component who comprises 60-88 mole % terephthalic acid (TPA) and 12-40 mole % M-phthalic acid and comprise 75-90 mole % ethylene glycol and at least a diethylene glycol that is selected from of 10-25 mole %, triethylene glycol, the diol component of neopentyl glycol and butanediol makes.
6, according to the long filament of claim 1, wherein said inelastic body is a kind of polyethylene that is selected from, polypropylene, and the polyolefin of polystyrene and polybutene, and the crosslink density of polyurethane (Y) is at least 6 micromoles per gram.
7, according to the long filament of claim 1, wherein said polyurethane core component contains the polyurethane of multi isocyanate crosslinking, and crosslink density (Y) is at least 6 micromoles per gram.
8, according to the long filament of claim 7, wherein this cross-linked polyurethane is based on the allophanate cross-linked structure.
9,, has the shape of cross section that core component and skin component have common center of gravity substantially according to the long filament of claim 1.
10, a kind of fabric construction that comprises the elastic core and sheath type bicomponent filament yarn, this bicomponent filament yarn is by becoming fine thermoplasticity inelastic body skin component and polyurethane core component to form, and the crosslink density (Y) (micromoles per gram) of the core of described long filament/skin conjugate ratio (X) and polyurethane satisfies following inequality simultaneously:
3≤X≤100
Y 〉=0 reaches
Y≥-8.7X+52
11, according to the fabric construction of claim 10, be a kind of women's hosiery, inelastic body wherein is a polyamide.
12, according to the fabric construction of claim 11, wherein said polyamide is a PA-12.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP114,130/90 | 1990-04-27 | ||
| JP2114130A JP2786514B2 (en) | 1990-04-27 | 1990-04-27 | Composite yarn and stockings |
| JP90,011/91 | 1991-03-27 | ||
| JP3090011A JP2869206B2 (en) | 1991-03-27 | 1991-03-27 | Polyester / polyurethane composite elastic yarn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1058813A true CN1058813A (en) | 1992-02-19 |
Family
ID=26431474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91103483 Pending CN1058813A (en) | 1990-04-27 | 1991-04-26 | Elastic core and sheath type bicomponent filament yarn and contain the fabric construction of this bicomponent filament yarn |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0454160A3 (en) |
| CN (1) | CN1058813A (en) |
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| JPS5846573B2 (en) * | 1980-12-27 | 1983-10-17 | カネボウ合繊株式会社 | Manufacturing method of polyurethane elastic yarn |
| JPS57205520A (en) * | 1981-06-05 | 1982-12-16 | Teijin Ltd | Conjugate fiber |
| JPS61194221A (en) * | 1985-02-18 | 1986-08-28 | Chisso Corp | Elastic conjugated yarn and cloth using same |
| JP2580780B2 (en) * | 1988-06-30 | 1997-02-12 | 東レ株式会社 | Polyurethane / polyamide composite fiber |
-
1991
- 1991-04-26 EP EP19910106833 patent/EP0454160A3/en not_active Withdrawn
- 1991-04-26 CN CN 91103483 patent/CN1058813A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072285C (en) * | 1996-06-03 | 2001-10-03 | 钟纺株式会社 | Elastic polyurethane yarn and method of manufacturing the same |
| CN102257195A (en) * | 2008-10-17 | 2011-11-23 | 英威达技术有限公司 | Fusible bicomponent spandex |
| CN102257195B (en) * | 2008-10-17 | 2014-12-10 | 英威达技术有限公司 | Fusible bicomponent spandex |
| CN104066350A (en) * | 2012-01-20 | 2014-09-24 | 株式会社岛精机制作所 | Footwear, and knitting method for knit fabric |
| CN104066350B (en) * | 2012-01-20 | 2016-04-27 | 株式会社岛精机制作所 | The weaving method of footgear and braid |
| CN105133087A (en) * | 2015-09-30 | 2015-12-09 | 华南理工大学 | Uvioresistant sheath-core composite self-adaptive fiber for Z-pinch wire-array load and preparing method thereof |
| CN105541149A (en) * | 2015-12-08 | 2016-05-04 | 余姚市交通规划设计研究院 | Modified concentric composite fine fiber for bituminous pavement surface layer and use thereof |
| CN107287694A (en) * | 2017-06-27 | 2017-10-24 | 太仓市玛雅针织有限公司 | The good composite fibre of antistatic property |
| CN107435171A (en) * | 2017-08-31 | 2017-12-05 | 浙江理工大学 | A kind of preparation method of cross-linked structure orientation filling enhancing chemical fibre |
| CN107435171B (en) * | 2017-08-31 | 2019-10-29 | 浙江理工大学 | A kind of preparation method of cross-linked structure orientation filling enhancing chemical fibre |
| CN110945166A (en) * | 2017-08-31 | 2020-03-31 | 东丽株式会社 | Sea-island composite fiber, adsorption carrier, and medical column having the adsorption carrier |
| CN110945166B (en) * | 2017-08-31 | 2022-03-18 | 东丽株式会社 | Sea-island composite fiber, adsorption carrier, and medical column having the adsorption carrier |
| CN110886033A (en) * | 2019-07-03 | 2020-03-17 | 海西纺织新材料工业技术晋江研究院 | Stretch yarn of low modulus elastic fiber and preparation method thereof |
| CN115012069A (en) * | 2022-07-20 | 2022-09-06 | 上海华峰新材料研发科技有限公司 | Composite fiber with skin-core structure and preparation method and application thereof |
| CN115012069B (en) * | 2022-07-20 | 2023-11-03 | 上海华峰新材料研发科技有限公司 | Composite fiber with sheath-core structure and preparation method and application thereof |
| CN115896965A (en) * | 2022-11-16 | 2023-04-04 | 中纺院（浙江）技术研究院有限公司 | Eccentric sheath-core polyamide-ammonia composite fully drawn yarn and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0454160A3 (en) | 1992-03-04 |
| EP0454160A2 (en) | 1991-10-30 |
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