US3651198A - Drawing and heat treatments of polyester filaments - Google Patents

Drawing and heat treatments of polyester filaments Download PDF

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US3651198A
US3651198A US798426A US3651198DA US3651198A US 3651198 A US3651198 A US 3651198A US 798426 A US798426 A US 798426A US 3651198D A US3651198D A US 3651198DA US 3651198 A US3651198 A US 3651198A
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filaments
stage
heat treatment
heat
temperature
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Yukio Mitsuishi
Masanori Matsuura
Toshimasa Kuroda
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Teijin Ltd
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Teijin Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • 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
    • D02J1/229—Relaxing

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  • 264-235 v Claims ABSTRACT OF THE DISCLOSURE Process for drawing and heat-treating polyester filaments comprising subjecting undrawn polyester filaments to a first drawing at a relatively low temperature (T subjecting the filaments to a second drawing at a temperature (T lower than T at draw ratio at least 80% of the maximum draw ratio at this stage, subjecting the filaments to a first heat treatment under tension at a temperature (T higher than T and thereafter subjecting the filaments to single or multi-staged second heat treatment performed at temperatures higher than temperature T under tension, the temperature of at least one stage of the second heat-treatment being 110 C.
  • This invention relates to a novel process for drawing and heat-treating polyester filaments.
  • Polyester filaments are known for their high crystallinity and high melting point, and also for their other excellent properties such as high resistances to heat, chemicals and light, great strength and high elastic modulus. Because of those favorable properties, the filaments are very important as clothing and industrial materials. Particular- 1y, their importance as a tire cord material is rapidly increasing as a recent trend. While there are a number of requirements particularly important for tire cord material, the most significant are that the material should possess high strength, elongation, toughness, dimensional stability and fatigue resistance.
  • polyester filaments as tire cord material are compared with polyamide filaments such as 6-nylon, 6,6-nylon, etc.
  • the former excel in thermal dimensional stability, but are not necessarily superior to the latter in strength, elongation, and mechanical fatigue resistance. Therefore, it is expected that, if polyester filaments could retain the high dimensional stability and furthermore possess still improved mechanical strength, elongation, and fatigue resistance, such filaments will have much increased utilities not only as tire cord, but also in the field of clothing and interior decoration.
  • An object of the invention is to provide a novel drawing and heat-treating process for making polyester filaments having high breaking strength, breaking elongation and large Youngs modulus.
  • Another object of the invention is to provide a drawing and heat-treating process consisting of unique and novel combination of drawing steps and heat treatments, for
  • polyester filaments particularly suited as tire cord having high toughness, fatigue resistance, and a strengthconversion ratio (percent conversion of the strength of the starting yarn).
  • a drawing and heat-treating process of polyester undrawn filaments containing at least mol percent of ethylene terephthalate units comprises the following steps to be performed in the order stated:
  • Second heat treatment wherein the filaments are heat-treated, at least once, at temperatures higher than that employed in the step (3), at least one stage of the heat treatment being performed at a temperature not lower than C., the filaments being subjected in each stag to a tension that will maintain the filament length treatment at 9 5-130% of that of an immediately preceding stage, and furthermore the tension exerted on the filaments in each stage of step (4) being so adjusted that the filament length after the final stage of step (4) becomes at least 90% of that immediately before step (3).
  • the characteristic features of the invention in sequence are as follows: preparation of highly oriented but non-crystalline drawn filaments of polyester by twostage drawing of polyester undrawn filaments at relatively low temperatures as described in the steps (1) and (2): preparation of drawn filaments of polyester having a uniform structure in the directions both parallel and perpendicular to the filament axis, and being highly oriented but still non-crystalline from the drawn filaments obtained in steps (1) and (2), by the first heat treatment under tension of step (3); and preparation of polyester filaments having a very uniform structure in the directions both parallel and perpendicular to the filament axis and being highly oriented and highly crystalline from the drawn filaments obtained in step (2) by the singleor multi-stage second heat treatment of step (4).
  • the polyester filaments thus obtained in accordance with the invention exhibit remarkably high breaking strength and breaking elongation due to their unique structure, and as the result possess very high toughness.
  • they show excellent fatigue resistance and high strength-conversion ratio.
  • Youngs modulus the drawback of fiat spots is remarkably improved, when compared with nylon tire cord.
  • the polyester filaments obtained in accordance with the subject process are clearly distinguishable from conventional products, in that they are simultaneously excellent in all of the many important mechanical properties.
  • FIG. 1 is a load-elongation curve of the polyester filaments prepared in accordance with one embodiment of the process of this invention.
  • FIG. 2 shows load-elongation curves of the polyester filaments prepared in accordance with another embodiment of the process of this invention and the polyester filaments prepared in accordance with the conventional process.
  • polyester undrawn filaments employed in the invention are composed of high molecular weight polyethylene terephthalate, i.e., a polymer containing at least 85 mol percent, preferably at least 90 mol percent, of a recurring structural unit of the formula,
  • the undrawn filaments may be those which are spun by optional spinning means conventionally employed.
  • polyester is used in the specification and claims, in the sense including modified polyethylene tcrephthalate by the addition of no more than approximately 15 mol percent of other ester-forming units.
  • ester-forming units the following may be named'by Way of examples: diethylene glycol, other polymethylene glycols of 1-10 carbons, hexahydro-pxylylene glycol; aromatic dicarboxylic acids such as isophthalic, dibenzoic, p-terphenyl-4, "-dicarboxylic, and hexahydroterephthalic acids; aliphatic acids such as adipic acid; hydroxy acid such as hydroxyacetic acids; and the like.
  • polyester filaments employed in the invention are inclusive of monofilaments.
  • the properties of the undrawn filaments are not critical, but the filaments having an intrinsic viscosity of at least 0.3 and a birefringence ranging 0.0005-0.0120 are preferred.
  • the undrawn filaments having a birefringence outside the specified range tend to produce drawing failure or increase filament breakage during drawing operation.
  • the density of the undrawn filaments is preferably no higher than 1.35 g./cm. Otherwise the filament breakage during drawing tends to be increased.
  • Intrinsic viscosity of a polymer is given as a norm of degree of polymerization of that polymer, which is defined below:
  • v is normally referred to as relative viscosity, obtained by dividing the viscosity of a dilute solution of a polymer by the viscosity of employed solvent which is measured at the same temperature. Also is the polymer concentration in the solution expressed by g./100 cc.
  • the intrinsic viscosities given in the present specification are calculated from the values measured at 35 C., using ortho-chlorophenol as the solvent.
  • load-elongation curve and breaking strength and breaking elongation calculated from the curve are variable in shape and value according to the length of test specimen and extension rate.
  • the tensile. test is performed with 204cm.
  • grade of inclination on load-elongation curve is expressed by differential coefiicient of strength tovthe elongation at each point on the load-elongation curve, viz., grade of tangent. Incidentally, correction-of the values with respect to the decrease infilament deniers accompanying the elongation is not performed.
  • the polyester undrawn filaments are first subjected to the first stage drawing, to be drawn by 1.1-4-0X. Preferably 1.2-3.0X, at a temperature within within a range of 40-100 0., preferably 60-100 C., as described in step 1).
  • Optional heating medium may be employed in this step, i.e., non-solvent liquids being preferred.
  • the filaments are then subjected to "the second stage drawing in the step (2), under the following conditions. That is, the filaments are drawn at a temperature within a range of 1085 (3., "preferably 4075 C., which is lower than the drawing temperature employed in the first stage (step (1)), preferably lower by at'leastj 10 C.,' r
  • the type of heating medium in this step is not critical, but non-solvent'liquids such as water and ethylene-glycol are preferred.
  • maximum draw ratio tion and claims signifies the maximum draw ratio of the filaments under the specific drawing conditions, at which no filament breakage takes place. Obviously the maximum draw ratio is dependent on the properties of the filaments to be drawn, but is also affected by the drawing conditions such as temperature, mediumv in which the filaments are drawn, and drawing rate, etc.
  • the polyester filaments after' drawing are then subjected to the first heattreatment instep (3), under the following conditions. That is, the filaments are heat-.
  • the polyester filaments must be under a tension there will maintain the filament length at 130% of that immediately beforethe step 3), i.e., after completion of step (2 In other words, the polyester filaments are either stretched or elongated by at most 30%, or maintained at the same angel, shrunk by at most 5%.
  • the polyester filaments of the invention exhibit a marked tendency for shrinkage after the two-stage drawing of steps (1) and (2). as above-described, and under the temperature condition applied in the heat treatment of step (3), normally show a free shrinkage of at least 20%
  • free shrinkage used herein means spontaneous shrinkage expressed by percent, which occurs when the filaments are exposed to the temperature'condition free from tension. Therefore, when the polyester filaments are maintained at the state'that will allow no more than 5% shrinkage during the heat treatment of step (3),
  • the filaments are given a sufiicient tension since the free. shrinkage is far greater than the allowable shrinkage. Consequently, the filaments never exhibit configurational change such as formation. of crimps,- and are free from i.
  • heat treatment under tension signifies a heat treatment which is performed while either restricting the filaments ata limited shrinkage of not more than 5 which is far less than the free shrinkage the same filaments under the employed heat-treating conditions, or maintaining their constant length, or extending the filaments with astretch of 'singleormulti-stage heat treatments under tension.
  • the treating temperatures in all of the stages under tensu ch' as water and ethylene-glycol used in the specificasion of step (4) must be higher than the temperature em; ployed in step (3 preferably byyat least lfl" (3., andvin at least one stage'of the heat treatment of step .(4), the filaments must be subjected to heat treatrnentat a temperatnre not lower .than 110 C., preferably not lower than 120 C., more preferablynot lower than 150 C.
  • the filaments are maintained at such a state to have a length corresponding to 95-130% of that of the filaments after completion of the preceding heat treatment stage and immediately before the pertinent stage. Furthermore, the tension at each stage must be so adjusted that the filaments after the final heat treatment stage of step (4) should have a filament length corrmponding to at least 90% of that of the filaments after the second stage drawing of step (2) and immediately before the first heat treatment of step (3). 7
  • the filaments are maintained at such a state in each stage of they step (4), heat treatment satisfying the above two requirements, the filaments are always tense throughout the second heat treatment, by the same reasons as described as to the first heat treatment.
  • the limited or allowable shrinkage in the heat treatments of steps (3) and'(4) is preferably not more than 3%, and generally more satisfactory results are obtained when the heat treatments are. performed maintaining constant filament length or under stretching by at most 30%, rather than the cases of heat-treating the filaments with a shrinkage within the specified range.
  • the treating time of either step (3) or (4) is not critical, but normally that ranging 0.0ll,000 seconds is preferred.
  • the heat treatment of step (3) and that of step (4) may be practiced using separate apparatus, or using a single heat-treating apparatus comprising multi-zones, in each of which the heat treatment of each stage isperformed respectively.
  • TDR total draw ratio
  • step (4) can be raised as high as 600 C., or even higher, if, for example, a known non-contact type salt heater is employed.
  • polyester filaments obtained in one embodiment of the subject process can show a very characteristic type load-elongation curve.
  • a load-elongation curve of polyester filaments has first and second yield points.
  • the yield point present at the side of low load and low elongation is referred to as the first yield point, and the other, as the second yield point.
  • first yield point the yield point present at the side of low load and low elongation
  • second yield point the second yield point.
  • the grade of inclination after the second yield point is characteristically very small.
  • polyester filaments showing very unique mechanical behavior quite different from that of conventional products, such as a minimum grade of inclination of no more than 9 g./d. above the point of 7.0 g./d. on the load-elongation curve can be obtained in accordance with the invention.
  • step (4) comprises two heat treatments and if all of the heat treatments of steps (3) and (4) are performed while the filament length in every stage 95-ll0% of that immedi-.
  • the resulting filaments can show the above-described type of load-elongation curve.
  • polyester filaments showing this type of load-elongation curve can be prepared by an embodiment of the invention, i.e. a drawing and heat-treating process of polyester undrawn filaments containing at least mol percent, preferably at least mol percent, of polyethylene terephthalate units, which comprises the following steps to be performed in the order stated:
  • step (4) (i) first stage of second heat treatment wherein the filaments are treated at a temperature within a range of l00-l70 C., while being subjected to a tension that will maintain the filament length during the treatment at 95115%, preferably 95-l10%, of that immediately before the same heat treatment, and (ii) second stage of second heat treatment whereby the filaments are further treated at a temperature exceeding 170 C., while being subjected to a tension that will maintain the filament length during the treatment at 95-1 15%, preferably 951l0%, of that immediately before the same heat treatment; the tensions exerted on the filaments in the stages (i) and (ii) of step (4) being so adjusted that the filament length after the stage (ii) of step (4) becomes at least 90% but less than preferably at least 95% but less than 120%, of that immediately before the foregoing step (3).
  • polyester filaments having above-described type of load-elongation curve are characterized by the fact that when they are used as tire cord, the cord exhibits markedly improved fatigue resistance and strength-conversion ratio.
  • polyester filaments showing still different type of load-elongation curve it is also possible to make polyester filaments showing still different type of load-elongation curve, by another embodiment'of the invention.
  • That different type of load-elongation curve shows high initial Youngs modulus, andthe maximum grade of in clination after the first yield point much greater than that -'on load-elongation curve of conventional polyester filaments.
  • the maximum grade after the first yield point on the curve is greater than that between the'origin and first yield point, as illustrated in FIG. 2.
  • Such abnormal mechanical behavior is never seen in conventional polyester filaments.
  • the curves (a) and (b) are load-elongation curves of the polyester filaments of this invention and the ordinary polyester filaments, respectively.
  • the filaments showing such load-elongation curve can be obtained, for example, by performing all the heat I treatments in steps (3) and (4), maintaining the filaments under tension that will render the filament length in each of the treatments 100-130% of that immediately before that treatment, while adjusting the tensions in such a manner that the filaments after the final stage heat treatment of step (4) should have a filament length corresponding to 120150% of that immediately before the heat treatment of step (3).
  • polyester filaments showing this type of load-elongation curve can be prepared by an embodiment of the invention as described below.
  • polyester filaments can be made by a drawing and heat-treating process of polyester undrawn filaments containing at least 90 mol percent of ethylene terephthalate units, which comprises the following steps to be performed in the order stated:
  • the filaments having above-described type of load-elongation curve of course exhibit excellent properties such as high strength and Youngs modulus, and furthermore possess characteristically high mechanical, dimensional stability since their distortion due to elongation under a heavy load is relatively little. Because of such characteristics, these types of filaments are valuable as a material for belt, radial, tire, etc. which are required to have relatively small elongations under heavy loads.
  • polyester filaments characteristically possessing a great number of excellent mechanical properties simultaneously can be obtained by the subject process, is presumably as follows:
  • the filaments prepared in accordance with the inven tion thus exhibit various excellent properties, and are very valuable not only for industrial usages, 'for example, as tire cord, but also for clothing usages. In the latter field, the filaments may be used as they are, or cut into staples. The filaments also command wide utilities in the field of interior decoration.
  • the invention will be explained in further detail with reference to working exampleswhich are given strictly for illustration purpose, but in no way to limit the scope of subject invention.
  • EXAMPLE 1 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.81, a size of approximately 6,100 d./250 fil. and a birefringenceof 0.0015, which had been melt-spun in conventional mannenwere drawn by 2.0x in a -cm. long, warm aqueous bath of 85 C., and further by 3.0x in another -cm. long, warm aqueous bath of 65 C. The filaments were then'heattreated in a 120-cm. long Warm aqueous bathof 85C. while being stretched by 1.05X, followed by the second heat treatment in which the filaments were wound on a.
  • the obtained yarn was 860deniers in size, and had a breaking strength of 12.5 g./d'.',-breaking elongation of 15% and Youngs modulus of 2,000 kg./mm.
  • the toughness thereof was 0.94 g./d. The same.
  • yarn was made into tire cord of 860 .d./2 by imparting thereto right hand under-twisting of 5 6.5 turns: per 10 cm., followed byupper twisting of .two strands together;
  • EXAMPLE 2 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.92, a size of approximately 7,200 d./ 250 fil. and a birefringence of 0.0028, which had been melt-spun in conventional manner, were drawn by 2.0x in a 100-cm. long, warm aqueous bath of 90 C. and fur- 10 strengthing by 5% ther by 3.0x in a 120-cm. long, warm aqueous bath of 70 C.
  • the filaments were sub ected to three suc- Second heat treatment cessive heat treatments as follows, and thereafter wound (i) Temperature 120 (2, up at a rate of 100 m./min.: the filaments were heat- H t ll f 150 'q, treated in a 120-cm. long, warm aqueous bath of 90 C. Stretching by 10% while being stretched by 10%, then wound on a hot roller (ii) Temperature 180 C. of 150 C. and 150 mm. in diameter, to be heat-treated H t ll f 150 mm g under a tension of 10% stretching, and finally wound on Stretching by 10% a hot roller of 200 C. and 150 mm. in diameter while may being stretched by 10%.
  • the obtained yarn was 1,000 1 1 g deniers in size, and had a breaking strength of 13,.5 g./d., Approximately 100 m./m1n. elongation of 16%, and Youngs modulus of 1,900 kg./
  • Second stage drawing: temperature 7.6) 7.0 16 1,100 0.56
  • First heat treatment stretching by Stretching inoperable V 40%. more than 30%.
  • Second heat treatment (i): tempera- Stretching of stage (i) in ture 80 0. lower than first heat second heat treatment treatment temperature. inoperable.
  • EXAMPLE 3 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.92, a size of approximately 6,100/d./120 fil., and a birefringence of 0.0020, which had been melt-spun in conventional manner, were drawn by 3.0x in a 100-cm. long warm aqueous bath of 85 C., and further by 2.0x in a l20-crn. long warm aqueous bath of 73 C. Then the filaments were heat-treated in a 120-cm. long, warm aqueous bath of 90 C. under a tension of stretching. As the second heat treatment, the filaments were wound on a hot roller of 150 C. and 150 mm.
  • the resulting yarn had a breaking strength of 12.8 g./d., breaking elongation of 16%, Youngs modulus of 1850 kg./mm. and a toughness of 1.02 g./d.
  • EXAMPLE 4 From polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.80, a size of approximately 6,100 d./250 fil., and a birefringence of 0.0015, which had been melt-spun in conventional manner, a cm. long sample was cut. The sample was drawn by 2.0x at a rate of 10% /min. in an aqueous bath of 55 C. using a frame-type drawing machine, and further by 3.2x at a rate of 50% /min. in an aqueous bath of 45 C. The sample was then heat-treated in 170 C. water while maintaining the constant filament length, further in a 120 C. silicone oil bath under tension of stretching, and finally in a 180 C.
  • EXAMPLE 5 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.80, a size of approximately 6,100 d./250 fil., and a birefringence of 0.0015, which had been melt-spun in conventional manner, were drawn by 2.0x in a 100-cm. long warm aqueous bath of 70 C., and further by 3.2x in a 120-cm. long warm aqueous bath of 45 C., at a drawing rate of 40 m./min. Thus drawn filaments were withdrawn after elmination of bath water. The sample was then heat-treated in a l20-cm. long silicone oil bath of 80 C. while being maintained at the constant filament length.
  • the sample was treated in a 100-cm. long silicone oil bath of 120 C. under a tension of 23% stretching, and further in a 100-cm. long silicone oil bath of 185 C. under a tension of 6% stretching.
  • the silicone oil was eliminated from the resulting yarn which was subsequently taken up at a rate of 40 m./min.
  • the yarn had a size of 760 deniers, breaking strength of 11.8 g./d., breaking elongation of 20%, and Youngs modulus of 1900 kg./mm.
  • the calculated toughness of the product was 1.18 g./d.
  • the same undrawn filaments were drawn by 4.3x by means of a hot pin of 90 C. and 60 mm. in diameter, further by 1.3x on a 50-cm. long hot plate of 190 C., and heat-treated on a 50-cm. long plate of 210 C. while being maintained at the contaut filame le h-The arnwas sub equen y ta n.
  • the resulting yarn had a size of 1,100 deniers, breaking strength of 9.5 g./d., breaking elongation of 13.8%, and a Youngs modulus of 1250 kglmmfi.
  • the calculated toughness of the yarn was 0.65
  • the former product exhibits 1-2 markedly higher strength than that of the latter product.
  • the former also has agreater elongation.
  • EXAMPLE 6 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.78, a'size of approximately 6,100 d./250 fil., anda birefringence of 0.0016, which had been melt-spun in conventional manner, were cut into the sample length of 10-cm.
  • the sample was drawn by 2.0x in an aqueous bath of6 8 C. at a rate of 25 min., using a frame-type drawing: machine, and further by 3.4x in an aqueous bath of 30 C. at a rate of 100%/ min.
  • the same sample was heat-treated for-,5 minutes in an C. silicone oil bath, under. a tensionof 6 stretching, followed by another heat treatment of 10minutes in a 125 C.
  • the resulting yarn had a breakingielon gation of 12.5 g./d., an elongation of 17%, and a Youngs modulus of 2050 kg./mm.
  • the calculated toughness of the product was 1.06 g./d. i
  • EXAMPLE 7 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.80, a size of approximately 6,100 d./250 fil., and a birefringence of 0.0015, which had been melt-spun in conventional manner, were drawn by 2.0x in a -cm. long, warm aqueous bath of 93 C., and further drawn by 3.0x in a -cm. long, warm aqueous bath of 65 C. at a drawing rate of 100 m./min.- The filaments were treated to eliminate'thebath water and subsequently heat-treated in a 120-cm.v long, warm: aqueous bath of 93 C., while being stretched" by 10%.
  • the filaments were wound on a hot roller of C. and 150 mm. in diameter by two turns, to be heat-treated under a tension causing 10% stretching, and then wound on a hot roller of 220 C. and 150 mm. in diameter to be heat-treated under atension causing 10% stretching. Thereafter the resulting yarnwas 'withdrawn from the roller at a rate of 100 m./min.
  • the yarn had a size of 860 deniers, a breaking strength of 11.8 g./d., a breaking elongation; of 18%, and a Youngs modulus of 1,800 kg./mm.
  • the calculated toughness was 1.00, g./d. 1
  • EXAMPLE 8 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.80, a size of approximately 6,100 d./250 fil., anda birefringence of 0.0015, which. had been melt-spun in conventional manner, were drawn v by 2.0x in a 100-cm.”long, warm aqueous bath of 80 C., and further by 3.0x in'a l20-cm.long, warm aqueous bath of 40 C. at a drawing rate of 40 m./min. The filaments were then treated to eliminate the water and wound. Thus drawn filaments were heat-treated in a 100 cm. long silicone oil bath of 80 C. while beingimparted with 5% stretching, then in a 100-cm.
  • EXAMPLE 9 14 ther by 3.0x in a 120-cm. long warm aqueous bath of 65 of 24%. The strength-conversion ratio in making the cord from the yarn was 92%.
  • Second stage drawing: Temp. 90 C., (6.5) 7. 0 16 12 higher than 85 C. and first stage I drawing temp.
  • the filaments were subjected to three successive EXAMPLE 11 heattreatments as follows: they were treated in a 120-cm. long, warm aqueous bath of 85 C. under a tension of 3% stretching, then'as'the second heat treatment, in a 80-cm. long silicone oil bath of 120 C., under a tension of 5% stretching, and finally in a 80-cm. long silicone oil bath of 200 C., under a tension maintaining the constant filament length.
  • the filaments were then wound up at a rate of 100 m./ min.
  • the resulting yarn was 1,000 deniers in size, and had a breaking strength of 9.4 g./d., elongation of 2 2%, Young?s modulus of 1,600 kg./mm.
  • the cord had a breaking strength of 18 kg., and an elongation Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.80, a size of approximately 6,100 d./ 250 fil., and a birefringence of 0.0015, which had been melt-spun in conventional manner, were drawn by 2.0 x in a l00-cm. long, warm aqueous bath of 70 C., and further by 2.95 in a l20-crn. long, warm aqueous bath of 45 C., at a rate of 40 m./min. Thefilaments were then treated to eliminate the bath water and wound. The drawn sample was heat-treated in a -crn. long silicone oil bath of 80 C.
  • the resulting yarn had a size of 1,050 deniers, strength of 8.4 g./d., and a breaking elongation .of 26%.
  • the yarn was then given a right hand under-twisting at a rate of 51 turns per cm., and two strands thereof were upper twisted together, followed by a left hand twisting of 51 turns per 10-cm.
  • a tire cord of 1050 d./2 was prepared, which had a cord strength of 15.9 kg. and an elongation of 28%. From those results, the strength conversion ratio in making the cord from the yarn was calculated to be 90%.
  • EXAMPLE 12 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.78, a size of approximately 6,100 d./250 fil., and a birefringence of 0.0016, which had been melt-spun in conventional manner, were cut into a saman aqueous bath of 68 C. at a rate of 10% by 2.0x in an aqueous bath of 68 C. at a rated of 10% /min. using a frame-type drawing machine, and further drawn by 3.2x in an aqueous bath of 40 C. at a rate of 50%/ min. The sample was then heat-treated in silicone oil of 80 C. for 10 minutes, then in silicone oil of 120 C.
  • the resulting yarn had a strength of 8.1 g./d. when measured by the method described in the specification, and a breaking elongation of 32%. On the load-elongation curve, the minimum grade of the inclination above the point of 7.0 g./ d. was 4.1 g./d. The calculated toughness was 1.29 g./d.
  • the yarn had an intrinsic viscosity of 0.77 after the above-specified drawing and heating treatments.
  • EXAMPLE 13 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.78, a size of approximately 6,100 d./250 fil., and a birefringence of 0.0016, which had been melt-spun in conventional manner, were cut into a sample length of 15 cm.
  • the sample was drawn by 2.0x in an aqueous both of 68 C. at a rate of 10%/ min, using a frame-type drawing machine, and further by 3.2x in an aqueous bath of C. at a rate of 50% min.
  • the sample was heat-treated for 10 minutes in 80 C. silicone oil, for a further 10 minutes in 120 C. silicone oil, and finally for an additional 10 minutes in 185 C. silicone oil.
  • the sample was maintained at the constant filament length.
  • the sample was taken out into air, and subsequently thrown into carbon tetrachloride of room temperature to eliminate the silicone oil, and dried.
  • the resulting yarn had a strength of 8.1 g./d. when measured by the test method described in the specification, and a breaking elongation of 32%.
  • the minimum grade of the inclination after the second yield point was 4.1 g./ d.
  • the yarns calculated toughness was 1.29 g./d
  • EXAMPLE 14 Polyethylene terephthalate undrawn filaments having an intrinsic viscosity of 0.80, a size of approximately 6,100 d./ 250 fil., and a birefringence of 0.0015, which had been melt-spun in conventional manner, were drawn by 2.0x in a 100-cm. long, warm aqueous bath of 70 C., and further by 2.95 X in a 120-cm. long, warm aqueous bath of C. at a drawing rate of 40 m./min. Thus drawn filaments were treated to eliminate the water and wound.
  • the sample was then heat-treated in a 100-cm. long silicone oil bath of 80 C. while being maintained at the constant filament length, further in a 120cm. long silicone oil bath of 130 C. with a shrinkage by 2%, and finally in a 100-cm. long silicone oil bath of 190 C. under a tension of 3% stretching.
  • the resulting yarn was treated to eliminate the silicone oil, and wound at a rate of 20 m./min.
  • the yarn had a size of 1,050 deniers, a strength of 8.4 g./d., and a breaking elongation of 26%.
  • the similarly drawn samplepf the same filaments was heat-treated in av -cn1.. long silicone oil bath of C. while being allowed. to by 2%, and further in a 100-cm. long silicone oil'bathiof 185 C., under a tension causing 3% stretching.
  • the which was treated to eliminate the silicone oil and wound at a rate of 20 rn./min. had a size of 1050 deniers,"a strength of 8.2 g./d., and an elongation ;of. 17%,.
  • EXAMPLE 15 1 Polyethylene terephthalate undrawn'filamen ts having an intrinsic viscosity of 0.80, a size of approximately 6,10 0 d./250 fil., and a birefringence of0.0016,'"whi'ch"liadbeen melt-spun in conventional manner, were drawn by 2.0x in warm water of 68 C. at a rate of 10% /min., and further drawn by 3.1 X in warm .water of 40 C, atarate of 50% /min. The drawn filaments. had a ,specificigifavity measured at 20 C.
  • the resulting yarn had a size of 1,000'fidenier's; a strength of 8.4 g./d., and a. breakingelongation of j20% ⁇
  • the minimum grade of'the inclination aftij the second yield point was 4.8 g./d.
  • the calculated toiighf ness was 0.84 g./d.
  • EXAMPLE 17 Polyethylene terephthalate undrawn monofilament of 1,200 deniers having an intrinsic viscosity of 0.80 and a birefringence of 0.0035, which had been melt-spun in conventional manner, was drawn by 2.0x in warm water of 65 C. at a rate of 10%/min., using a frame-type drawing machine. The filament was further drawn by 3.1x in warm water of 45 C., at a rate of 100% /min., and thereafter heat-treated in warm water of 65 C., with stretching by 1.1x. As the second heat treatment, the filament was further treated in silicone oil of 120 C. with stretching, and then in silicone oil of 180 C. with 10% stretching. The resulting monofilament had a breaking strength of 13.8 g./d., breaking elongation of 16%, and a Youngs modulus of 1,900 kg./mm.
  • the resulting yarn had a strength of 7.5 g./d., and an elongation of 15 On the load-elongation curve, the minimum grade of inclination above the point of 7.0 g./d. was g./d. The calculated toughness was 0.56 g./d.
  • the yarn size was 1,100 deniers, and intrinsic viscosity was 0.88.
  • the same yarn was given a right hand under-twisting of 51 turns per 10 cm., and two strands thereof were together given an upper twist, followed by a left hand twisting of 51 turns per 10-cm. Thus a tire cord of 1,100 d./2 was obtained.
  • the cord had a strength of 14.4 kg, and an elongation of 17%.
  • the strengthconversion ratio in making the cord from the yarn was 82%.
  • a drawing and heat-treating process of polyester undrawn filaments containing at least 85 mol percent of ethylene tcrephthalate units which consists essentially of:
  • step (2) drawing said filaments drawn in step (1) in a second stage drawing at a temperature within a range of 10-85 C., said temperature being lower than that employed in step (1), at a draw ratio within a range of 1.2-7.0X, said draw ratio being at least 80% of the highest possible draw ratio under the conditions of drawing without filament breakage,
  • step (3) heat-treating the drawn filaments of step (2) in a first heat treatment at a temperature within a range of 55 -120 C. and higher than that employed in step (2), while subjecting said filaments to a tension that maintains the filament length during said first heat treatment at 95-130% of that immediately before said first heat treatment,
  • step (2) is lower than that employed in step (1) by at least 10 C.
  • step (3) is higher than the drawing temperature of step (2) by at least 10 C.
  • the heat-treating temperatures in all stages of step (4) are higher than that employed in step (3) by at least 10 C.
  • step (2) drawing said filaments drawn in step (1) in a a second stage drawing in water or ethylene glycol of l a temperature within a range of 10-85 C., said temperature being lower than the temperature employed in step (1) at a draw ratio of 1.27.0 said draw ratio being at least 80% of the highest possible draw ratio under the conditions of drawing without filament breakage,
  • step (3) heat-treating the drawn filaments of step (2) in a first heat treatment at a temperature not lower than 60 C. but lower than 100 C. and higher than the temperature employed in step (2), while subjecting the filaments to a tension that maintains the length of said filaments during said first heat treatment at 115% of that immediately before said first heat treatment,
  • step (3) further heat-treating the filaments from step (3) in a two-stage second heat treatment comprising a (i) first stage of second heat treatment at a temperature within a range of -170 C., while the filaments are subjected to a tension that maintains the length of said filaments during the first stage of second heat treatment at 95- of that immediately before the first stage of second heat treatment, and (ii) a second stage of second heat treatment at a temperature exceeding 170 C., while subjecting the filaments to a tension that maintains the length of said filaments during the second stage of second heat treatment at 95-115% of that immediately before the second stage of second heat treatment, the tension exerted on the filaments in stages (i) and -(ii) of step (4) being so adjusted that the filament length after stage (ii) of step (4) is at least 90% but less than of that immediatelyl before step (3).
  • step (2) drawing said filaments drawn in step (1) in a second stage drawing in water or ethylene glycol of a temperature within a range of 4 -75 C. and lower than that employed in step (1) by at least 1 0 C., at a draw ratio of 1.27.0 and which is at least C., at a draw ratio of 1.27.0 and which is at least of the highest possible draw into under the conditions of drawing without filament breakage,

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US798426A 1968-02-15 1969-02-11 Drawing and heat treatments of polyester filaments Expired - Lifetime US3651198A (en)

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CH (1) CH525967A (fr)
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894135A (en) * 1971-10-06 1975-07-08 Zimmer Ag Process for stretching a cable of polyester threads
US3963678A (en) * 1974-06-17 1976-06-15 E. I. Du Pont De Nemours And Company Large denier polyethylene terephthalate monofilaments having good transverse properties
DE2747690A1 (de) * 1976-10-26 1978-04-27 Celanese Corp Hochleistungs-polyesterfilamentgarn
DE2747803A1 (de) * 1976-10-26 1978-04-27 Celanese Corp Verfahren zur herstellung von verbesserten polyesterfilamenten hoher festigkeit und ungewoehnlich stabiler innerer struktur
US4571793A (en) * 1983-03-02 1986-02-25 Enterprise Machine And Development Corp. Air jet texturing system for the production of uniform textured yarn
US4639347A (en) * 1983-05-04 1987-01-27 E. I. Du Pont De Nemours And Company Process of making crimped, annealed polyester filaments
US4690866A (en) * 1984-07-09 1987-09-01 Teijin Limited Polyester fiber
US4704329A (en) * 1984-03-16 1987-11-03 E. I. Du Pont De Nemours And Company Annealed polyester filaments and a process for making them
US4950539A (en) * 1986-10-24 1990-08-21 Viscosuisse Sa Product and method of producing a smooth polyester yarn
US5106685A (en) * 1987-10-13 1992-04-21 Rhone-Poulenc Viscosuisse Sa Process for manufacturing a smooth polyester yarn and yarn so obtained
US6015616A (en) * 1990-05-11 2000-01-18 Arteva North America S.A.R.L. Drawn polyester yarn having a high tenacity, a high modulus and a low shrinkage
EP2159307A1 (fr) * 2007-05-24 2010-03-03 Teijin Fibers Limited Monofilament pour tissu d'écran et processus de fabrication de tissu d'écran

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2318887C3 (de) * 1973-04-14 1982-11-11 Akzo Gmbh, 5600 Wuppertal Verfahren zur Herstellung von Polyesterfäden durch Schrumpfbehandlung heißverstreckter Fäden in zwei Stufen
FR2750706B1 (fr) * 1996-07-04 1998-11-20 Rhone Poulenc Fibres & Polymer Filaments en matiere synthetique et procede de fabrication d'un tel filament

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894135A (en) * 1971-10-06 1975-07-08 Zimmer Ag Process for stretching a cable of polyester threads
US3963678A (en) * 1974-06-17 1976-06-15 E. I. Du Pont De Nemours And Company Large denier polyethylene terephthalate monofilaments having good transverse properties
DE2747690A1 (de) * 1976-10-26 1978-04-27 Celanese Corp Hochleistungs-polyesterfilamentgarn
DE2747803A1 (de) * 1976-10-26 1978-04-27 Celanese Corp Verfahren zur herstellung von verbesserten polyesterfilamenten hoher festigkeit und ungewoehnlich stabiler innerer struktur
US4195052A (en) * 1976-10-26 1980-03-25 Celanese Corporation Production of improved polyester filaments of high strength possessing an unusually stable internal structure
US4571793A (en) * 1983-03-02 1986-02-25 Enterprise Machine And Development Corp. Air jet texturing system for the production of uniform textured yarn
US4639347A (en) * 1983-05-04 1987-01-27 E. I. Du Pont De Nemours And Company Process of making crimped, annealed polyester filaments
US4704329A (en) * 1984-03-16 1987-11-03 E. I. Du Pont De Nemours And Company Annealed polyester filaments and a process for making them
US4690866A (en) * 1984-07-09 1987-09-01 Teijin Limited Polyester fiber
US4950539A (en) * 1986-10-24 1990-08-21 Viscosuisse Sa Product and method of producing a smooth polyester yarn
US5106685A (en) * 1987-10-13 1992-04-21 Rhone-Poulenc Viscosuisse Sa Process for manufacturing a smooth polyester yarn and yarn so obtained
US6015616A (en) * 1990-05-11 2000-01-18 Arteva North America S.A.R.L. Drawn polyester yarn having a high tenacity, a high modulus and a low shrinkage
US20100151244A1 (en) * 2007-05-04 2010-06-17 Teijin Fibers Limited Monofilament for screen mesh cloth, and method for producing screen mesh cloth
EP2159307A1 (fr) * 2007-05-24 2010-03-03 Teijin Fibers Limited Monofilament pour tissu d'écran et processus de fabrication de tissu d'écran
EP2159307A4 (fr) * 2007-05-24 2011-06-22 Teijin Fibers Ltd Monofilament pour tissu d'écran et processus de fabrication de tissu d'écran

Also Published As

Publication number Publication date
CH525967A (de) 1972-07-31
NL6902465A (fr) 1969-08-19
GB1247223A (en) 1971-09-22
NL145609B (nl) 1975-04-15
FR2001995A1 (fr) 1969-10-03
DE1907605A1 (de) 1969-10-02

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