CN1077233A - The preparation polyester fine filaments - Google Patents

The preparation polyester fine filaments Download PDF

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Publication number
CN1077233A
CN1077233A CN92103680A CN92103680A CN1077233A CN 1077233 A CN1077233 A CN 1077233A CN 92103680 A CN92103680 A CN 92103680A CN 92103680 A CN92103680 A CN 92103680A CN 1077233 A CN1077233 A CN 1077233A
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China
Prior art keywords
spinning
filament
long filament
polyester
polymer
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Granted
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CN92103680A
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Chinese (zh)
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CN1047634C (en
Inventor
R·J·科林斯
H·R·E·弗兰克福特
S·B·约翰逊
B·H·诺克斯
小E·E·莫斯特
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Invista Technologies Sarl
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EI Du Pont de Nemours and Co
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Priority to CA002101788A priority Critical patent/CA2101788C/en
Priority to ES92904563T priority patent/ES2104898T3/en
Priority to PCT/US1992/000359 priority patent/WO1992013119A1/en
Priority to DE69221739T priority patent/DE69221739T2/en
Priority to AU12310/92A priority patent/AU653207B2/en
Priority to EP92904563A priority patent/EP0646189B1/en
Priority to JP4504583A priority patent/JP3043414B2/en
Priority to TW081102473A priority patent/TW215113B/zh
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to CN92103680A priority patent/CN1047634C/en
Priority to US07/979,776 priority patent/US5356582A/en
Priority to US08/005,672 priority patent/US5288553A/en
Priority to US08/085,266 priority patent/US5384082A/en
Priority to US08/093,156 priority patent/US5417902A/en
Priority to US08/121,146 priority patent/US5407621A/en
Publication of CN1077233A publication Critical patent/CN1077233A/en
Priority to US08/214,717 priority patent/US5487859A/en
Priority to US08/289,553 priority patent/US5532060A/en
Priority to BR9205719A priority patent/BR9205719A/en
Priority to US08/378,132 priority patent/US5645936A/en
Priority to US08/378,137 priority patent/US5505894A/en
Priority to US08/397,325 priority patent/US5585182A/en
Priority to US08/468,908 priority patent/US5691057A/en
Priority to US08/475,122 priority patent/US5827464A/en
Priority to US08/475,141 priority patent/US5741587A/en
Publication of CN1047634C publication Critical patent/CN1047634C/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/082—Melt spinning methods of mixed yarn
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • 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
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/18—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by combining fibres, filaments, or yarns, having different shrinkage characteristics
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

By the viscosity and the spinning condition of selective polymer, prepare polyester fine filaments with the method for direct fabrics-orientation of simplifying.This filament has excellent mechanical performance and uniformity, and preferably has the good stainability and the balance of shrinkage.

Description

The preparation polyester fine filaments
The present invention relates to improvement, and be about polyester fine filaments, its preparation and purposes to polyester fine filaments, its preparation and purposes.
Past more or less is to be purpose to duplicate and/or to improve natural fabric, and the synthetic fiber (comprising polyester fiber) that are used for clothes are offered textile industry at large and are used for fabric and clothes.For many years, for example manufactured and be used to the synthetic textile filament of commodity of clothes, have basically and the similar filament denier (dpf) of more common natural fabric (being cotton and wool).Yet recently,, dpf scope (be about 1dpf) similar even the polyester filament at low dawn (promptly being lower than about 1dpf) can have been bought to natural silk although increase cost.Recently commercial to this lower for example about 1dpf of dpfs(), so that a variety of causes of being interested in of low dawn be suggested.
About this fine-denier polyester long filament is increased interest, write out many articles recently.Yet, for this filament of preparation, about the hell and high water in spinning (promptly extrude and reel) technology, disclosed ins and outs seldom, these spining technologies are used, and even desired have.Although those people that skill is skilled in this technology know traditional preparation and process technology can not be used for this filament.For example, in " Textile Month " 40-46 page or leaf in June nineteen ninety, for making microfibril three kinds of methods have been discussed, promptly 1) for the conventional spinning at thin dawn, 2) division bicomponent fiber (higher Denier), 3) from the bicomponent fiber of higher Denier, dissolve and remove a kind of component.Should be realized that, the 2nd and the 3rd kind of method comprise the bi-component spinning, at first form the long filament of higher Denier, handle this spun higher Denier long filament then, the long filament at the dawn that is reduced, but this process technology is not theme of the present invention.
The direct fabrics/method for winding that the present invention relates to by a kind of novelty are made filament, this and first spinning and be wound into the bicomponent filament of higher Denier, and the method that must further process then with the reduction dawn fine denier filament of wanting that obtains being used for textiles differs widely.The another kind of 2-step possibility of making the reduction denier filament is that spinning is greater than the long filament at 1 dawn, then at spinning operation after-drawing long filament.But this possibility has some significant drawbacks of having discussed in this technology; On the one hand the amount to the stretching that can realize has some actual restrictions; Compare with the long filament of direct fabrics-orientation in addition, elongate filaments also has some product shortcomings on performance; And must consider the cost of this processing (promptly stretch), especially formerly pack the long filament that spinning goes out after, when stretching as the operation of a separation, for example monofilament or warp thread stretch.The suggestion of this stretching may comprise conventional stretching technique, perhaps other technologies may have been comprised, heating again after for example aerodynamic action or long filament have been cured, but also advocate in the stretching (being sometimes referred to as space-stretching) of going down of enough tension force if under the situation that does not have the differential draw-off godet, carry out.The method of some direct fabrics that proposed depends on used specific polymers compositions, for example depend on specific viscosity, this has some shortcomings, therefore preferably adopts a kind of method, this method not to need to utilize the special viscosity or the characteristic of other special composition.
In a word, in this technology disclosed existing polyester filament technology of preparing do not have especially at the practice that is unsuitable for producing the fine-denier polyester long filament by single direct fabrics/operating winding, perhaps comprise some restrictions and shortcoming.Therefore, the direct fabrics method of the thin polyester filament of dpf that preferably provides a kind of like this manufacturing that does not have these shortcomings to have to want and performance.The invention solves this problem.Long filament of the present invention is " spinning-orientation ", and the implication of " spinning-orientation " is discussed in technology and hereinafter.
Be to make the commodity polyester filament at first by " division " method, this method spinning and not the stretching and winding long filament contain an independently stretching step later on.At the fifties, Hebeler proposes the possibility of polyester fondant high speed spinning in United States Patent (USP) 2604667 and 2604689.At the seventies, as Petrille in United States Patent (USP) 3771307 and Piazza and Reese described in the United States Patent (USP) 3772872, the high speed spinning of polyester fondant becomes the basis of method of the long filament of preparation spinning-orientation, and this long filament has been used as the feed yarns of stretching-distortion.The polyester fondant high speed spinning still is the basis of some other method, and these methods at first are disclosed the seventies, for example Knox in United States Patent (USP) 4156071 and Frankfort and Knox disclosed in United States Patent (USP) 4134882 and 4195051.
These technology have disclosed the basic difference on fine structure and performance between the long filament of spinning-orientation and the elongate filaments; The orientation-indicating of the polyester molecule of the long filament of spinning-orientation is obtained by (at a high speed) spinning; The orientation-indicating of elongate filaments is after the long filament of coiling spinning, produce by the stretching of long filament as a complete separating process, perhaps or even before reeling, but be after cold fuse-element forms the solid long filament, before this long filament that stretches, produce by the stretching of long filament as a kind of continuous process.
The purpose of this invention is to provide the filament with spinning-orientation characteristic, this is because this feature can provide favourable performance.
Following basis the invention provides several characteristics and example:
1) a kind of method for preparing the polyester fine filaments of spinning-orientation;
2) have the dawn number and be about spinning-oriented polyester filament below 1 or 1, this filament has the mechanical performance and the fiber number uniformity of enhancing, makes them be particularly suitable for the high speed fabrication processes;
3) spinning-oriented polyester filament, be particularly suitable at a high speed distortion, curl and winding process in be used as the stretching feed yarns;
4) polyester fine filaments of spinning-orientation is particularly suitable for the weaving silk that is used as directly-uses, and does not need other stretching or heat treatment in the single-layer woven fabrics of key dyeing and jersey; Be particularly suitable for as air jet texturing that does not need to stretch and the box curling feed yarns of obstruction; If desired, the cold stretch equably of this filament can be made the higher warp thread of shrinkage factor, this warp thread has the dyeing uniformity of the final-application that is suitable for crucial dyeing;
5) spinning-oriented polyester filament that has stretched is particularly suitable for being used as the weaving silk in the single-layer woven fabrics of key dyeing and jersey; And the method for preparing the fine filament of this meticulous stretching;
6) can under condition of normal pressure, dye and without the bulking polyester fine long filament of dyeing carrier; And the method for preparing the fine filament of this bulking;
7) long filament of Hun Heing, filament wherein are filaments of the present invention; And the long filament of Hun Heing particularly, wherein except in dawn number, cross section and/or shrink aspect the potentiality the difference, all long filaments all are long filaments of the present invention.
Particularly, provide following content according to the present invention:
A kind of method for preparing the polyester fine filaments of spinning-orientation, wherein,
(ⅰ) relative viscosity of selected polyester polymers (LRV) is about 13-23, and zero shears fusing point (TM °) is about 240-265 ℃, and glass transition temperature (Tg) is about 40-80 ℃;
(ⅱ) with the fusing of above-mentioned polyester be heated to above apparent melting point polymer (TM) aTemperature (Tp) scope be about 25-55 ℃, preferably be about 30-50 ℃;
(ⅲ) melt that obtains is filtered fast enough, the result is less than 4 minutes in the time of staying (tr) of the fusion temperature (Tp) of polymer;
(ⅳ) with the mass velocity (W) of about 0.7 Grams Per Minute of about 0.07-(g/min), extrude by spinning die wire hole crossing the melt that filters, the area of section (Ac) in the silk hole of selecting for use is about 125 * 10 -6Cm 2(19.4mils 2) to 1250 * 10 -6Cm 2(194mils 2), preferably be about 125 * 10 -6Cm 2(19.4mils 2) to 750 * 10 -6Cm 2(116.3mils 2) ratio (L/DRND) of its length (L) and diameter (DRND) is at least about 1.25, is preferably lower than approximately 6, particularly is lower than about 4;
(ⅴ) penetrate from spinning die wire hole when the melt of extruding, through at least about 2cm and be less than (12dpf approximately 1/2) during the segment distance of cm, prevent that the melt of extruding from directly cooling off, dpf there is the filament denier of the polyester fine filaments of spun orientation, the preferably about 1-0.2dpf of dpf, particularly about 0.8-0.2dpf; On average being lower than along the distribution (DS) of the dawn number of terminal direction (along-end) of wanting is about 4%, is preferably lower than approximately 3%, particularly is lower than about 2%;
(ⅵ) preferably use temperature (Ta) to be lower than the radial air that glass transition temperature of polymer (Tg) and speed (m/min) are about per minute 10-30 rice, the spinning threadling (spinline) that will attenuate is cooled to be lower than the Tg of polymer;
(ⅶ) for preparation be particularly suitable for the stretching long filament of feed yarns, this long filament is characterised in that percentage elongation is 7%(T 7) time strength range be about 0.5-1g/d, (ε a) scope is about 5.7-7.6, and (σ a) is about the 0.045-0.195 gram/dawn (g/d) to apparent spinning threadling internal stress, preferably is about 0.045-0.105g/d to taper to apparent spinning threadling strain; Be particularly suitable for the directly long filament of use for preparation, the feature of this long filament is that percentage elongation is 7%(T 7) time intensity be about 1-1.75g/d, (σ a) preferably is about 0.105-0.195g/d to taper to apparent spinning threadling internal stress;
(ⅷ) be about 50-140cm, preferably be about 50-(50+90dpf 1/2) distance (Lc) of cm, will cool off with the long filament boundling that has attenuated with a low-friction surface and become tow;
(ⅸ) tow is wound up, winding speed (V) is about 2-6 kilometer/minute (Km/min), preferably is about 2-5Km/min, particularly is about 2.5-5Km/min.
According to the present invention, also provide following spinning-polyester fine filaments of orientation and the product that obtains thus:
Filament denier (dpf) is about 1 or less than 1, the polyester fine filaments that preferably is about spinning-orientation of 0.8-0.2dpf, the feature of wherein said polyester is that relative viscosity (LRV) is about 13-23, and zero shears melting point polymer (TM °) is about 240-265 ℃ and glass transition temperature (Tg) and is about 40-80 ℃; And being further characterized in that of above-mentioned filament:
(ⅰ) boil shrinkage factor (S) less than maximum approximately contraction potentiality (Sm), wherein Sm=((550-E B)/6.5) %, and elongation at break (E B) % is about 40-160%,
(ⅱ) be higher than approximately 5-30 ℃ maximum temperature T(STmax of glass transition temperature of polymer (Tg)) time, maximum collapse tension force (STmax) is about 0.05-0.2g/d;
(ⅲ) percentage elongation is 7% o'clock intensity (T 7) be about 0.5-1.75g/d, like this so that ((T B) n/ T 7) ratio be at least about (5/T 7), preferably be at least about (6/T 7); Wherein, (T B) nBe that delustering agent for 20.8 reference LRV and 0% is (as TiO 2) the standard fracture strength of %;
What (ⅳ) meet the requirements on average scatters (DS) along the dawn number of terminal direction and is lower than approximately 4%, is preferably lower than approximately 3%, particularly is lower than about 2%.
Be particularly suitable for being characterised in that as the spinning-orientation filament of stretching feed yarns (DFY) boil shrinkage factor (S) and be at least about 12%, elongation at break (EB) is about 80-160%, percentage elongation is 7% o'clock intensity (T 7) be about 0.5-1g/d.
Be particularly suitable for being characterised in that, shrink rate variance (△ S=DHS-S) less than about 2% as the spinning-orientation filament of the long filament (DUY) that directly uses.Wherein, boiling shrinkage factor and dry-hot shrinkage all is about 2-12%, so that boils the filament denier dpf(ABO after the contraction) be about 1 or less than 1, preferably be about 1-0.2dpf, more preferably be about 0.8-0.2dpf; Percentage elongation is 7% o'clock intensity (T 7) be about 1-1.75g/d; Elongation at break (EB) is about 40-90%, and back surrender (post-yield) modulus (Mpy) is about 2-12g/d.
The spun orientation filament that can carry out even cold stretch is characterised in that, shrink rate variance (△ S=DHS-S) less than making an appointment with+2%, wherein, boiling shrinkage factor and dry-hot shrinkage all is about 2-12%, the beginning temperature T cc(DSC of cold crystallization) be lower than about 105 ℃, instantaneous stretching modulus (Mi) is at least about 0.
The spinning that stretched-oriented polyester filament is after boiling contraction, and its dawn is counted dpf(ABO) be about 1 or less than 1, preferably be about 0.8-0.2dpf, wherein, the long filament of above-mentioned stretching is further characterized in that:
(ⅰ) boil shrinkage factor (S) and dry-hot shrinkage (DHS) is 2-about 12%;
(ⅱ) percentage elongation is 7% o'clock intensity (T 7) be at least about 1g/d, consequently ((T B) n/ T 7) ratio be at least about (5/T 7), preferably be at least about (6/T 7), wherein, (T B) nBe that delustering agent for 20.8 reference LRV and 0% is (as TiO 2) the standard fracture strength of %; Elongation at break (E B) be about 15-55%;
(ⅲ) back yield modulus (Mpy) preferably is about 5-25g/d;
The average dawn number that (ⅳ) meets the requirements scatters (DS) less than about 4%, preferably less than about 3%, particularly less than about 2%.
The spinning of the bulking-dawn of oriented polyester filament after boiling contraction counted dpf(ABO) be about 1-0.2dpf, be preferably the about 0.2dpf of 0.8-; Above-mentioned bulking silk is further characterized in that, boiling shrinkage factor (S) and dry-hot shrinkage (DHS), to be 2%-about 12%, elongation at break (E B) being about 15%-55%, percentage elongation is 7% o'clock intensity (T 7) being at least about 1g/d, back yield modulus (Mpy) preferably is about 5-25g/d, is at least about 0.1 for the relative dispersion dyeing speed of the standard of 1dpf (RDDR).
Filament wherein is the combined filament yarn of filament of the present invention; Especially except dawn number, cross section and/or contraction potentiality difference, wherein all long filaments all are the combined filament yarns of long filament of the present invention.
(wherein M is an alkali metal cation owing to the ethylidene-5-M-sulfo--isophthalate construction unit that contains the 1-3 mole % that has an appointment, for example sodium or lithium), so the raw silk rings with stretching preferred above-mentioned spinning-orientation, bulking can both dye with cation dyes.
Particularly do not having under the condition of normal pressure of dyeing carrier, preferred above-mentioned spinning-orientation, bulking and raw silk rings that stretch be dispersion dyeing equably, they are characterised in that, dynamic loss modulus maximum temperature T(E " max) be lower than about 115 ℃, be preferably lower than about 110 ℃; And they are made of polyester polymers, and polyester polymers is polyethylene terephthalate basically, and it is to be (O-C by general formula basically 2H 4-O-) alkylene dioxy construction unit A and general formula be (C(O)-C 6H 4-C(O)-) alkylene dicarbonyl structure unit B alternately form, but, for example be about 240-265 ℃ zero shearing fusing point (TM °) and be about 40-80 ℃ glass transition temperature (Tg), also will carry out modification with more a spot of other alkyl dioxies construction unit A and/or alkylene dicarbonyl structure unit B that is different from the said structure unit for polyester polymers is had.
For the aesthetic feeling that increases sense of touch and vision and comfortable, long filament of the present invention can be non-circular, the form factor of this non-circular long filament (SF) is at least about 1.25, and the form factor here is with the long filament parameter of measuring (PM) with for the calculating parameter (P of the circular long filament of equal area of section RND) ratio determine.In order to make the lighter fabric of weight have bigger bulk density and long filament bending modulus,,, can be spun to tubular filament through later coalescent by arc spinning plate spinneret orifice to improve the drapability of fabric.
Other characteristic of the present invention and example will occur in this manual.
Fig. 1 is a speed (V) of drawing out spinning threadling and the graphic representation of the relation curve of distance (X), the speed (Vo) of spinning speed when extruding is increased to final (coiling) speed (Vc is generally in the dirty mensuration in boundling place) of finishing after the drawing-down among the figure; Among the figure, apparent spinning internal stress (σ a) with the spinning threadling viscosity (η) in constriction place N(that is, here find be approx with about ratio LRV/T 6 PBe directly proportional, wherein Tp is with a ℃ expression) and the velocity gradient (dv/dx) in constriction place (here find be approx with about V 2/ dpf particularly is directly proportional in being about the spinning speed scope of 2-4Km/min, and the about V when for example being about 4-6Km/min with higher spinning speed approx 3/2/ dpf is directly proportional) product be directly proportional.Also drawn the relation curve of spinning threadling temperature and spinning threadling distance (X), and observed, compared with the rapid increase of constriction place spinning threadling speed, the spinning threadling temperature is along with distance reduces equably.
Fig. 2 is the birefringence (△ n) and apparent spinning threadling internal stress (σ) of the long filament of spinning-orientation aThe graphic representation of relation curve; Slope among the figure is called as " stress-optical coefficient SOC ", and the SOC value of line A, B and C be respectively 0.75,0.71 and 0.645(g/d) -1; Average SOC value is about 0.7; Figure center line A is the typical characteristic curve that occurs in the document of relevant 2GT polyester with C.Apparent spinning threadling internal stress (σ a) value and document in the value that occurs in full accord.
Fig. 3 is that the long filament of spinning-orientation is 7% o'clock intensity (T at percentage elongation 7) with the graphic representation of the relation curve of apparent spinning threadling internal stress.As shown in Fig. 2 and 3, birefringence (△ n) and T 7(σ relation curve a) is near linear relationship, and this relation is allowed and used T with apparent spinning threadling internal stress 7Represent the feature of long filament average orientation as a useful parameter.For the measurement of dawn number less than 1 filament, birefringence (△ n) is the structural parameters that are difficult to.
Fig. 4 be draw out apparent spinning threadling internal stress (σ a) and percentage elongation be the intensity (T of long filament of spinning-orientation of 7% o'clock 7) preferred value be the spinning threadling ratio of elongation ER(=V/Vo of yardstick with the natural logrithm) graphic representation of the relation curve of (for example being represented as 0.2 and 2 on 200 and 2000 the ER value X-axis in the drawings, i.e. ER/1000); Natural logrithm 1n(ER among the figure) (ε a), V is final (coiling) spinning threadling speed among the figure, and Vo is the extruded velocity in a hole to be called as apparent spinning threadling strain here.Describe method of the present invention with enclosed areas ADLI, enclosed areas ADLI comprises the regional ADHE(II of the long filament that preferred for preparation is directly used) and the area E HLI(I of preferred for preparation stretching feed yarns).What area B CGF and FGK I were represented is particularly preferred method.
Fig. 5 is representational Instron (Instron) load-extension curve of an expression " secant " back yield modulus (Mpy) GRAPHIC CALCULATION, and " secant " back yield modulus (Mpy) wherein is by being 7% o'clock intensity (T with putting percentage elongation that C represents 7) and be 20% o'clock intensity (T with the percentage elongation represented of some A 20) calculate, and be with formula (1.07T 7-1.2T 20)/0.13 is determined; And " secant " Mpy(is expressed as tan β in the drawings) be expressed as tan α in the drawings with " tangent line " Mpy(, i.e. the slope of line segment AB) compare.For instantaneous modulus Mi(=d(stress)/d(elongation)) long filament greater than about 0, the value of tan β and tan α are roughly the same.
Fig. 6 is the tan β among secant Mpy(Fig. 5) with the graphic representation of the relation curve of the birefringence (△ n) of spinning-oriented yarn.For identical with the tan β basically long filament of tan α among the figure, back yield modulus (Mpy) becomes a kind of useful mensuration of molecularly oriented.
Fig. 7 is for the relative dispersion dyeing speed (RDDR) of the standard of 1dpf and the graphic representation of average filament birefringence (△ n) relation curve.
Fig. 8 is the amorphous free volume (Vf of the long filament of fiber, am, as hereinafter defined) with the maximum temperature T(E of the dynamic loss modulus of fiber " max) the graphic representation of relation curve; this maximum temperature is regarded as this glass transition temperature generally is higher than 20 ℃ to about 50 ℃ of polymer Tg to the measuring of glass transition temperature here.Corresponding to bigger amorphous free volume (Vf, am), T(E " max) value reduces, and therefore improved stainability, here according to being at least about 0.1 relative dispersion dyeing speed (RDDR) value (to the 1dpf standard) mensuration stainability.
Fig. 9 is the graphic representation of the relation curve of filament density (ρ) and birefringence (△ n); Its bend is represented the density (ρ) of amorphous orientation (fa) of the mark that increases and the combination of (△ n), is used for the free volume Vf.am described in the calculating chart 8.
Figure 10 is the collection of illustrative plates of a typical differential scanning calorimetry (DSC), it demonstrates the thermal transition corresponding to glass transition temperature (Tg), the Tcc(DSC of beginning " cooling " crystallization) and the zero shearing fusing point TM of fiber, because the orientation and the crystalline effect of fiber fusing point, TM is higher than zero of polymer and shears TM ° of fusing point.Shear fusing point (TM °) in order to measure zero of polymer, the DSC fiber sample that has melted is in advance carried out DSC heating second time, so that the DSC spectrum of polymer to be provided, rather than the DSC that extrudes fiber composes.
Figure 11 is a typical shrink tension (the ST)-TEMPERATURE SPECTROSCOPY of spinning of the present invention-orientated polymer fine filament, it has shown maximum collapse tension force ST(max), maximum temperature T(STmax) and preferred heat-set temperature Tset, be lower than this preferred heat-set temperature Tset, heat setting can not have the opposite effect to dyeability significantly.
Figure 12 is for the present invention's feed yarns (curve C) that typically stretches, for the typical long filament (curve B) that directly uses of the present invention, and for the preferred long filament that directly uses of the present invention who (promptly is similar to the back of dyeing) after the lax heat treatment, the relation curve of representational intensity (T=load (gms)/original dawn number) and percent elongation.
Figure 13 is according to (TB) n/T 7Ratio as T 7The function of inverse (promptly as 1/T 7Function) relation draw, to the offset correction of LRV the preferred value of fracture strength (TB) n and delustering agent (TiO for example 2) graphic representation of percentage; Curve A wherein: ((TB) n/T 7)=(5/T 7), curve B: ((TB) n/T 7)=(6/T 7).
Figure 14 is ratio T 7/ (V 2/ dpf) as each long filament extrude boundling the monofilament number ( #C) with ratio Dref/Dsprt) 2The curve map of function of product, wherein Dref and Dsprt are respectively the diameter (for example about 75cm) of the spinning plate of reference and the diameter of test spinning plate.Find that natural logrithm-natural logrithm (1n-1n) slope of a curve " n " is about negative 0.7(-0.7); That is to say, find that percentage elongation is 7% o'clock intensity (T 7) and (V 2/ dpf) and and (( #C) (Dref/Dsprt) 2) -0.7Change pro rata; That is to say, along with long filament is extruded density to increase to exponential be positive 0.7(+0.7), percentage elongation is 7% o'clock intensity (T 7) be similar to linearly and reduce; Therefore long filament can be extruded density is used as with the technological parameter of higher spinning speed (V) spinning than the long filament of thin dawn number.When spinning speed was higher, when for example being about 4-6Km/min, along with the increase of spinning speed, apparent spinning stress increased not too soon, promptly found it and (V 3/2/ dpf) be directly proportional.
Prepare the polyester polymers that the long filament of the present invention of spinning-orientation is used with following feature selecting: relative viscosity (LRV) is about 13-23, zero shears fusing point (TM °) is about 240-265 ℃, glass transition temperature (Tg) is about 40-80 ℃, and wherein TM ° is that the firing rate with 20 ℃ of per minutes is measured according to the DSC thermal cycle second time under blanket of nitrogen with Tg.Above-mentioned polyester polymers is the linear condensation polymer that alternately is made of construction unit A and B, wherein A is that structure is the alkylene dioxy unit of (O-R '-O-), B be structure be (C(O)-the alkylene dicarbapentaborane unit of R " C(O)-), wherein R ' is (C basically 2H 4-), resemble at ethylidene dioxy (1,2-ethylene glycol) unit (O-C 2H 2-O-) like that, R " is (C basically in 6H 4-), resemble 1, and 4-benzene dicarbapentaborane unit (C(O)-C 6H 4-C(O)-) in like that, come like this configuration example as at least about 85% resemble ethylene glycol terephthalate (O-C 2H 4-O-C(O)-C 6H 4-C(O)-) such constitutional repeating unit.
Can constitute polymer by the following method based on the polyethylene terephthalate (being expressed as PET or 2GT here) that is fit to, by the book " Polyester Fibers; Chemistry and Technology " of H.Ludwig at him, John Wiley and Sons Limited(1971) the DMT-method described in, and in the TPA-method described in the United States Patent (USP) 4110316 of Edging.In order to improve low temperature dispersion dyeing, comfortableness and aesthetic, in copolyesters, for example also comprise and reach alkylene dioxy and/or the alkylene dicarbapentaborane unit that the different alkylene dioxy of about 15% usefulness and alkylene dicarbapentaborane unit replace.In the United States Patent (USP) 4444710(of Most embodiment VI), United States Patent (USP) 3748844(the 4th hurdle of Pacofsky) and people's such as Hancock United States Patent (USP) 4639347(the 3rd hurdle) in, can find suitable replacement unit.
Can also carry out modification to polyester polymers by means of the dyeing part of ion.Ethylidene-5-M-sulfo-isophthalate for example, wherein M is an alkali metal cation, for example sodium or lithium; For example, as United States Patent (USP) 4041689(embodiment VI at people's such as the United States Patent (USP) 3018272 of Griffing and Remington, Hagewood United States Patent (USP) 4929698, Duncan and Scrivener) and the United States Patent (USP) 3772872(embodiment VII of Piazza and Reese) in disclosed, ethylidene-5-sodium-sulfo-isophthalic acid ester group of the about 3 moles of % of 1-can be added, so that the stainability of polyester filament for cation dyes to be provided.Stainability or other performances of the elongate filaments that obtains for the long filament of adjusting spinning-orientation with by it, as the United States Patent (USP) 4025592 of Bosley and Duncan is disclosed, and the chain branching agent described in the United States Patent (USP) 4945151 of cooperation Goodley and Taylor, some diethylene glycol (DEG)s (DEG) can be added on the polyester polymers.
According to the present invention, the method for the polyester filament of preparation spinning-orientation is provided, the fiber number of this polyester filament for example is about 1-0.2 filament denier (dpf), preferably is about 0.8-0.2 filament denier (dpf);
(a) as foregoing, with the fusing of above-mentioned polyester polymers be heated to temperature (Tp), temperature (Tp) is higher than about 25-55 ℃ of apparent fusion temperature (TM) a, preferably about 30-50 ℃, wherein, owing to the shear action of polymer, make (TM) a be higher than zero and shear fusion temperature (TM °) in the extrusion, here (TM) a is defined as:
（TM）a＝〔TM°+2×10 -4（L/D RND）Ga〕
Wherein, L is the length in a hole, D RNDBe the diameter in circular or non-circular silk hole, for non-circular silk hole, D RND(cm) be by same cross-sectional area A c(cm 2) the equivalent diameter in circular wire hole calculate Ga(Sec -1) be the apparent silk hole shear rate that hereinafter defines,
(b) in spinneret cavity (with shown in Fig. 2-31 of the United States Patent (USP) 3249669 of Jamieson identical), for example as Phillips described in the United States Patent (USP) 3965010, filter the polymer melt of formation fast enough by inert media, to cause the time of staying (tr) to be less than about 4 minutes, wherein, by the free volume (V of filter chamber (filling) with the inertia filter medium F, cm 3) with polymer melt volume flow rate (Q, cm by filter chamber 3/ min) ratio (V F/ Q) come definition of T r.The definition of the polymer melt volume flow rate (Q) by filter chamber is, silk hole mass velocity (W, g/min) with the silk hole count in every chamber ( #C) product (is taken as about 1.2195g/cm here divided by fusant density 3); That is to say Q= #CW/1.2195.By the liquid replacement method of standard,, can sample plot determine the free volume (V of filter chamber (filling) with the inertia filter medium with the liquid (for example ethanol) of low surface tension F, cm 3).In above-mentioned formula for melt residence time tr, by W=[(dpfV with its equivalent)/9] (wherein V is a winding speed, represent with Km/min) replace a silk hole mass velocity (W), find time of staying tr with the monofilament radical of filament denier, winding speed (V) and each filter chamber ( #C) increase and reducing, and along with filter chamber free volume (V F) reduce and reduce.By volume that changes the spinneret cavity and the inert material that utilizes the strainability that under the situation of less free volume, provides enough, can reduce the free volume (V of cavity F) for certain silk number, can be by from single filter chamber, extruding more than one multifilament bundled, increase each filter chamber monofilament (i.e. a hole) radical ( #C), that is to say that spinning goes out more monofilament radical, then endless tow is split the less endless tow that (being called many-end here) becomes the filament denier want, this method is preferably by using some to be arranged on about 50cm to pact (50+90dpf 1/2) the most advanced and sophisticated thread guide (metered finish tip separator guides) that separates of metering oil supply at cm place carries out;
(c), extrude by the polymer melt that spinning die wire hole will filter, and select a silk hole, area of section Ac=(π/4 by following condition being about the mass velocity of 0.07-0.7 Grams Per Minute (g/min)) D RND 2Scope be about 125 * 10 -6Cm 2(19.4mils 2) to 1250 * 10 -6Cm 2(194mils 2) preferably be about 125 * 10 -6Cm 2(19.4mils 2) to 750 * 10 -6Cm 2(116mils 2), length (L) and diameter (D RND) be such so that L/D RNDRatio be about 1.25-6, preferably be about 1.25-4; When extruding.
Ga（sec -1）＝〔（32/60π）（W/ρ）/D RND 3〕
W is the mass velocity (g/min) in a hole, and ρ is that the density of polyester fondant (is taken as 1.2195g/cm 3), D RNDIt is silk bore dia (defined in front) centimetre to be unit;
(d) penetrate from spinning die wire hole when the polymer melt of newly extruding,, be less than (12dpf approximately through at least about 2cm 1/2) the segment distance L of cm DQThe time, prevent its direct cooling, dpf wherein is the filament denier of the polyester fine filaments of spun orientation;
(e) carefully the melt of extruding is cooled to be lower than the glass transition temperature (Tg) of polymer, the horizontal blast-cold radiator cooler of laminar flow (described in the United States Patent (USP) 4529368 of Makansi) of phantastron can be housed by use, preferably by radial air (described in the United States Patent (USP) 3067458 of Dauchert) the above-mentioned cooling of realization, wherein, the temperature of quench air (Ta) is lower than about Tg, and the speed of quench air is about 10-30m/min;
(f) (ε a) is about 5.7-7.6, and when preferably being about 6-7.3, apparent spinning threadling strain stress a equals spinning threadling ratio of elongation (E when chilled melt being tapered to apparent spinning threadling strain R) natural logrithm (1n), E RBe a winding speed (V) and a ratio of hole extruded velocity (Vo); That is to say, in centimetre D RND, ε a can represent with following formula:
1n（E R）＝1n（V/Vo）＝1n〔（2.25×10 5πρ）（D RND 2/dpf）〕;
(g) in the process of attenuating, (σ a) is about 0.045-0.195g/d, for the preparation feed yarns (DFY) that is particularly suitable for stretching, it is characterized in that percentage elongation is 7% o'clock intensity (T to make apparent spinning threadling internal stress 7) value is about the long filament of spinning-orientation of 0.5-1g/d; σ a preferably is about 0.045-0.105g/d, is particularly suitable for the directly long filament (DUY) of use for preparation, it is characterized in that percentage elongation is 7% o'clock intensity (T 7) be about the long filament of spinning-orientation of 1-1.75g/d.(σ a) preferably is about 0.105-0.195g/d; (σ a) equals the apparent viscosity (η m) of the melt that attenuates and the product of finishing the spinning threadling velocity gradient (dv/dx) at the place that attenuates (being called " constriction place " here) basically to apparent here spinning threadling internal stress; And at certain spinning plate surface area (Ao, cm 2) and the situation of polymer temperature (Tp) under, find apparent spinning threadling internal stress (σ a) increases with the increase of polymer LRV and winding speed (V), with the dpf of long filament and monofilament number ( #C) increase and reducing; Here with the analyze relationship formula of following experiment represent (σ a):
（σa）＝K（LRV/LRV 20.8）（TR/TP） 6（V 2/dpf）（Ao/＃C） 0.7
Wherein the approximation of K is 10 -2(ρ m/SOC), ρ m are that the density of the long filament of spinning-orientation (for example is about 1.345-1.385g/cm 3, promptly about 1.36g/cm 3), SOC is the stress-optical coefficient (for example for the 2GT homopolymers, be unit with the inverse of g/d, be about 0.7) of polyester polymers; T RBe the polymer reference temperature by (TM °+40 ℃) definition, TM ° is zero shearing (DSC) melting point polymer; Tp is a polymer melt spinning temperature ℃; V is the winding speed of representing with Km/min; #C be with #C/cm 2Expression for certain monofilament radical of extruding surfaces A o (promptly thread hole count); LRV is a polymer viscosity of measuring (laboratory), LRV 20.8Be when the LRV of 2GT homopolymers value be 20.8 to have the identical zero corresponding reference LRV-value (LRV is defined in hereinafter) of shearing the polyester polymers of " newton " (" Newtonian ") melt viscosity (η o) during at 295 ℃, (for example, the polyester of finding the 15LRV of cationically dyeing has a melt viscosity of representing with the pressure drop of silk hole, this viscosity is in LRV is about the scope of 20 2GT homopolymers, therefore for the polymer of this modification, preferred reference LRV is about 15.5, and this is to determine by the silk hole drop measurement sample plot of standard);
(h) be about 50-140cm on distance spinning plate surface, preferably be about 50-(50+90dpf 12) cm distance (Lc) locates, with a low-friction surface (promptly, in the mode of neither wearing and tearing and not blocking long filament again), for example use a finish roll, preferably with a most advanced and sophisticated applicator of metering oil supply (described in the United States Patent (USP) 4926661 of Agers), the long filament boundling that has attenuated fully of cooling is become a multifilament bundled, the needs that depend on final-use processing, normally a kind of aqueous emulsion that is about the 5-20% solid weight of the oil supply here, oil supply accounts for the 0.4-2% of solid weight on long filament;
(i) basically as Bunting and Nelson in United States Patent (USP) 2985995 and Gray described in the United States Patent (USP) 3563021, with an air nozzle interlaced filament bundle, here, entanglement degree between long filament (be called quick pin number RPC at this, it is to measure according to the United States Patent (USP) 3290932 of Hitt) is to select according to the packing of long filament and the needs of final use;
(j) with winding speed (V), multifilament bundled is wound up, here winding speed (V) equals the superficial velocity of first driven voller, is about 2-6Km/min, preferably is about 2-5Km/min, especially is about 2.5-4.5Km/min; As Harris described in the United States Patent (USP) 4932109, in order to prevent to form the oil supply deposition on the interlacing nozzle surface, adopt the method (except using hot interlacing nozzle fluid for example hot-air or water saturation air) of heating, but the about 0.5-of overfeeding about 5%, make the long filament between first live-roller and the take up roll lax, reduce retraction force like this from aerodynamic drag.
Method with direct fabrics-orientation (SDSO) of simplifying prepares polyester fine filaments of the present invention, this method does not contain stretching or heat treatment, and the preferred balance of shrinkage and stainability performance is provided, make polyester fine filaments of the present invention be particularly suitable for replacing natural long filament, for example silk.By the parameter of careful selection SDSO method, can make and have excellent mechanical properties and inhomogeneity filament; Like this thus shrinkage can be used to the long filament (DUY) of the direct use of multifilament form less than about 12% filament, and can high speed woven and knitting in process and can not form broken filament; Shrinkage is preferably more than about 12% long filament can be in the stretch process of weaving at a high speed, for example friction twisting distortion, air jet texturing, filling box curl and radial drawing in, be used for the stretching feed yarns (DFY) of multifilament form, and can not form broken filament.
Long filament of the present invention is characterised in that to have good mechanical performance, this performance allows to be used for weaving processing at a high speed and can not formed broken filament by the yarn that these long filaments constitute, and for example is used for draw false twisting and air jet texturing, radial drawing, stretching gear crimping and clogs box curling and the jet weaving of empty G﹠W and through compiling; Long filament of the present invention is further characterized in that having the good dawn counts uniformity (use along the dawn number distribution DS of terminal direction and define) here, and this performance allows these long filaments to be used for the fabric of crucial dyeing.Long filament of the present invention can be as the long filament in the stretching feed yarns (and tow), particularly boils shrinkage factor (S) and dry-hot shrinkage (DHS) and all is particularly suited for the feed yarns that stretches greater than about 12% long filament; Shrinkage is particularly suitable for the long filament of flat not textured multifilament yarn less than about 12% long filament of the present invention, and resemble the long filament that the box such deformation processing that does not wherein need to stretch of curling of air jet texturing, gear crimping and filling is used, and the flat long filament with distortion of the present invention can be cut into staple and Soft flocks; And can be as Knox and Noe described in the United States Patent (USP) 5066447, with shrinkage less than about 12% long filament cold stretch equably.
Form contrast with polyester fine filaments prepared in accordance with the present invention, the feature of the filament of being made by such spinning technique (this technology for example comprises stretching and/or the heat treatment step pneumatic or machinery in order to reduce filament denier and/or to carry out for the orientation that improves molecule and/or degree of crystallinity) is usually: 1) greater than the high shrink tension (STmax) of about 0.2g/d; When 2) the highest shrink tension appears at temperature T (STmax) and is higher than about 100 ℃ (promptly being higher than the dyeing at normal pressure temperature); 3) surpass the textile dyeing of the routine that is about 100-180 ℃ and put temperature in order with handling temperature, and the dry-hot shrinkage increase (that is to say, for T=100-180 ℃, d(DHS)/d T＞0), and differential is shunk (△ S=DHS-S) greater than about+2%, wherein S boils shrinkage factor, DHS is a dry-hot shrinkage, therefore need carry out high-temperature process before dyeing or after the dyeing to polyester fine filaments or by the fabric that it is made, give the fabric fibre that forms by these filaments to give enough thermal dimensional stabilities; 4) Cha stainability need dye with the chemical staining auxiliary agent that is called carrier under the condition of high-temperature pressurizing, to obtain the fabric of dark and level dyeing.
Especially, according to the invention provides:
1. the polyester fine filaments of spinning-orientation, it has about 1 or less than 1 dpf, particularly less than about 0.8dpf, especially less than about 0.6dpf and greater than about 0.2dpf; The relative viscosity of above-mentioned polyester (LRV) is about 13-23, and zero shears polymer melted temperature (T M°) being about 240-265 ℃, glass transition temperature of polymer (Tg) is about 40-80 ℃; Described long filament is further characterized in that:
(a) shrinkage poor (△ S=DHS-S) is preferably less than approximately+1%, especially less than about 0% less than making an appointment with+2%; Wherein S boils shrinkage factor, and DHS is the dry-hot shrinkage that records at 180 ℃;
(b) maximum collapse tension force (STmax) is about 0.05-0.2g/d, the maximum temperature T(STmax of maximum collapse tension force) is about (Tg+5 ℃)-(Tg+30 ℃), that is to say, be about 70 ℃ polyethylene terephthalate, T(STmax) be about 75-100 ℃ for polymer Tg;
(c) percentage elongation is that 7% o'clock intensity is about 0.5-1.75g/d, ((T B) n/T 7)-ratio is at least about 5/T 7), preferably at least about (6/T 7), (T wherein B) n is that delustering agent for 20.8 reference LRV and 0% is (as Tio 2) the standard fracture strength of %, it is defined as:
（T B）n＝（T B）〔20.8/LRV） 0 75〕（1-X） -4
Fracture strength (T B)=T(1+E B/ 100); Extension at break percentage E BBe about 40-160%; X is the percetage by weight of delustering agent with fraction representation; T equals the intensity of fracture load (gram) divided by former beginning and end stretching dawn number;
(e) on average scatter (DS) less than about 4% along the dawn number of terminal direction, be preferably less than about 3%, especially less than about 2%.
2. the filament of spinning-orientation is particularly suitable for for example being used for the box distortion of high-speed stretch false twisting and air jet texturing, stretching warping, crimping by stretching and obstruction as stretching feed yarns (DFY), and wherein said long filament is further characterized in that:
(a) boil shrinkage factor (S) and dry-hot shrinkage (DHS) all greater than about 12% and less than about maximum collapse potentiality (S M=((550-E B)/6.5)) %, elongation at break is about 80-160%;
(b) percentage elongation is that 7% o'clock intensity is about 0.5-1g/d.
3. the filament of spinning-orientation is specially adapted to the directly long filament (DUY) of use, and it is further characterized in that:
(a) boil shrinkage factor (S) and dry-hot shrinkage (DHS) all is to be about 2-12%, for the woven 6-12% that preferably is about, for the woven 2-6% that preferably is about, like this so that the filament denier dpf(ABO after boiling)=dpf(BBO) * ((100/(100-S)), be about 1-0.2dpf, preferably be about 0.8-0.2dpf, especially be about 0.6-0.2dpf;
(b) percentage elongation is 7% o'clock intensity (T 7) be about 1-1.75g/d, and elongation at break (E B) be about 40-90%;
(c) back yield modulus (Mpy) is about 2-12g/d, and it is (that is Mpy=(1.2T, that is determined by the secant tan β among Fig. 5 20-1.07T 7)/0.13).
4. the filament of spinning-orientation, can be by cold stretch and without heat setting, so that the spinning long filament to be provided, it is further characterized in that:
(ⅰ) boil shrinkage factor (S) and dry-hot shrinkage (DHS) all less than about 12%;
When (ⅱ) Tcc(DCS) being lower than about 105 ℃, the beginning cold crystallization, this is the rate of heat addition with 20 ℃ of per minutes, records with differential scanning calorimetry (DSC);
(ⅲ) instantaneous stretching modulus Mi (=d(stress)/d(percentage elongation)) * 100, greater than about 0; (d(stress)/d(percentage elongation wherein)) being the dawn number of stress (gram)/stretching) curve is to the tangent of percentage elongation; Wherein tensile stress is a tensile force (gram) divided by the dawn number that stretches, the dawn number that the dawn number that regulation stretches equals not stretch and residual stretch-and than (RDR=1+E B, %/100) ratio;
Do not increase and the further significantly temperature that reduces as long as back heat-set temperature (Tset) is less than about shrink tension greatly, under the situation of losing stainability indistinctively, if desired, can reduce the shrinkage factor (S) of above-mentioned elongate filaments with temperature; That is to say, preferably keep Tset to be less than about the beginning temperature of (again) crystallization rapidly greatly.Here, the maximum of Tset is defined as, shrink tension is to slope (the d(ST)/dT of TEMPERATURE SPECTROSCOPY) temperature when numerically reducing (becoming less negative) sharp, referring to Figure 11.
5. pass through the preferred drawn yarn of the long filament preparation of stretching above-mentioned spinning of the present invention-orientation, this drawn yarn is characterised in that:
(a) boil filament denier dpf(ABO after the contraction) be about 1-0.2dpf, preferably be about 0.8-0.2dpf;
(b) boil shrinkage factor and dry-hot shrinkage and all be about 2-12%, preferably, for the knitting 2-6% that is about, for the woven 6-10% that is about;
(c) percentage elongation is 7% o'clock intensity (T 7) be at least about 1g/d, so consequently ((T B) n/T 7)-than being at least about (5/T 7), preferably at least about (6/T 7), wherein, (T B) n is that delustering agent for 20.8 reference LRV and 0% is (as TiO 2) the standardized fracture strength of percentage, E BBe about 15-55%;
(e) back yield modulus (Mpy) is about 5-25g/d;
(f) be at least for the relative dispersion dyeing speed of the standardization of 1dpf (RDDR) about 0.1, preferably at least about 0.15;
(g) dynamic loss modulus maximum temperature T(E " max) be lower than about 115 ℃, preferably be lower than about 110 ℃;
(h) on average scatter (DS) less than about 4%, preferably less than about 3%, especially less than about 2% along the dawn number of terminal direction.
6. bulk aerophane (or tow), it is to form by bulking process with qualified filament of the present invention, for example by air jet texturing, false twist texturing, the box curling and gear crimping technology of filling; Wherein, above-mentioned bulk long filament is characterised in that, filament denier (after the contraction) is less than about 1, preferably less than about 0.8, boil shrinkage factor (S) and dry-hot shrinkage (DHS) less than about 12%, T(E " max) be lower than about 115 ℃, be preferably lower than about 110 ℃; RDDR is at least about 0.1, preferably is at least about 0.15.
Be used for directly using the feature of the particularly preferred long filament of yarn (or tow) also to be:
(a) by wide-angle x-ray scattering (WAXS) with the average crystallite size (CS) of 0.10 plane survey be about the 50-90 dust ( ), for being about 1.355-1.395g/cm 3Work the density value (ρ m) of correction of delustering agent aspect, the volume crystallinity Xv=(ρ m-1.335 of mark)/0.12, be about 0.2-0.5;
(b) n ° (△ n ° is average intrinsic birefringence to the average orientation of mark function f=△ n/ △, stipulate that here it equals 0.22), be about 0.25-0.5, the amorphous orientation function f a=(f-Xvfc of mark)/(1-Xv)), less than about 0.4, be preferably less than approximately 0.3, wherein (△ n) is average birefringence, fc is the crystalline orientation function f c=(180-COA of mark)/180, COA is the crystalline orientation angle that records by WAXS;
(c) (Vf am) is at least about 0.5 * 10 to the amorphous state free volume 6Cubic angstroms (
Figure 921036809_IMG2
3), preferably at least about 1 * 10 6
Figure 921036809_IMG3
3, Vf here, am equals (CS) 3((1-Xv)/Xv)) ((1-fa)/fa), dynamic loss modulus maximum temperature T(E " and max) be lower than about 115 ℃, preferably be lower than about 110 ℃;
(d) be at least approximately 0.1 for the relative dispersion dyeing speed of normal pressure (RDDR) of 1dpf standard, preferably be at least about 0.15.
Except following characteristic, measure the characteristic of long filament resembling in United States Patent (USP) 4134882,4156071 and 5066447, dispersion dyeing speed (RDDR) is standard with 1dpf relatively, dry-hot shrinkage (DHS) records at 180 ℃, laboratory (1ab) relative viscosity (LRV) is to determine according to the United States Patent (USP) 4712998 of Broaddus, it equals (HRV-1.2) approximately, and HRV provides in United States Patent (USP) 4134882 and 4156071.With LRV 20.8Value regard as shear the identical polyester polymers of " newton " melt viscosity η o with zero of the 2GT homopolymers of 20.8LRV reference LRV(for example, when mass velocity is identical with temperature, provide identical silk hole pressure drop).In table 1-VIII, the numeral that " rises to power " with symbol " へ " expression (for example 10 2=10 へ 2); For convenience's sake, very little or very big numerical example such as 0.00254cm and 254000cm/min are expressed as 0.254 and 254, unit wherein is expressed as " cm * 10 へ 2 " and cm/sec * 10 へ-3 respectively; It is measured that dotted line (-) on digit position represents that this value does not have; This value that " NA " expression on digit position records can not be used; Dotted arrow (→) is used to represent value and front clauses and subclauses identical of a certain parameter of certain clauses and subclauses.With sign indicating number/minute measure spinning speed (V), in text, it has been scaled kilometer/minute, and 4 houses 5 are gone into to second decimal place (for example, 4500ypm=4.115Km/min=〉4.12).
By following examples, illustrate preferred embodiment of the present invention:
Polyethylene terephthalate, it has following characteristic, the LRV of polymer is about 13-23(corresponding to (η) that be about 0.5-0.7), for the polyester of ion ground modification, LRV preferably is about 13-18, for the polyester of nonionic ground modification, be about 18-23, zero shears fusing point (T M°) being about 240-265 ℃, glass transition temperature (Tg) is about 40-80 ℃, and it contains more a spot of delustering agent and surface friction modifiers (TiO for example 2And SiO 2), with it at polymer temperature Tp(℃) fusing, and by inert media filter through stop (continuing) time (tr, min), then, by diameter (D RND) and the spinning die wire hole of length (L), with silk hole mass velocity W (=(dpfV/9), g/min), with apparent silk hole shear rate (Ga, sec -1=((32/60 π) (W/ ρ)/D RND 3)) be condition, above-mentioned polyethylene terephthalate is extruded, here,, with Km/min unit representation winding speed (V) centimetre to be unit representation silk hole dimension.
Though as long as the pattern (arrangement of long filament) in silk hole is suitable for the pattern (promptly radially blowing horizontal) of quenching and " shielding " and the length/distribution (seeing the embodiment I) of air velocity distribution of initial delay cooling most, just might spinning and quenching go out to have to resemble the tow of extruding filament density high about 25, but, the long filament that the silk hole spinning that generally is about 2.5-13 from filament density/extrude surface area goes out herein most of embodiment; Wherein, the density of extruding long filament equal the monofilament radical ( #C) (that is, divided by the ratio of extruding surface area (Ao) #C/Ao, cm -2) divided by " shielding ", the long filament newly extruded of " shielding " protection is at least about 2cm be not more than (12dpf approximately 1/2, distance cm) does not directly contact with quench air; Then, here be to be about 22 ℃ preferably with temperature T a() be lower than about polymer Tg (herein, for the 2GT homopolymers, Tg is about 70 ℃) and linear velocity Va(m/min) be about the air of the radially direct projection of 10-30m/min, be cooled to be less than about the temperature of polymer Tg carefully.The used spinning equipment that is fit to is described in United States Patent (USP) 4134882,4156071 and 4529368 basically.
Though for the continuity of spinning has been selected Tp, by balancing delay cooling length (L DQ), quench air temperature (Ta), quench air flow rate (Va) and boundling length (Lc), the variation (DTV) that can scatter (DS) and tensile stress along the dawn number of terminal direction reduce to minimum.The spinning temperature (Tp) that improves polymer (but is lower than ((T approximately M) a+55 ℃) generally can increase the continuity and mechanical performance (that is T, of spinning B, g/d), but generally can reduce along the uniformity of terminal direction and increase shrinkage.
When requiring in the high temperature spinning,,, heat can be passed to the long filament of extruding by the silk hole (being the silk hole of minor diameter) of using high-rate of shear (Ga) in order to reduce to minimum along the inhomogeneity loss of terminal direction with the mechanicalness the subject of knowledge and the object of knowledge.But, as high shear silk hole and high L/D RNDWhen ratio was used together, the operability of spinning degenerated out of a clear sky, for example used the silk hole (seeing the embodiment III) of 9 * 50mil.Can infer under the situation of this low silk hole mass velocity and high shearing condition, the initial stage having occurred shears the molecular order (for example lower chain entropy and possible initial stage " nucleation ") of the polymer melt that causes, particularly the time of staying (tr) thinks here that more than 4 minutes polymer melt this molecular order (possible initial stage nucleation) makes apparent melting point polymer from zero shear force (T when filtering before extruding M°) be increased to apparent value (T M) aThis has the spinning of reducing temperature difference Tp-(T M) aEffect.In order to keep enough big enough spinning temperature difference, need to find further to increase the bulk polymer temperature Tp, this increase is according to being used for selected L, D RNDFormula 2 * 10 with the Ga value -4(L/D RND) Ga, a ℃ determined amount is carried out.
In order to obtain spinning continuity, mechanical performance and along the inhomogeneity balance of terminal direction, when control melt extension strain ε a was about 5.7-7.6, (σ a) was controlled at the about 0.195g/d of about 0.045-to the apparent spinning threadling internal stress that " necking point " located.To attenuate becomes multifilament bundled with chilled long filament boundling, and (V Km/min) reels with the spinning speed that equals the first driven voller superficial velocity.Before packing, by at overfeeding (usually between about 0.5%-5%) slightly between first driven voller and the batching apparatus, eliminate the spinning threadling that causes by friction surface (and air drag) tension force outward.Carry out oil supply and form entwining at the boundling point, preferably after first driven voller.Be chosen in the amount (weight %) of oil supply on the long filament and the degree (RPC) of filament entanglement, to satisfy the processing needs of final use.
Polyester fine filaments of the present invention has good mechanical performance and uniformity, its line density is approximately less than natural silk, but approximately greater than spider silk, promptly filament denier is about 1-0.2, and it has the ability that is dyeed equably under the situation without high temperature and chemical staining auxiliary agent; That is to say that comparing class is similar to these character of natural silk.
Advantageously, if desired, can put in order in spinning in (invention of in the patent application of awaiting the reply jointly 07/420459 of application on October 12nd, 1989, being told about according to Grindstaff and Reese) and handle the fine denier filament yarn, with the hydrophily that improves them and improve moisture transfer and comfortableness with caustic soda.Can reduce the filling of long filament and long filament with the mixed filament in different dawn numbers and/or cross section, improve the aesthetic feeling and the comfortableness of sense of touch thus.By long filament blend with different polymer modifications, can obtain fabulous stainability effect, for example, homopolymers can be used disperse dyeing, and the ion-type copolymer can be used cationic dyeing.
If desired, add partial content in the United States Patent (USP) 4883032,4996740 and 5034174 of United States Patent (USP) 4156071 by resembling Knox, the United States Patent (USP) 4092229 of Maclean and Reese is described and be equivalent to about 0.1% mole chain branching agent, and/or, can obtain the filament of low shrinkage by increasing polymer viscosity pact+0.5-pact+1.0LRV monofilament.
Elongated gauze of the present invention for example is suitable for radial drawing, air jet texturing, false twist texturing, gear crimping and clogs box curling; And the long filament of low shrinkage can be used as the flat weaving silk of direct use and wherein not need the air jet texturing that stretches and the feed yarns of clogging box curling usefulness.Long filament (with the tow that is made of long filament) can also be curled (if desired) and be cut into staple and Soft flocks.The fabric that is formed by these long filaments that improved can carry out surface treatment by habitual napping and velvet brushing process, to produce the sense of touch of chamois leather shape.Can be by selecting cross section, delustering agent and changing the mantle friction performance of long filament by processing resemble the caustic corrosion.The yarn strength and the inhomogeneity combination that have improved make these long filaments be particularly suitable for the processing of final use, and the elongated gauze of these processing requests does not have broken filament (fracture of wire) and dyes equably with critical dyestuff.
The polyester filament of thin monofilament yarn dawn number of the present invention is particularly suitable for making the moisture barrier fabric of high filament density, for example raincoat and medical coat.Can be with the surface removal hair knot (brush or sand milling) of knitting and woven fabric.In order further to subtract Denier, can handle the long filament form of fabric (preferably with) with conventional alkaline process.Elongated gauze, elongated gauze that especially can cation stain, preferably by Strachan at the air interlacing described in the United States Patent (USP) 3940917, can also be used as the covering yarn that elasticity is handled yarn.Fine filament of the present invention can carry out blend online or off-line in the spinning with polyester (or nylon) long filament of high Denier, the cross dyeing effect is provided and/or mixes the postbulkable potentiality of contraction, expanded can the generation by off-line here, for example during warping/warp sizing under the situation of heating overfeeding, perhaps, for example in dye bath, take place with the form of fabric.According to the aesthetic feeling of weave needs of processing and the yarn/fabrics of finally wanting, the degree that selection is entwined and the kind/quantity of oil supply.
Further specify method of the present invention and product obtained by this method by following examples:
The embodiment I
Be equivalent to about 0.60 (η) with 19LRV() and contain the TiO of 0.3% weight 2Polyethylene terephthalate spinning nominal be 100 and the yarn of 300 threads of 0.5dpf.Spinning plate spinning 300-filament yarn with different structure; For example, constitute like this: (ⅰ) by control silk hole to the distance in silk hole greater than about 40mils(1mm) with the formation 2 of single head forsner bit or more a plurality of holes and unlikely causing fuses between long filament; (ⅱ) 300 " equidistant placement " monofilament holes; (ⅲ) 300 silk Kongzui original treaties of arranging with the donut form occupied available " outside " of extruding surface area (Ao) half 50%, make like this and effectively extrude filament density (EFD) and be increased to about 25 from about 12.5; But, the polymer molten fluid of extruding back spinning plate (ⅲ) just converge at once form one with spinning plate (ⅰ) and (ⅱ) similar tapering bundle; And have thus be equivalent to spinning plate structure (ⅰ) and (ⅱ) effectively extrude filament density (EFD); Promptly less than 25 with greater than 12.5, effectively extrude filament density (EFD) for what this non-long filament that is equally spaced was arranged here, determine according to graphic method sample plot among Figure 14.At once just present similar shapes owing to extrude the back endless tow, spread all over the whole long filament of extruding area and, have roughly the same effective long filament and extrude density with the long filament of arranged in form on circumference of donut so sample plot is found equidistant placement.The data of table in the I are about the 300-filament yarn, and this filament yarn is the silk hole spinning of arranging in order to the donut shape, and above-mentioned silk Kongzui original treaty has occupied available 50% of the surface area of extruding.Except for 3500ypm(3.2Km/min) yarn of spinning has length (L DQ) be about the protection " shielding " of 1 inch (2.54cm), for 4500ypm(4.12Km/min) yarn of spinning has L DQThe protection " shielding " that is about 2.25 inches (5.72cm) with the radial quench unit described in United States Patent (USP) 4156071 basically, is cooled to room temperature with the long filament of newly extruding in addition.With 3500ypm(3.2Km/min) filament yarn of spinning has the high shrinkage factor (S) of boiling, and these yarns for example are particularly suitable in stretching warping, stretching air jet texturing, draw false twisting distortion and crimping by stretching as the stretching feed yarns.When spinning speed is increased to 4500ypm(4.115Km/min) time, the value of boiling shrinkage factor (S) reduces to and is lower than 12%, differential shrinkage (△ S=DHS-S) is lower than+and 2%, maximum collapse tension force (STmax) when maximum temperature T(STmax) being lower than 100 ℃ is lower than 0.175g/d, and yield strength (approaches percentage elongation here and be 7% o'clock intensity T 7) greater than 1g/d, make these long filaments not needing be suitable for the purposes of stretching in addition or heat treated direct use fully, for example be used as flat long filament, air jet texturing and the box curling textile filament yarn of filling.
As can be seen, be 176.8mils by area of section (Ac) 2(0.1140mm 2, 1.14 * 10 -3Cm 2) the long filament that goes out of spinning die wire hole spinning, its fracture strength (T B) to be lower than by Ac be 28.3mils 2(0.0182mm 2, 1.82 * 10 -4Cm 2) the long filament that goes out of spinning die wire hole spinning.The intensity of the yarn of present embodiment I is lower, also partly be since lower polymer LRV(19 to 20.8).T BStandard value (use (T here B) n represents) fracture strength (T that equals to record B) and coefficient (20.8/LRV) 0.75(1-X) -4Product, be about 1.057 for this coefficient of these yarns; Therefore, be 20.8 and TiO with reference LRV 2% is 0% when comparing, standard fracture strength (T B) n exceeds about 6%.
Under condition of normal pressure (100 ℃), situation without dyeing carrier, the elongated gauze of present embodiment can be dyed dark color, with relative dispersion dyeing speed (RDDR) value (is standard with 1dpf) of the full drawing of routine is 0.055 to compare, and the RDDR value of the elongated gauze of present embodiment is about 0.16.
In order to form the less long filament number yarn of (with low dawn number), for example, preferably in the exit of quench chamber radially, by means of using the most advanced and sophisticated thread guide that separates of metering oil supply, the yarn beam splitting of 300 threads might be become respectively be 2,3 or 4 yarn bundles of 150,100 and 75 threads.The multiple terminals is allowed with the cavity of higher quality flow velocity (W) by filter pack, and has been reduced the time of staying (tr) of each strand in the cavity of filter pack thus.
The embodiment II
Except postponing " shielding " length (L DQ) be about 2.25 inches (5.72cm) in addition, basically described as the embodiment I, with 4000ypm(3.66Km/min) winding speed (V), use radial quench unit, with about 0.65 (η) of 20.8LRV(of nominal) and contain 0.1% weight TiO 2Polyethylene terephthalate be spun to fine filament.The operability of embodiment II-5 and II-6 is very poor, and does not collect yarn.For with 4000ypm(3.66Km/min), with 15 * 60mil(0.38 * 1.52mm, 0.038 * 0.152cm) the silk hole, the 0.5dpf long filament that spinning goes out thinks that low apparent shear rate (Ga) is one of reason that causes poor operability and broken filament.Even temperature Tp is increased to about 299 ℃, can not provide a kind of acceptable method.Owing to worry to count the uniformity variation, so be not higher than the test of about 299 ℃ of-300 ℃ of temperature along the dawn of terminal direction.The details of method and product is summarised in the table I.
The embodiment III
In the embodiment III, spinning go out 68-and 136-(not twisted with twisted) filament yarn, except for embodiment III-1 to III-9 and III-11 to III-25, be to carry out carrying out spinning according to the embodiment I basically beyond the boundling with a metering oil supply tip described in United States Patent (USP) 4926661.Embodiment III-the 10th as described in embodiment I and the II, makes the long filament boundling with the surface of metering finish roll.Other process detail is summarized in table I and the II.Embodiment III-1 to III-5 and III-12 to III-15 has the T greater than about 1g/d 7-value, this is particularly suitable for as the feed yarns in long filament in the textile filament yarn that directly uses and the air jet texturing that wherein do not stretch them; And if desired, in the warping described in the United States Patent (USP) 5066447 of Knox and Noe stretches (and air jet texturing), can heat (cooling), stretch equably.T 7-value be lower than about 1g/d embodiment III-6,7 and III-16 to the long filament of III-25, long filament in the feed yarns (DFY) is particularly suitable for stretching, for example draw false twisting distortion (FTT) and stretching air jet texturing (AJT) perhaps is specially adapted to the feed yarns in the warp direction stretching.
To III-5, spinning goes out the 68-filament yarn of 50 dawn numbers from the cavity of single nozzle block in embodiment III-1, and it is formed the 136-filament yarn of 100 dawn numbers with excellent mechanical properties at converging guide place twisted.For example, the filament yarn of embodiment III-4 has the spinning continuity of 0.39 place fracture/1000 pounds (0.86/1000kg), and this equals about 9.5 places fracture/10 9Rice.For the air jet texturing that does not have stretching that carries out with Barmag FK6T-80, the gauze of coiling embodiment III-4 under the situation of (measuring) of entwining at about 10cm with the quick pin number method described in the United States Patent (USP) 3290932,, reel under the situation that about 5-7RPC entwines as flat weaving silk woven and in compiling for directly.In embodiment III-6 and the III-7 respectively with 1.44 * and 1.7 * stretch, do not have broken filament, produce the 68-filament yarn at 35 dawn that stretch.Because the spinning productivity ratio of embodiment III-6 (spinning dawn number * spinning speed) is about 25% greater than embodiment III-7, thus compare with embodiment III-7, embodiment III-the 6th, preferred.In the embodiment III-6 with 1.44 * draw ratio successfully carried out the warp-wise cold stretch.Reckon with, according to Frankfort and Knox in the method described in the United States Patent (USP) 4134882, with 9mil(0.229mm, the L/D of spinning die wire hole 0.0229cm) RND-ratio is increased to 5.56 from 2.22, by for the shearing heating that increases the extruded polymer melt creates conditions, can improve mechanical performance significantly; Wherein, the degree of silk hole shearing heating is with the formula in the patent of Frankfort and Knox: 660(WL/D 4) 0.685, ℃ estimation, in the formula, D represents that with mils W is with a Pounds Per Hour expression; But, observed broken filament for embodiment III-8 and III-11.
Embodiment III-12 has obtained qualified performance; Wherein, compare long filament, reduced the time of staying (tr) in the cavity of nozzle block during filtering by spinning 136-with the 68-long filament.Endless tow can be wound into independent 136-endless tow, or the yarn bundle of riving and being wound into two 68-long filaments.In order under the situation of " charging " polymer temperature (Tp) that need not be high, to carry out spinning, find for high L/D RNDThe spinning plate in silk hole, the time of staying, (tr) must be less than 4 minutes.The embodiment IX is seen in the relevant more detailed argumentation of using the spinning plate spinning in high shear silk hole.In embodiment III-12 to III-15, spinning 136-filament yarn, use be 136 9 * 36mil(0.229 * 0.916mm of each spinning plate, 0.0229 * 0.0916cm) the silk hole, and make the filtration time of staying (tr) reduce 50% thus, so that the yarn with excellent mechanical properties to be provided.The yarn of high long filament number be specially adapted to stretch air jet texturing (AJT) and false twist texturing (FTT), wherein, the stretching of straight line-texturing machine configuration is preferred.As described in the embodiment XII, will come from the warp direction stretching flat filament that embodiment III-19,22,24 and 25 yarn are used to prepare nominal 0.5dpf.
The structural behaviour of embodiment III-10 long filament is the representative that shrinkage factor is lower than the long filament of spinning of the present invention-orientation of 6%.The density of the long filament of the embodiment III-10 ((ρ-0.0087(%TiO of the ρ=fiber of measurement 2)) be 1.3667g/cm 3(for 0.03%TiO 2Revised), provide the mark volume crystallinity (Xv=(ρ m-1.335)/0.12 of calculating) be 0.264, weight percent degree of crystallinity (Xw=(1.455/ ρ c) Xv) be 0.281; Average crystallite size (CS) be 70 dusts (
Figure 921036809_IMG4
); The average crystallite angle of orientation (COA) is 12 degree, and it is equivalent to crystalline orientation function (fc=(180-COA)/180) be 0.93; Average birefringence (△ n) is 0.0744, the average orientation function that provides (f=△ n/0.22) is 0.34, amorphous orientation function (fa=(f-Xvfc)/(1-Xv)) be 0.13, the amorphous state free volume ((Vf, am)=((1-Xv)/Xv) ((1-fa)/and fa) CS 3) be about 6 * 10 6Cubic angstroms (
Figure 921036809_IMG5
3).The birefringence of present embodiment long filament poor (△ 95-5) is 0.0113, Niso is 1.5882, the velocity of sound (SV) is 2.72Km/sec, the sound wave modulus (Mson) that provides is 83.6g/d, at maximum temperature T(STmax) maximum collapse tension force (STmax) when being 80 ℃ is 0.143g/d, boiling shrinkage factor (S) is 4.6%, the contraction modulus (Ms=(STmax/S) 100 that provides) is 3.1g/d, dry-hot shrinkage (DHS) is 5.0%, provide contraction rate variance (△ S=DHS-S) to be lower than+1%, original modulus is 71.6g/d, back yield modulus (Mpy) is 5.35g/d, uncorrected dispersion dyeing speed is 0.144, is that the relative dispersion dyeing speed RDDR of standard is 0.104 with 1dpf.
The embodiment IV
Except postponing the length (L of " shielding " DQ) be about 2-5/8 inch (6.7cm), measure the oil supply tip with beyond the endless tow boundling with using apart from one of spinning plate surface 43 inches (109cm), basically press described in the embodiment I, with a quenching device for spinning radially, the spinning poly ethylene glycol terephthalate, this polymer has about 0.66 (η) of 21.2LRV(of nominal), its TiO 2% weight is 0.035,0.3 and 1.In table III and IV, summed up other process detail.Find to increase TiO 2Weight percent, make the fracture strength (T of these filaments B) reduce.TiO 2Consumption between following scope, change usually, for MIN yarn and metal and yarn and thread friction,,, be lower than approximately 1.5% for the mechanical performance and the visual sense of beauty of hope for about 0.035%, relatively be typically and be lower than about 1%.
The embodiment V
Use similar in appearance to the device of embodiment IV about 0.655 (η) of the 21.1LRV(of spinning nominal) and contain 0.3TiO 2The polyethylene terephthalate of % weight.Embodiment V-1 to V-4, IV-9 and IV-10 used 12 * 50mil(0.305 * 1.270mm, 0.0305 * 0.127cm) spinning die wire hole.Embodiment V-5,7,8 and 11-13 use 9 * 36mil(0.229 * 0.914mm, 0.0229 * 0.0914cm) spinning die wire hole, embodiment V-6 is used 6 * 18mil(0.152 * 0.457mm, 0.0152 * 0.0457cm) spinning die wire hole removes the warp direction stretching at 85 dawn of spinning 100-long filament and the feed yarns of stretching air jet texturing (AJT) usefulness.In embodiment V-8 and V-10, the length (L of quenching will be postponed DQ) be increased to 4-5/8 inch (11.7cm) from 2-5/8 inch (6.7cm).Owing to increased delay length (L DQ), so along the inhomogeneities of terminal direction increased by 4 *, and by the inhomogeneities of dawn number between the long filament of tow cross section optical measurement increased by 2 *.When postponing length (L DQ) be lower than approximately (12dpf 1/2) during cm, can obtain good uniformity.
Embodiment V-11 is to V-the 13rd, with 2400,3000 and 3500ypm(2.2,3.05 and 3.35Km/min) repeat embodiment V-7; Wherein, for the spin-drawing feed yarns, change the mass velocity in silk hole, thus the dpf of spinning will be stretched to about 0.5dpf final dawn number (here, stretching dpf=spinning dpf/ draw ratio=spinning dpf * (drawn yarn RDR/ spinning long filament RDR) wherein residual stretch compare RDR=(1+E B, %/100)).Embodiment V-11 to the long filament of V-13 is 7% o'clock intensity (T at percentage elongation 7) value is lower than about 1g/d, makes them be specially adapted to the feed yarns that stretches, though the shrinkage factor of undrawn yarn is lower than 12%.The result of warp direction stretching is summarized in the embodiment VII.
The embodiment VI
In the embodiment VI,, postpone quenching length (L in order to change spinning dawn number DQ), the length (Lc) of spinning temperature (Tp) and converging guide is with 3300ypm(3.02Km/min) repetition embodiment V-13.The dawn number scatter (DS) be the long filament of 3.8% embodiment VI-2 successfully stretched 1.35 *, produce the 0.3dpf 100-filament yarn that stretches, it is 2.3% that its dawn number scatters, intensity is 4.4g/d, E BBe 32.5%, boiling shrinkage factor (S) is 6.3%.In the present embodiment, find when total yarn bundle dawn number and each long filament dawn, number was reduced the time, if balancing processing again not will degenerate along the uniformity of terminal direction.In order under the situation of this low-quality flow, to guarantee good spinning continuity, need to improve the temperature of polymer.Postpone length (L by making DQ) reduce to about 2.9cm and make boundling length (Lc) reduce to 81cm from 109cm, make along the dawn number of terminal direction and scatter (DS) from 12.1%(embodiment VI-1) be improved to and be lower than 4%.Be lower than 0.5 yarn for dpf, it is difficult reaching the DS-value identical like that with the yarn of the about 1dpf of 0.5-.In table III and IV, summed up the details of technology and product.
The embodiment VII
With about 0.65 (η) of nominal 21LRV() contain 0.035TiO 2The fine filament of the polyethylene terephthalate spinning trilobal of % weight, what use is to have 9 * 36mil(0.229 * 0.914mm, 0.0229 * 0.0914cm) and 12 * 50mil(0.305 * 1.270mm, 0.0305 the spinning plate of * 0.127cm) dip hatch, and area (Ac) is about 197mils 2(1.27mm 2, 0.0127cm 2) the spinneret orifice of Y type outlet, spinneret orifice is equivalent to about 15.9mils(0.40mm, D 0.04cm) RNDWith the L/D that is about 1.5 RND(basically as described in the embodiment 45-47 of United States Patent (USP) 4195051).Compare with the metering silk hole of 12 * 50mil, the metering silk hole of 9 * 36mil provides better mechanical performance and has counted uniformity along the dawn of terminal direction.The 100-filament yarn can be stretched to 50 dawn of nominal, or about 0.5dpf, and do not form broken filament.
The embodiment VIII
Spinning nominal LRV is about the about 2 moles of % ethylidene of 15.3 usefulness-5-sodium-ester modified polyethylene terephthalate polymer of sulfo-isophthalic acid, use to postpone length and be that the laminar flow of 2.2 inches (5.6cm) is horizontal blows chilling apparatus (basically as United States Patent (USP) 4529638 described in) and locate with metering oil supply tip thread guide the endless tow boundling at about 43 inches (109cm).Because the ion position is played crosslinking agent and is caused higher melt viscosity, so for the polyester of ion modification, usually preferred lower LRV.Used here 15LRV has the melt viscosity of 20LRV homopolymers.But if people want spinning to hang down the LRV homopolymers, it generally is favourable adding tackifier so, for example adds silicic acid tetraethyl ester (as described in the United States Patent (USP) 3335211 of Mead and Reese).Usually preferably, spinning LRV is about the ion modification polyester of 13-18 and the nonionic modified polyester that LRV is about 18-23.With winding speed from 2400ypm(2.2Km/min) be increased to 3000ypm(2.74Km/min).The same with what expect, the cation copolymer yarn has the lower T based on its low LRV B-value.For the filament yarn that is used for napping or brushing fabric with for the tow that will be cut into Soft flocks, lower LRV is preferred.The yarn that spinning goes out can be stretched to the 100-filament yarn at about 50 dawn and broken filament can not occur.Compare with the 0.125RDDR-value of the 2GT homopolymers of spinning under condition of similarity, the RDDR-value of cation-modified polyester is 0.225.
The embodiment IX
Use similar in appearance to the device of embodiment IV, with the air velocity of about 30m/min, about 0.67 (η) of spinning nominal 21.9LRV() and contain 0.3TiO 2The polyethylene terephthalate of % weight.Embodiment IX-1 to IX-3 is used 12 * 50mil(0.305 * 1.270mm, 0.0305 * 0.127cm) spinning die wire hole, embodiment IX-4 to IX-8 is used 9 * 36mil(0.229 * 0.914mm, 0.0229 * 0.0914cm) spinning die wire hole, embodiment IX-9 to IX-11 is used 6 * 18mil(0.152 * 0.457mm, 0.0152 * 0.0457cm) spinning die wire hole, remove the 100-long filament low-shrinkage yarn at 50 dawn of spinning nominal, this yarn is applicable to through compiling and woven direct use weaving silk and be applicable to and wherein do not need aerojet that stretches and the feed yarns of clogging box distortion.
Expect in United States Patent (USP) 4134882, to be told about,, can improve mechanical performance by increasing the shear rate (Ga) in a hole as Frankfort and Knox.Silk hole for 9 * 36mil is compared with the silk hole of 12 * 50mil, has seen this improvement, and still, beyond thought is that the silk hole spinning with 6 * 18mil needs higher polymer temperature.According to calculating since the polymer temperature that the higher shear rates in 6 * 18mil silk hole causes increase, expect to compare with the silk hole of 12 * 50mil with 9 * 36, in fact the silk hole of 6 * 18mil will need lower polymer temperature (Tp), as what Frankfort and Knox lectured.But,, must increase about 5-6 ℃ of polymer temperature for the spinning plate with 6 * 18mil silk hole of high shear provides qualified spinning continuity.By inference, when this low-quality flow (W), the higher shearing in 6 * 18mil silk hole causes the molecular order of polymer melt, and even may cause having and increase apparent melting point polymer (T M) nucleation of a effect, use (T here M) a represents (T as the following empirical equation of the function of silk hole shear rate (Ga) M) a: i.e. (T M) a=T M°+2 * 10 -4((L/D RND) (Ga)], ℃.The polymer spinning temperature difference here is defined as:
〔Tp-（T M）a〕＝〔（Tp-T M°）-〔2×10 -4（L/D RND）Ga〕，
Along with apparent shear rate (Ga) and L/D RNDThe increase of the product of ratio, the polymer spinning temperature difference reduces effectively; Therefore for the continuity of spinning, need to increase polymer temperature Tp, to keep the minimum spinning temperature difference, preferably at least about 30 ℃ at least about 25 ℃.This with expect according to the instruction of Frankfort and Knox opposite.Summed up the result of technology and product in table IV and the V.
The embodiment X
With the device similar to the embodiment IV, air velocity does not wait to about 30m/min from about 11m/min, about 0.67 (η) of spinning nominal 21.9LRV() and contain 0.3TiO 2The polyethylene terephthalate of % weight.Embodiment X-1 to X-9 is used 12 * 50mil(0.305 * 1.270mm, 0.0305 * 0.127cm) spinning die wire hole, embodiment X-10 to X-16 is used 9 * 36mil(0.229 * 0.914mm, 0.0229 * 0.0914cm) spinning die wire hole, remove the low-shrinkage yarn of 100 long filaments at 70 dawn of spinning nominal, the T of this yarn 7-value is greater than about 1g/d, and this yarn is specially adapted to through compiling and woven direct use weaving silk and wherein do not need the aerojet that stretches and the feed yarns of clogging box distortion.According to observations, with higher polymer temperature and lower air velocity mechanical performance is improved.For the long filament of higher dpf, as (Deutsche Bundespatent 2814104 of Bayer) that be noted, change the distance L c of converging guide, to almost not effect of mechanical performance.Regrettably, the technique change of improvement mechanical performance makes along the dawn of terminal direction and counts the uniformity variation.Successfully spinning has excellent mechanical properties and the inhomogeneity fine filament of dawn number, need carry out balance between cooling off for " heat " polymer of mechanical performance with for " rapidly " of inhomogeneity polymer.This instruction with Frankf-ort and Knox is opposite, in their instruction, in order to provide the dawn number greater than 1 high-quality long filament, adopt " heat " polymer to combine with slow quenching, quenching wherein is by means of using low quenching speed, postponing to shield and/or add the heat lag quenching to realize.Higher " charging " polymer temperature (Tp) with by means of than the shearing of small diameter wire hole spinning plate heating with by means of the short length (L that postpones DQ) fast quench between balance, the performance of balance yarn preferably usually.Shorten boundling length (Lc) and can improve uniformity, and because air drag is lower, winding tension reduces.When pressing the method spinning high Denier of Frankfort and Knox,, find not significant the improvement for shortening boundling length.In table V and VI, summed up the result of technology and product.
The embodiment XI
Respectively with 1.45 *, 1.5 * and 1.55 * draw ratio, with the cold stretch and 155 ℃ of stretchings equably of the feed yarns of embodiment V-11,12 and 13 fine filament, provide the drawing of 50 dawn 100 of the nominal long filament that can be used as flat weaving silk.The elongated gauze that stretched has good mechanical performance and counts uniformity along the dawn of terminal direction, and less than about 6% the shrinkage factor of boiling.The shrinkage factor of cold stretch yarn is slightly smaller than the yarn of hot-stretch, and more even a little.Because the less degree of entwining and different oil supply, can the instruction in United States Patent (USP) 5066447 according to Knox and Noe, these yarns are carried out the cold stretch air jet texturing.The feed yarns of box/friction twisting distortion usefulness that also yarn that these fine filament spinning can be gone out is used as stretching aerojet/filling.In the table VII, the technology of warp direction stretching and the details of product have been summed up.
The embodiment XII
Come repetition embodiment III-20 to 25 by changing spinning speed and spinning dawn number, form the stretching feed yarns of 35 dawn 68-filament yarns to provide to be stretched.To have the yarn cold stretch that the inhomogeneity nominal 50-60 dawn spinning of excellent mechanical properties and dawn number goes out, and, obtain the low-shrinkage long filament of nominal 0.5dpf yarn, and do not lose mechanical performance and count uniformity along the dawn of terminal direction 160-180 ℃ of heat setting.In table IV and V, sum up the details of spinning technique and product, in the table VII, summed up the details of corresponding drawing process and product.
Embodiment X III
In embodiment X III, studied and obtained high T 7The ability of elongated gauze.Use to the embodiment X in similar device for spinning.By 9 * 36mil(0.229 * 0.914mm, 0.0229 * 0.0914cm) spinning die wire hole is extruded nominal 20.8LRV(0.65 (η)) contain 0.3TiO 2The polyethylene terephthalate of % weight, and use except that delay length is about 2.25 inches (5.7cm), the radial quench unit described in the embodiment I cools off.By means of using the most advanced and sophisticated thread guide of metering oil supply, locate in the boundling length (Lc) on distance spinning plate surface about 32 inches (81.3cm), chilled long filament boundling is become tow.Winding speed is from 4500ypm(4.12Km/min) to 5300ypm(4.85Km/min) do not wait, so that T to be provided 7-be worth direct use weaving silk for 68 and the 100-long filament of about 1-1.5g/d.In the table VI, summed up the details of technology and product.Compare with the embodiment X, owing to used lower polymer-melt temperature (Tp) and higher quench air flow rate (Va), so the tension force of embodiment X III is very poor.
Embodiment X IV
Use Barmag FK6T80, with 300Km/min, will be according to 91 dawn 100-filament yarn air jet texturings of embodiment IV preparation; Wherein, with 1.0 *, 1.1 *, 1.2 * and 1.32 * draw ratio, the yarn cold stretch (about 40 ℃) that spinning is gone out, then, with conventional air nozzle with 125 pounds/inch 2(8.8kg/cm 2) pressure carry out air jet texturing, with provide filament denier serve as about 0.7-0.9(boil shrink the back) and about 0.77-0.94dpf(boil contraction afterwards) bulky yarn.The dawn numerical table of the modified continuous filament yarn that does not stretch is bright, because expanded (for example, long filament forms circle), it is about 11% that yarn Denier has increased, herein ratio (dawn number) AJT/ (dawn number) FLATMore preferably greater than about 1.1; But the bright dawn number of the dawn numerical table of long filament does not increase.As what expected, because long filament forms circle, so the intensity of textured yarns is lower than the flat yarn of stretching; But, be applicable to the final use of bulk fabric.Even with 1.32 * draw ratio, provide residual elongation and be 27.2%(and be equivalent to 1.27 residual stretch than RDR) textured yarns, it boils shrinkage factor (S) and dry-hot shrinkage (DHS) also is respectively about 12.7% and 11%, shrinks rate variance (△ S=DHS-S) less than about (1.7%).If necessary, through heat setting, can make these shrinkage factors be reduced to about 2%.As regulation here, in the process of drawing, by maintenance at least about 1.4 * RDR, carry out the uniform part cold stretch of embodiment X IV-1 and 2.The argumentation in United States Patent (USP) 5066447 according to Knox and Noe, as long as percent thermal shrinkage is lower than about 12%, preferably be lower than about 10%, particularly be lower than about 8%, the ability that these fine filament are stretched by part equably just be considered to long filament that spinning goes out crystalline texture caused.In embodiment X IV-5 to 8, sequentially with the yarn cold stretch and the air jet texturing of 68-long filament.As long as the shrinkage factor of AJT yarn is higher, shrinkage factor just increases with draw ratio.In the table VIII, the technology of embodiment X IV and the data of product are provided.
Make the textile yarn blend (yarn plying) of 2 or more cold stretch AJT yarns, wherein at least one AJT yarn is lower than about 3% by heat setting to shrinkage factor, other AJT yarn is not by heat setting, therefore have very high shrinkage factor, provide a kind of formation to mix the method for simplifying that shrinks yarn like this.Can provide similar mixing to shrink yarn with the component than low-shrinkage, this component is by means of another kind of technology, for example by means of hot-stretch, carries out or does not carry out heat setting and form.Therefore, can provide by 2 or more endless tows that stretched of blend and mix the AJT yarn that shrinks, endless tow wherein all is to stretch under the situation that does not have back heat treated by cold stretch, these tow are cold drawn to reach different elongations but make, and preferably about 10% or more than 10%.The mixing contraction stretching yarn that makes can be carried out AJT and handle, a kind of distortion (expanded) yarn that mixes contraction is provided.Long filament be can also reduce with the mixed filament in different dawn numbers and/or cross section to the piling up of long filament, and the aesthetic feeling and the comfortableness of sense of touch improved thus.Elongate filaments by the different polymer modifications of blend can obtain unique stainability effect, for example with the homopolymers of disperse dye dyeable look and the blend of the elongate filaments of the ion-type copolymer of using cationic dyeable.In the table VIII, summed up the details of AJT technology and product.
Embodiment X V
In embodiment X V, spinning is used for the stretching feed yarns of false twist texturing (FTT).In embodiment X V-1, with D/Y-than be 1.707 L-900PU machine with 500m/min, 1.628 * draw ratio, make the 68-long filament distortion at 58 dawn of nominal, the 68-long filament textured yarns at 37 dawn of nominal (0.54dpf) is provided, and its intensity (T) is 4.1g/d, extension at break (E B) be 26.8%, percentage elongation is 7% o'clock intensity (T 7) be 2.19g/d, original modulus (M) is 44.6g/d.In embodiment X V-2, except with 1.59 D/Y-ratio, with 1.461 * draw ratio beyond, in embodiment X V-1, processing is used for the stretching feed yarns of false twist texturized 118 dawn of nominal 200-long filament, the 200-long filament textured yarns at 83.5 dawn of nominal (0.42dpf) is provided, and its intensity (T) is about 3.25g/d, extension at break (E B) be about 23.9%.The instruction in United States Patent (USP) 5066447 according to Knox and Noe, with 1.49 * draw ratio, also successfully with yarn " part " ground warp of 200-long filament to stretching, form the flat yarn of 79.6 dawn of nominal 200-long filament, its intensity is 4.81g/d, extension at break (E B) be 45.1%.In embodiment X V-3, in order to be used for the stretching feed yarns of false twist texturing and warp direction stretching, the 100-filament yarn at processing 38 dawn of nominal.The technological operation in the silk of embodiment X V-3 usefulness 6 * 18mil(0.152 * 0.457mm) hole is than with 9 * 36mil(0.229 * 0.914mm) hole is good.The yarn of warp direction stretching embodiment X V-3 in the condition and range of embodiment X VIII is provided for the 100-filament yarn of the 0.22-0.27dpf of woven and knit goods.
Embodiment X VI
In embodiment X VI, metering pore and area by 9 * 36mil(0.229 * 0.914mm) are 318mils 2(0.205mm 2) the outlet spinneret orifice in slat cross section of four rhombus ripples, at 285 ℃, extrude and contain 0.035TiO 2The 21.2LRV polyester polymers of % weight.Use the radial quench unit that 2.9cm postpones length that has that uses in the embodiment III, the 100-endless tow at 80 dawn of quenching, at 109cm place, distance spinning plate surface, carry out boundling by means of a most advanced and sophisticated applicator of metering oil supply, and with 2350ypm(2.15Km/min) spinning speed reel.Yarn with the quenching of 47.5mpm air at room temperature has, and the dawn number along the terminal direction of about 1.6-1.8% scatters (DS), about 2.8% BOS, 92.9% average extension at break (E B), the fracture strength (T of 4.56g/d B), make (T B) n/T 7-ratio is about 4.3.When quench air speed is reduced to 21.7m/min, T BBe increased to about 4.64g/d, meanwhile (T B) n/T 7-ratio is about 4.5.Lower T B-value (promptly, be lower than about 5) be because the result of corrugated filament cross section shape, such long filament can be used in some technologies, for example false twist texturing (FTT) and air jet texturing (AJT), spin more aesthetic feeling of staple fibre yarn outward appearance in order to make, in these two kinds of distortion, require long filament to break, to produce the more long filament of refinement (that is, also lacking) than about 0.2dpf.
Embodiment X VII
In embodiment X VII, with 3500ypm(3.2Km/min) and 4500ypm(4.12Km/min) the spinning void concentration be about the 50-long filament at 43 dawn of nominal of 16-17%.Basically described as following patent, use has the bracket-hairs tubule spinneret orifice of metering pore of 15 * 72mil(0.381 * 1.829mm) at 290 ℃, back merging by means of nominal 21.2LRV polymer, form hollow yarn, these patents are the BP 1106263 of people's such as Champaneria United States Patent (USP) 3745061, Farley and Barker, United States Patent (USP) 3924988(Fig. 1 of Hodge), United States Patent (USP) 4444710(Fig. 3 of Most), BP 838141 and 1106263.Adjust the geometry of inlet pore (dip hatch), with the protrusion of preferred extrudate with too early flat the contracting of hollow melt spinning line minimized to the arc spinneret orifice.The internal diameter of the ring section that adjustment is formed by the arc spinneret orifice and the ratio of external diameter reach greater than about 10% and more preferably greater than about 15% voids content percentage.Find that voids content is with the area of extruding the space (π ID 2/ 4), the increase of mass velocity, polymer malt viscosity (that is, being directly proportional) and winding speed (V) and increasing with LRV/Tp, and select above technological parameter to obtain, preferably at least about 15% voids content (VC) at least about 10%.For example, except air velocity being reduced to about 16m/min and carrying out with the most advanced and sophisticated applicator of metering oil supply less than about 140cm distance beyond the boundling, as described in the embodiment X VI, radial quench unit with short delay shielding is housed makes thin hollow yarn quenching.The percentage elongation that has the intensity/elongation/modulus that is respectively about 3gpd/90%/45gpd and be about 0.88g/d with the yarn of 3.2Km/min spinning is 7% o'clock intensity (T 7).The percentage elongation that has the intensity/elongation/modulus that is respectively about 2.65gpd/46%/64gpd and be about 1.5g/d with the yarn of 4.115Km/min spinning is 7% o'clock intensity (T 7) with 3.2 and the yarn of 4.12Km/min spinning have and between about 3-5%, boil shrinkage factor (S).
Embodiment X VIII
In embodiment X VIII, from 1.4 * to 1.7 * the draw ratio scope in, the yarn that the spinning of stretching embodiment X V-3 goes out provides the dawn number to be respectively 26.6 to 22.2 elongate filaments yarn; Along with the increase of draw ratio, intensity is increased to 5.61g/d from 4.38g/d, extension at break (E B) reduce to 15.8% from 36.6%.The shrinkage factor of boiling of all drawings all is about 4%.Summary for technology and product sees Table VIII.
Embodiment X IX
In embodiment X IX-1 and X IX-2, in order in woven and knit goods, to be used as the flat filament of direct use, with 4400ypm(4.02Km/min), the 200-long filament of spinning nominal 0.5dpf and 168-the filament yarn feed yarns of embodiment X V-3 and 4 (respectively from).These yarn air jet texturings (AJT) can not also be stretched, so that the low-shrinkage AJT yarn of nominal 3% shrinkage factor to be provided.
The embodiment XX
In the embodiment XX, by long filament cospinning with low denier filament of the present invention and higher Denier, the preparation combined filament yarn, the long filament of higher Denier for example be by Knox the low-shrinkage long filament described in the United States Patent (USP) 4156071 and/or by Piazza and Reese at the high shrinkage long filament described in the United States Patent (USP) 3772872, come like this for the contraction that mixes (for example in fabric back expanded) provides potentiality, for example under the situation when low-shrinkage long filament of the present invention is mixed with the high shrinkage long filament of Piazza and Reese.For the low-shrinkage filament yarn that mixes dpf, for example pass through cospinning long filament of the present invention and Knox filament yarn in the preparation of the long filament described in the United States Patent (USP) 4156071, by means of using heat pipe or steam jet to carry out online heat treatment, this processing does not reduce filament denier (promptly basically, there is not the space to stretch), the route that obtains unique postbulkable filament yarn of mixing shrinkage factor is provided thus, in this filament yarn, the shrinkage factor of low denier filament of the present invention remains unchanged basically, and the long filament of higher Denier (for example, shrinkage factor 2-4dpf) is increased to greater than 10% from the shrinkage factor (S) of initially boiling that is lower than about 6-10%, is typically and is increased to about 15-35%.The mixing shrinkage factor yarn for preparing by means of above-mentioned medium heat treatment is different from by mixing the yarn than the acquisition of high shrinkage long filament of low-shrinkage long filament of the present invention and Piazza and Reese, in this a kind of yarn in back, heat treated high shrinkage long filament (has for example improved shrink tension significantly, at least about 0.15g/d), even in structure very closely in the woven fabric, this yarn also can produce by the shrinkage factor of mixing cause expanded.Till now,, then carry out or do not carry out process annealing, only obtain high shrinkage and high shrink tension (being called convergent force here) and make up for example by the complete general LOY/MOY/POY that stretches.Low denier filament of the present invention moves on to the surface by mixing punctured bit, even and also can provide a kind of luxurious tactile aesthetics of softness the most closely in the fabric in structure.Generally be to be lower than its glass transition temperature and to heat-treat later on long filament being attenuated fully and be quenched to, and heat treatment carries out as follows, during heating treatment the quantity of the quantity of the tension force of the Zeng Jiaing shrink tension that increases by means of this heat treatment that equals to be seen.Select heat treated condition to be, temperature is approximately higher than cold crystallization temperature Tcc(DSC) (generally being about 95-115 ℃), and be less than about high crystallization temperature Tc(for most of polyester, generally be about 150-180 ℃), this selection has produced (for example has good stainability, the long filament of high shrink tension high RDDR), and be higher than the heat treatment of carrying out under the temperature of Tc has produced the long filament of the high shrink tension that stainability reduced.Not by means of passing high pressure superheated steam (for example 40-140psi, at about 245 ℃), by means of passing a heat pipe, long filament can being heated exactly.Can be high and the long filament of low dpf from the cavity spinning of the nozzle block that separates, merge the tow that forms a single mixing dpf then, perhaps can wherein, select a silk hole dimension (L and D) and a hole count from a single nozzle block cavity spinning #C is to provide different mass velocities; For example, by selecting a silk hole, ((dpf) with the ratio that causes the filament denier that spinning goes out b/ (dpf) a) equal approx ((LaDb/LbDa) n* (Va/Vb) * (Db/Da) 3), the long filament of its a and the different dawn numbers of b representative; For newton's polymer melt, n=1(and here be that sample plot is determined according to habitual silk hole pressure drop test), and with the average dpf that causes measurement equal (( #A dpf a+ #B dpf b)/( #A+ #B)).Above-mentioned heat treatment method can also be used to, by specific final use need defined like that, increase the lower shrinkage factor of the low denier filament of the present invention, for example, for hard-packed woven, along with the increase of higher shrink tension (and convergent force), shrinkage factor increases to about 6-8% from about 3%.
Embodiment X XI
In embodiment X XI, the flat weaving of the not stretching of 50 dawn of cold stretch 68-long filament silk equably, and heat-treat at 160,170 and 180 ℃ provides the drawn yarn of 36 dawn 50 of nominal long filament, and what it had about 4-5% boils shrinkage factor (S), the T of about 3.5g/d 7, the intensity of about 4.5g/d and about 27% extension at break.The Wu Site of this drawn yarn (Uster) % is about 2.1-2.4%, and the fabric that can be used to critically dye.
Embodiment X XII
Lectured in United States Patent (USP) 3940917 as Strachan, spray by high-speed air and tangle, fine denier filament of the present invention can be used for coated elastomer silk (and band).Polyester fine filaments with the polymer manufacture of cation dyeable aspect modification is specially adapted to elastomer yarn, for example Lycra
Figure 921036809_IMG6
, from these elastomer yarns, " ooze out " (" bleeding ") to prevent dyestuff, for example for the Lycra that uses through the homopolymers polyester coating of nonionic disperse dyeing
Figure 921036809_IMG7
Viewed.Coat for air-entangled, direct use long filament of the present invention be preferred (and have the increase described in the embodiment XX the long filament of shrinkage factor, shrink tension and convergent force be particularly preferred), these long filaments can make the elastomer yarn of coating be colored under the condition of normal pressure without carrier, for example, similar in appearance to the dye bath condition (except dyeing) of dying the elastomer yarn that Tynex coats with anion acidity dyestuff.
Some examples with the fabric of yarn manufacturing of the present invention are: 1) medical barrier fabric, it is that POY warp thread with the conventional warp direction stretching of the direct use flat filament weft yarn of 70 dawn 100 of low-shrinkage long filament and 70 dawn 34 long filaments constitutes, and it is woven with the speed of per minute 420 weft yarns with the high speed water-jet loom, produces the plain weave fabric of per inch 164 warp thread and per inch 92 weft yarns thus; 2) business suit satin, it is to use silk to match with the false twist texturized weft yarn of 60 dawn 100 long filaments as warp thread with about 70 dawn 100 long filaments direct to constitute, the satin of per inch 172 warp thread and per inch 100 weft yarns is provided thus; With 3) elephant crepe fabric, it is to use silk to constitute as weft yarn as the stretch textured yarn of warp thread and 60 dawn 100 of 2-thigh long filament with 70 dawn 100 long filaments direct.
For convenience's sake, list the used symbol in front, conversion coefficient and analytical expression below:
The PET polyethylene terephthalate
2GT PET
TiO 2Titanium dioxide
SiO 2Silica
() f " fiber "
() p " polymer "
() m " measurement "
Dpf filament denier (/ 9000 meters of 1 grams)
Dpf(ABO) boil DPF after the contraction
Dpf(BBO) boil perisystolic DPF
DS scatters (± 3 sigma) along the % dawn number of terminal direction
The variation of DTV tensile stress (%)
(η) inherent viscosity (IV)
LRV relative viscosity (laboratory)
The IV inherent viscosity
LRV 20.8In the time of 295 ℃ and the homopolymers of 20.8LRV
(unmodified 2GT) has the LRV that identical melt zero is sheared the polyester polymers of newton's melt viscosity
The C celslus temperature scale
The apparent melt viscosity of η a (pool)
The melt viscosity of η o shear rate-＞0 o'clock
The weight percent of X delustering agent
T M° zero shear melting point polymer (℃)
(TM) aThe apparent fusing point of polymer (℃)
The Tg glass transition temperature of polymer (℃)
Tp polymer melt spinning temperature (℃)
Ta quench air temperature (℃)
Ts spinning threadling surface temperature
Tr filters the time of staying (min)
W silk hole mass velocity (gpm)
Q silk pore volume flow velocity (cm 3/ min)
The flow velocity of Q spinneret (gpm)
#The monofilament number of each spinneret of C
V FFree volume (the cm of nozzle block (filling) 3)
L silk hole length (cm)
L/D RNDThe ratio of silk hole length-diameter
D RNDBe equivalent to identical *-the silk bore dia in the circle silk hole of area of section (Ac)
D RefThe diameter of the spinning plate of reference
D SprtThe diameter of test spinning plate
Area of section (the cm in Ac silk hole 2)
The apparent silk of Ga hole shear rate (sec -1)
The apparent spinning threadling strain of ε a
E RApparent spinning threadling ratio of elongation
The filament density that EFD extrudes
The dv/dx velocity gradient
The apparent spinning threadling internal stress of σ a (g/d)
Va quench air laminar velocity (m/min)
L DQThe delay length of quenching
Lc boundling length
The spinning speed (Km/min) at Vc boundling place
V spinning (coiling) speed (Km/min)
The extruded velocity (m/min) in Vo silk hole
The Ao nozzle block extrude area (cm 2)
Dv/dx spinning threadling velocity gradient (min -1)
η melt viscosity (pool)
DQ postpones quenching
The value that () N records at " constriction " point
Ypm, the yardage of y/min per minute
Mpm, the rice number of m/min per minute
Gpm, the gram number of g/min per minute
Fibre density (the g/cm that ρ m measures 3)
ρ c has done the fibre density of revising for delustering agent
Amorphous density (the 1.335g/cm of ρ a 3)
Density (the 1.455g/cm of ρ x crystallization 3)
Xv volume crystallinity percentage
Xw weight crystal degree percentage
S boils contraction percentage
The xeothermic contraction percentage of DHS
△ S shrinks rate variance (DHS-S)
The maximum potential minification (%) of Sm
S TShrink tension (g/d)
STmax maximum collapse tension force (g/d)
T(STmax) maximum temperature of shrink tension (℃)
Ps contractility (g/d) (%)
The highest setting temperature of Tset
Mi instantaneous stretching modulus (g/d)
M initial (Young) stretch modulus (g/d)
Yield modulus behind the Mpy (g/d)
T 7Percentage elongation is 7% o'clock a intensity (g/d)
T 20Percentage elongation is 20% o'clock a intensity (g/d)
T intensity (g/d)
T BFracture strength (g/dd)
(T B) n normal intensity T B(g/d)
Gpdd, the gram number at every stretching dawn of g/dd
Gpd, the gram number at every (the former beginning and end stretch) dawn of g/d
SF form factor (=P M/ P RND)
P MThe girth of measuring (P)
P RNDThe P of round long filament of the same area
The relative dispersion dyeing speed of RDDR (min 1/2)
DDR dispersion dyeing speed (min 1/2)
RDR residual stretch ratio
1.abX for example, the draw ratio of value " 1.ab "
E BExtension at break (%)
Yield modulus (g/d) after the tan α secant
Yield modulus (g/d) behind the tan β tangent
△ n birefringence
The birefringence of △ a amorphous areas
The birefringence of △ c crystal region
△ ° of intrinsic birefringence
SOC stress-optical coefficient (gpd) -1
Fa amorphous orientation function
Fc crystalline orientation function
COA crystalline orientation angle (WAXS)
LPS long period interval (SAXS,
Figure 921036809_IMG8
)
Average (WAXS, the 010) crystal size of CS (
Figure 921036809_IMG9
)
Tcc(DSC) the DSC-cold crystallization temperature (℃)
T(E " max) E " maximum temperature (T α)
E " dynamic energy consumption modulus (g/d)
M SonSound wave modulus (g/d)
Ms shrinks modulus (g/d)
The SV velocity of sound (Km/min)
Vf, am amorphous state free volume (
Figure 921036809_IMG10
3)
Figure 921036809_IMG11
Dust
Mil mil (0.001 inch=0.0254mm=25.4 micron)
μ micron (10 -6M=10 -4Cm=10 -3Mm)
The Km/min kilometer/minute=10 3Rice/minute
A alkylene dioxy unit (O-R '-O-)
B alkylene dicarbapentaborane unit (C(O)-R " C(O)-)
R ', R " alkylene
C, H, O carbon, hydrogen, oxygen
-O-" oxygen " (ether) key
-C(O)-carbonyl
The quick pin number of RPC
The weight percent of FOY oil supply on long filament
The AJT air jet texturing
The silk of the low orientation of LOY
The silk of the medium orientation of MOY
The silk of the high orientation of HOY
The silk that POY is partially oriented
The silk of SOY spinning-orientation
DUY directly uses silk
The FDY fullly drawn yarn (FDY)
The postbulkable silk of PBY
WDFY warping stretching feed yarns
DFY stretching feed yarns
The DTFY draw textured feed yarn
The FTT false twist texturing
The SBC filling is box curls
SBT clogs box distortion
Direct fabrics-orientation that SDSO simplifies
The WAXS wide-angle x-ray scattering
The SAXS small angle X ray scattering
The DSC differential scanning calorimetry
RAD is quenching radially
XF is horizontal to blow quenching
DT tensile stress (gpd)
The DTV tensile stress changes (%)
The dawn is counted uniformity between the IFDU long filament
The RND circle
The TRI trilobal
RIB band shape
HOL hollow
After ABO boils contraction
Before BBO boils contraction
The RV relative viscosity
The void content of FVC mark
The void area that EVA extrudes
The ID internal diameter
The OD external diameter
The diameter of d long filament (cm)
Niso is respectively to refractive index
HRV LRV+1.2
RV 1.28（HRV）
(0.0653(LRV+1.2) of (η o) 2GT in the time of 295 ℃ 3.33)
（ηo）TP （ηo）295℃×（295/T p） 6
ft 30.0284m 3
μ (micron) 10 -4Cm
The mil(0.001 inch) 2.54 * 10 -3The cm=25.4 micron
0.9144 yard/minute of m/min
/ 9000 meters of dpf 1 grams
g/min 0.132pph
d（cm） 11.89×10 -4（dpf/ρ） 1/2
（T M）a （T M）°+2×10 -4（L/D）Ga，℃
Ga(second -1) (32/60 π) (W/1.2195) (1/D RND) 3, second -1
t R(branch) (1.2195V F(cm 3))/(W #C), divide
σa 10 -3（ρ/SOC）（LRV/LRV 20.8）（T R/T P） 6〔V 2/dpf〕〔Ao（cm）/ ＃C〕 0.7，g/d
E RV/Vo＝2.25×10 5（1.2195π）（D RND 2/dpf）
ε RL n（E R）
T S660(WL/D 4) 0.685, ℃; W=pph wherein, L and D are unit with the mil
T R（T M）a+40℃
W dpfV（mpm）/9000＝dpfV（Km/min）/9，g/min
D RND2（Ac/π） 1/2，cm
Xv （ρ-ρa）/（ρc-ρa）
Xw （ρc/ρ）Xv
ρc 1.455g/cm 3
ρa 1.335g/cm 3
ρ Corρ-the 0.0087(%TiO that measures 2), g/cm 3
△S （DHS，%-S，%）
Sm （550-E B，%）/6.5，%
Mpy （1.2T 20-1.07T 7）/（1.2-1.07），g/d
T B(intensity, T) (RDR), g/d
RDR （1+E B，%/100）
（T B） nT B×LRV 0.75（1-X） -4
△n △c+△a＝△°〔Xvfc+（1-Xv）fa〕
fc （1-COA/180）
f △n/△°＝1/2（3＜COS＞ 2-1）
△° 0.220
SOC △n/σa＝0.7（g/d） -1
Vf，am CS 3〔（1-Xv）/Xv〕〔（1-fa）/fa〕，
Figure 921036809_IMG12
3
△ p=4(L/D RND) nη aG a, n=is 1 to newton's melt and when the Ga-＞0
（dpf） b（dpf） a〔（L/D） a/（L/D） b〕 n〔（Va/Vb）（Db/Da） 3
△ P 4(L/D) τ wall η aGa=4(L/D)
τ wall η aGa
Ga (32/ π ρ) (W/D 3), second -1
Vo (W/ ρ)/(area), cm/min
G/d 1.0893 newton/dtex
1 gram 0.9804 * 10 3Dyne
1 newton 10 3Dyne
PSI(is poundage per square inch) 0.0703 kilograms per centimeter 2
G/cm 2(gram per centimeter 2) 0.9(ρ) (g/d)=(ρ) (gram/dtex)
EVA π（ID 2/4）
FVC （ID/OD） 2
Ps （ST，g/d）×（S，%）
ABO BBO〔100/（100-S）〕
Figure 921036809_IMG13
Figure 921036809_IMG14
Figure 921036809_IMG15
Figure 921036809_IMG16
Figure 921036809_IMG18
Figure 921036809_IMG19

Claims (19)

1, the dawn number is about the preparation method of polyester fine filaments of spinning-orientation of 1-0.2,
Wherein,
(i) relative viscosity of selected polyester polymers (LRV) is about 13-23, and zero shears fusing point (TM °) is about 240-265 ℃, and glass transition temperature (Tg) is about 40-80 ℃;
(ii) fusing of above-mentioned polyester and temperature (Tp) scope that is heated to above apparent melting point polymer (TM) a are about 25-55 ℃;
(iii) the melt that obtains is filtered fast enough, the time of staying (tr) is less than about 4 minutes as a result;
(iv) the melt that will filter with the mass velocity (W) of about 0.7 Grams Per Minute of about 0.07-is extruded by spinning die wire hole, and the area of section (Ac) in the silk hole of selecting for use is about 125 * 10 -6Cm 2To 1250 * 10 -6Cm 2, its length (L) and diameter (DRND) they are such, consequently (L/DRND) ratio is at least about 1.25 and be less than about 6;
(v) the melt that ought extrude penetrates from spinning die wire hole, through at least about 2cm and when being less than the segment distance (LDQ) of (12dpf 1/2) cm approximately, prevent that the melt of extruding from directly cooling off, and dpf there is the filament denier of the polyester fine filaments of spinning one orientation;
(vi) the melt of extruding is cooled to be lower than the glass transition temperature (Tg) of polymer, and it is tapered to apparent spinning threadling strain, and (ε a) is about 5.7-7.6, and (σ a) is about 0.045-0.195g/d to apparent spinning threadling internal stress;
(vii) locate being about the distance of 50-140cm (Lc) then, chilled long filament boundling is become multifilament bundled with a low-friction surface;
(viii) winding speed (V) to be about 2-6km/min, with the multifilament bundled circle around getting up.
2, according to the process of claim 1 wherein that described polyester contains the ethylidene of the about 3 moles of % of the 1-that has an appointment-5-M-sulfo-isophthalate, M wherein is an alkali metal cation.
3, according to the process of claim 1 wherein that described polyester is polyethylene terephthalate basically, it is by first kind of alkylene dioxy construction unit A (O-C 2H 4-O-) and alkylene dicarbonyl structure unit B ((O) C-C 6H 4-C(O)-) alternately form, for example, polyester polymers is about 240-265 ℃ zero shearing fusing point (T for being had M°) and be about 40-80 ℃ glass transition temperature (Tg) and also will carry out modification to above-mentioned polyester with more a spot of other alkylene dioxies construction unit A and/or alkylene dicarbonyl structure unit B that is different from above-mentioned first kind of alkylene dioxy construction unit A that replaces and alkylene dicarbonyl structure unit B.
4, according to the process of claim 1 wherein that (ε a) is about 6-7.3, and to control apparent spinning threadling internal stress (be 7% o'clock intensity (T to obtain by percentage elongation σ a), in apparent spinning threadling strain 7) expression average orientation, this intensity (T 7) scope be about 0.5-1.75g/d.
5, according to any one the method for claim 1-4, wherein polymer temperature (Tp) is approximately higher than apparent melting point polymer (T greatly M) a30-50 ℃, the area of section of spinning die wire hole (Ac) is about 125 * 10 -6Cm 2To 750 * 10 -6Cm 2, extrude long filament density ( #C/Ao) be about 2.5-25 threads/cm 2; Be less than about glass transition temperature of polymer (Tg) with temperature (Ta), the radial air that speed (Va) is about 10-30m/min carries out above-mentioned cooling, and above-mentioned boundling is by at about 50-(50+90dpf 1/2) the most advanced and sophisticated thread guide of metering oil supply located of the distance (Lc) of cm carries out, winding speed (V) is about 2-5Km/min.
6, according to any one the method for claim 1-4, wherein filament denier is about 0.6-0.2, and the dawn number scatters (DS) less than about 2%.
7, fiber number is the polyester filament of the spinning-orientation of about 1-0.2 filament denier, and wherein said polyester is characterised in that relative viscosity (LRV) is about 13-23, and zero shears melting point polymer (T M°) being about 240-265 ℃, glass transition temperature of polymer is about 40-80 ℃; Above-mentioned filament is further characterized in that:
(ⅰ) boil shrinkage factor (S) less than maximum approximately potential minification (Sm), wherein Sm=((550-E B)/6.5) %, and elongation at break (E B) % is about 40-160%;
(ⅱ) be higher than approximately 5-30 ℃ maximum temperature T(STmax of glass transition temperature of polymer (Tg)) time, maximum collapse tension force (STmax) is about 0.05-0.2g/d;
(ⅲ) percentage elongation is 7% o'clock intensity (T 7) be about 0.5-1.75g/d, like this so that ((T B) n/ T 7) ratio be at least about (5/T 7), (T wherein B) nBe the fracture strength of standard, and elongation at break (E B) be about 40-160%;
(ⅳ) average dawn number distribution (DS) along the terminal direction is lower than about 4%.
8, according to the long filament of claim 7, for example be particularly suitable for it is characterized in that as the stretching feed yarns, boil shrinkage factor (S) and dry-hot shrinkage (DHS) all is at least about 12%, elongation at break (E B) being about 80-160%, percentage elongation is 7% o'clock intensity (T 7) be about 0.5-1g/d.
9, according to the long filament of claim 7, for example be particularly suitable for weaving silk as direct use, it is characterized in that, shrink rate variance (△ S) less than about+2%, wherein, boil shrinkage factor (S) and dry-hot shrinkage (DHS) all is about 2-12%, so that the filament denier after shrinking is less than about 1; T 7Be about 1-1.75g/d, (E B) being about 40-90%, back yield modulus (Mpy) is about 2-12g/d.
10, according to the long filament of claim 7, has the ability of carrying out even cold stretch, it is characterized in that, shrink rate variance (△ S) less than about+2%, wherein, boil shrinkage factor (S) and dry-hot shrinkage (DHS) all is about 2-12%, the beginning temperature T cc(DSC of cold crystallization) be lower than about 105 ℃, instantaneous stretching modulus (Mi) is at least about 0.
11, the polyester filament of the spinning-orientation that has stretched, it has boils the dawn that is about 1-0.2dpf after the contraction and counts dpf(ABO), wherein said polyester is characterised in that relative viscosity (LRV) is about 13-23, zero shears melting point polymer (T M°) being about 240-265 ℃, glass transition temperature of polymer (Tg) is about 40-80 ℃; And the above-mentioned long filament that has stretched is further characterized in that:
(ⅰ) boil shrinkage factor (S) and dry-hot shrinkage (DHS) all is about 2-12%.
(ⅱ) percentage elongation is 7% o'clock intensity (T 7) be at least about 1g/d, consequently ((T B) n/ T 7) ratio be at least about (5/T 7), wherein, (T B) nBe the fracture strength of standard, elongation at break (E B) be about 15-55%,
(ⅲ) back yield modulus (Mpy) is about 5-25g/d,
(ⅳ) average dawn number along the terminal direction scatters (DS) less than about 4%.
12, the polyester filament of the spinning-orientation of bulking, its fiber number are about 1-0.2dpf(and are boiling the contraction back), wherein said polyester is characterised in that relative viscosity (LRV) is about 13-23, zero shears melting point polymer (T M°) being about 240-265 ℃, glass transition temperature of polymer is about 40-80 ℃; And above-mentioned long filament is further characterized in that:
(ⅰ) boil shrinkage factor (S) and dry-hot shrinkage (DHS) all is about 2-12%,
(ⅱ) percentage elongation is 7% o'clock intensity (T 7) be at least about 1g/d, elongation at break (E B) being about 15-55%, back yield modulus (Mpy) is about 5-25g/d.
13, according to the long filament of claim 11 or 12, wherein long filament is further characterized in that, dynamic loss modulus maximum temperature T(E " max) be lower than about 115 ℃.
14, according to the long filament of claim 11 or 12, wherein long filament is further characterized in that, dispersion dyeing speed (RDDR) is at least about 0.1 relatively.
15, according to any one the long filament of claim 7-6, wherein long filament has the form factor (SF) at least about 1.25.
16, according to any one the long filament of claim 7-6, wherein the dawn number of long filament is about 0.6-0.2dpf.
17, according to any one the long filament of claim 7-6, wherein long filament scatters (DS) less than about 2% along the dawn number of terminal direction.
18, according to any one the long filament of claim 7-6, wherein said polyester fiber contains 5-ethylidene-M-sulfo--isophthalate construction unit of about 1-3 mole %, and wherein, M is an alkali metal cation.
19, according to any one the long filament of claim 7-12, wherein said polyester is polyethylene terephthalate basically, and it is by first kind of alkylene dioxy construction unit A (O-C 2H 4-O-) and alkylene dicarbonyl structure unit B (C(O)-C 6H 4-C(O)-) alternately form, for example, polyester polymers is about 240-265 ℃ zero shearing fusing point (T for being had M°) and be about glass transition temperature of polymer (Tg) between 40-80 ℃, also to carry out modification to above-mentioned polyester with more a spot of above-mentioned first kind of alkylene dioxy construction unit A that replaces and other alkylene dioxies construction unit A of alkylene dicarbonyl structure unit B and/or the dicarbonyl structure unit B of alkylene of being different from.
CN92103680A 1986-01-30 1992-04-11 Preparing polyester fine filaments Expired - Fee Related CN1047634C (en)

Priority Applications (23)

Application Number Priority Date Filing Date Title
ES92904563T ES2104898T3 (en) 1991-01-29 1992-01-29 PREPARATION OF FINE POLYESTER FILAMENTS.
PCT/US1992/000359 WO1992013119A1 (en) 1991-01-29 1992-01-29 Preparing polyester fine filaments
DE69221739T DE69221739T2 (en) 1991-01-29 1992-01-29 MANUFACTURE OF FINE POLYESTER FILAMENTS
AU12310/92A AU653207B2 (en) 1991-01-29 1992-01-29 Preparing polyester fine filaments
CA002101788A CA2101788C (en) 1991-01-29 1992-01-29 Preparing polyester fine filaments
EP92904563A EP0646189B1 (en) 1991-01-29 1992-01-29 Preparing polyester fine filaments
JP4504583A JP3043414B2 (en) 1991-01-29 1992-01-29 Polyester thin filament manufacturing method.
TW081102473A TW215113B (en) 1991-01-29 1992-04-01
CN92103680A CN1047634C (en) 1991-01-29 1992-04-11 Preparing polyester fine filaments
US07/979,776 US5356582A (en) 1986-01-30 1992-11-09 Continuous hollow filament, yarns, and tows
US08/005,672 US5288553A (en) 1991-01-29 1993-01-19 Polyester fine filaments
US08/085,266 US5384082A (en) 1986-01-30 1993-06-29 Process of making spin-oriented polyester filaments
US08/093,156 US5417902A (en) 1986-01-30 1993-07-23 Process of making polyester mixed yarns with fine filaments
US08/121,146 US5407621A (en) 1991-01-29 1993-09-17 Process for preparing polyester fine filaments
US08/214,717 US5487859A (en) 1986-01-30 1994-03-16 Process of making fine polyester hollow filaments
US08/289,553 US5532060A (en) 1986-01-30 1994-08-12 Continuous hollow filaments, yarns, and tows
BR9205719A BR9205719A (en) 1991-01-29 1994-11-21 Preparation of thin polyester filaments
US08/378,132 US5645936A (en) 1986-01-30 1995-01-24 Continuous filaments, yarns, and tows
US08/378,137 US5505894A (en) 1986-01-30 1995-01-24 Process of making spin-oriented, biconstituent filaments
US08/397,325 US5585182A (en) 1986-01-30 1995-03-01 Process for polyester fine hollow filaments
US08/468,908 US5691057A (en) 1986-01-30 1995-06-06 Polyester mixed yarns with fine filaments
US08/475,122 US5827464A (en) 1991-01-29 1995-06-07 Making high filament count fine filament polyester yarns
US08/475,141 US5741587A (en) 1991-01-29 1995-06-07 High filament count fine filament polyester yarns

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US64737191A 1991-01-29 1991-01-29
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CN92103680A CN1047634C (en) 1991-01-29 1992-04-11 Preparing polyester fine filaments

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CN1090689C (en) * 1992-08-05 2002-09-11 纳幕尔杜邦公司 Drawn polyester continuous hollow filament yarn
CN1092721C (en) * 1995-08-04 2002-10-16 纳幕尔杜邦公司 Making high filament count fine filament polyester yarns
CN1320179C (en) * 2002-04-25 2007-06-06 帝人纤维株式会社 Method for producing polyester extra fine multi-filament yarn and polyester extra fine false twist textured yarn, polyester extra fine multi-filament yarn, and polyester extra-fine false twist texture
CN110938882A (en) * 2019-12-11 2020-03-31 诸暨市百乐化纤有限公司 High-performance polyester POY preparation device and method
CN111041578A (en) * 2019-12-24 2020-04-21 江苏恒力化纤股份有限公司 PET (polyethylene terephthalate) double-component elastic yarn with different viscosities and preparation method thereof
CN111893586A (en) * 2020-07-21 2020-11-06 陆超杰 Polyester fiber processing technology
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KR100488381B1 (en) * 1995-08-04 2006-04-21 이.아이,듀우판드네모아앤드캄파니 Making High Filament Count Fine Filament Polyester Yarns
DE19821778B4 (en) 1998-05-14 2004-05-06 Ems-Inventa Ag Device and method for producing microfilaments of high titer uniformity from thermoplastic polymers
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US20080006970A1 (en) 2006-07-10 2008-01-10 General Electric Company Filtered polyetherimide polymer for use as a high heat fiber material
US9416465B2 (en) 2006-07-14 2016-08-16 Sabic Global Technologies B.V. Process for making a high heat polymer fiber
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CN1090689C (en) * 1992-08-05 2002-09-11 纳幕尔杜邦公司 Drawn polyester continuous hollow filament yarn
CN1092721C (en) * 1995-08-04 2002-10-16 纳幕尔杜邦公司 Making high filament count fine filament polyester yarns
CN1320179C (en) * 2002-04-25 2007-06-06 帝人纤维株式会社 Method for producing polyester extra fine multi-filament yarn and polyester extra fine false twist textured yarn, polyester extra fine multi-filament yarn, and polyester extra-fine false twist texture
CN110938882A (en) * 2019-12-11 2020-03-31 诸暨市百乐化纤有限公司 High-performance polyester POY preparation device and method
CN110938882B (en) * 2019-12-11 2020-12-29 诸暨市百乐化纤有限公司 High-performance polyester POY preparation device and method
CN111041578A (en) * 2019-12-24 2020-04-21 江苏恒力化纤股份有限公司 PET (polyethylene terephthalate) double-component elastic yarn with different viscosities and preparation method thereof
CN111893586A (en) * 2020-07-21 2020-11-06 陆超杰 Polyester fiber processing technology
CN115233324A (en) * 2022-08-05 2022-10-25 常州德利斯护理用品有限公司 Spinning-bonding drafting device for preparing special-shaped fibers with different cross sections
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