EP0173221B1 - Hochfestes Polyestergarn und Verfahren zu seiner Herstellung - Google Patents

Hochfestes Polyestergarn und Verfahren zu seiner Herstellung Download PDF

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Publication number
EP0173221B1
EP0173221B1 EP85110418A EP85110418A EP0173221B1 EP 0173221 B1 EP0173221 B1 EP 0173221B1 EP 85110418 A EP85110418 A EP 85110418A EP 85110418 A EP85110418 A EP 85110418A EP 0173221 B1 EP0173221 B1 EP 0173221B1
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EP
European Patent Office
Prior art keywords
yarn
threads
shrinkage
yarns
stretching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85110418A
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German (de)
English (en)
French (fr)
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EP0173221A2 (de
EP0173221A3 (en
Inventor
Hans Dr. Thaler
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INVISTA TECHNOLOGIES Sarl
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Hoechst AG
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Publication date
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Priority to AT85110418T priority Critical patent/ATE49026T1/de
Publication of EP0173221A2 publication Critical patent/EP0173221A2/de
Publication of EP0173221A3 publication Critical patent/EP0173221A3/de
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Publication of EP0173221B1 publication Critical patent/EP0173221B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/902—High modulus filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the present invention relates to a high-strength, low-shrinkage polyester yarn for industrial use, i. H. the use in particular in the form of twists, fabrics, braids, etc. as reinforcements in technical products such as tarpaulin fabrics, tires, drive belts, conveyor belts, etc., and a manufacturing process for such yarns from high-orientation filaments.
  • the tenacity of this material is around 76 cN / tex with an elongation at break of 11%.
  • a yarn still has a high thermal shrinkage; at 200 ° C hot air treatment, for example, it is still about 18%.
  • the determination of thermal shrinkage at 200 ° C has become common, since 200 ° C is generally the highest temperature that can occur when coating fabrics made from such yarns.
  • a yarn material that still has a shrinkage of, for example, 18% leads to strong and uncontrollable dimensional changes in such a coating process. It is therefore necessary to reduce the S 200 thermal shrinkage from the 18% specified above. This is done in the usual way by thermomechanical shrinking processes, in which the yarns are shrunk under controlled tension.
  • the maximum tensile strength and maximum tensile strength values are not suitable for sufficiently characterizing the properties of such a yarn.
  • the curve b in the KD diagram of FIG. 1 shows which changes in the physical properties can result after a shrinking process. This curve is the measurement of a commercially available yarn with low shrinkage. From the curve b of Figure 1, the formation of the so-called "shrink saddle" is clearly visible.
  • a low spinning take-off speed means at the same time less conveyance per spinneret. It is known that there is a sharp increase in the conveyance per spinneret with increasing spinning take-off speed, such as e.g. B. is shown in Figure 1 of German Offenlegungsschrift 2 207 849. Attempts to produce high-strength yarns by rapid spinning alone have so far failed due to the low strength and the high elongation at break of yarns produced in this way, which were first described in US Pat. No. 2,604,667.
  • German Auslegeschrift 2 254 998 a method is described to first fold and twist high-speed spun threads and then to stretch the cord thread obtained.
  • the necessary excessive twisting of the cord thread before stretching is difficult to apply, the process is too susceptible to faults and therefore has no practical significance.
  • FR-A-2 369 360 describes a multi-stage process consisting of spinning sections and subsequent separate multiple drawing stages.
  • a polyester material is spun in such a way that the filament obtained is given an "essential orientation".
  • This relatively high orientation is expressed in a birefringence value of the undrawn filaments of 0.009 to 0.07, preferably 0.009 to 0.03.
  • the degree of orientation of these spun filaments is thus of the same order of magnitude as that of the supply yarn used according to the invention.
  • a major difference between the teaching of the citation and the method according to the invention lies in the drawing process.
  • the spun material is reduced to at least 50% z. B. 50 - 80% of its max. Draw ratio stretched.
  • FR-A-2 369 360 is technically complex because it requires a spinning drawing device and, in addition, a multi-stage drawing device. For technical reasons, it can only spin at relatively low tensile speeds are operated, which not only economically reduces the polyester throughput but also requires special measures in the actual spin stretching area. For example, when coarse titers are spun, it is very difficult to generate the required spin stretching tension, which is why the method is mainly restricted to finer, non-technical titers.
  • the filaments produced by this known method show improvements over the previously known high-strength filaments made of polyester with regard to their thermal stability, but have the major disadvantage of a relatively low stability against the action of hot water or chemicals.
  • This disadvantage already mentioned in European patent application 0 080 906 and in Japanese patent application Sho-58-23914, could be due to the relatively low degree of crystallinity, since the possibility of action of the chemicals on amorphous polyethylene terephthalate is considerably greater than on crystalline ones.
  • the method is primarily suitable for the production of fine individual titers, which further increases the sensitivity to chemicals.
  • the filament material of FR-A-3 369 360 also has a relatively high heat shrinkage, which is a serious disadvantage for technical use, e.g. B. means as a tire cord. It is therefore recommended in this document to optionally carry out a shrinking treatment of the filaments. However, the elasticity of the material increases again, which is also disadvantageous for technical all-round use.
  • the object of the present invention was to provide a technically simplified process for the production of polyester filaments which do not have the above-mentioned disadvantages of the filaments produced according to FR-A-2 369 360, but on the basis of their combination of properties are suitable for universal use in the technical field.
  • European patent application 0 089 912 is also intended to work at an increased winding speed of over 1500 m / min.
  • a method is described with which, by changing the previously used spinning conditions, a spinning fader is obtained at high take-off speed, which leads to high strength after stretching.
  • Japanese patent application Sho-51-53019 shows that stretched polyester threads with a birefringence value of 0.03 or more can be stretched to high-strength threads, which are then subjected to a shrinking treatment.
  • the yarns obtained in this way have a thermal shrinkage at 150 ° C. of less than 2.5%, but their elongations at break are above 15, mostly in the range between 16 and 22%.
  • these threads or yarns have a "shrink saddle", as was shown in curve b of FIG.
  • pre-oriented threads which have a certain minimum crystallinity are to be subjected to stretching at at least 85 ° C.
  • the physical values of the threads or yarns thus obtained are relatively poor. These yarns are only intended for areas of application in which a thermal treatment is carried out before the finished articles are manufactured.
  • the patent application mentions the dip process customary in tire cord twists for heat setting and curing the resorcinol / formaldehyde / latex finish.
  • the aim of the present invention is high-strength, low-shrinkage and low-stretch polyester filaments for all technical fields of application.
  • the stability quotient SO used to define the yarns according to the invention is a dimensionless parameter. It is calculated using the following formula As already defined above, the term ED 20 is understood to mean the degree of elasticity at a load of 20 cN / tex den, the value S 200 represents the thermal shrinkage in percent at 200 ° C and the value D 54 the reference elongation at a load of 54 cN / tex.
  • the course of the KD diagram for the yarns according to the invention shows the curve in FIG. 1.
  • the crystallinity of the individual filaments is 56 to about 65%.
  • the yarns preferably consist of polyethylene terephthalate, the thread-forming substance optionally having up to 2% by weight of other comonomer units. Yarns with an S 200 thermal shrinkage of less than 3%, preferably less than 2%, are preferred. The same applies to yarns that have a crystallinity of 60% to 63%.
  • the crystallinity is calculated from the density of the threads according to the following equation
  • the density d of the threads can be determined with the aid of a gradient column, the density of the amorphous portion d a has been set at 1.335 g / ml and the density of the crystalline material d k at 1.455 g / ml.
  • Such yarns are produced according to the invention by stretching polyester yarns which have a pre-orientation corresponding to a birefringence of at least 0.025 and an average molecular weight corresponding to a relative solution viscosity of approximately 1.9 to 2.2.
  • Such threads are subjected to hot drawing, the drawing ratio used being at least 90% of the maximum cold drawing ratio, and the drawing tension in this drawing being between 19 and 23 cN / tex under the selected conditions. Preferred ranges for this yield stress are 20 to 23 cN / tex.
  • Untwisted yarns have little or no protective twist; for 1100 dtex yarns e.g. B. 60 T / m widely used. These yarns are either used directly as reinforcements, e.g. B. used in coating fabrics or serve as a starting material for threads, z. B. in Re i fenbau.
  • High-tenacity yarns usually have a tenacity of more than 65 cN / tex.
  • the thermal shrink S 200 is the relative change in length of a yarn that has shrunk freely for 10 minutes at an air temperature of 200 ° C.
  • the degree of elasticity ED 20 is determined according to DIN 53 835.
  • the yarn is loaded in a tensile testing machine up to a defined force limit and then completely relieved. It is determined how high the total elongation at the defined load limit ( ⁇ ges.) And the remaining residual elongation ( ⁇ rest ) is after the yarn is relieved.
  • a wet for the elastic behavior is the elastic expansion ratio (ED) or also called degree of elasticity. This is calculated using the formula Figure 2 shows the dependence of the degree of elasticity on the applied load for a commercially available low-shrinkage yarn (curve a). In this curve, a spontaneous drop in the degree of elasticity can be observed from around 10 cN / tex.
  • the reference elongation D 54 also serves to characterize the mechanical behavior of the yarn according to the invention in this application. It is the value of the elongation at a load of 54 cN / tex. The value of the load of 54 cN was chosen arbitrarily. It corresponds to about 75% of the tenacity of these yarns and also allows a good statement about the elastic behavior of the yarns, but in particular whether or not there is a "shrink saddle" in the KD diagram of the yarn examined. Of course, the reproduction of the complete force-elongation diagram has the best informative value about the mechanical behavior of an examined yarn, but numerical values are more suitable for comparisons.
  • the initial module also called Young's module
  • Young's module which can mainly be found in Anglo-Saxon literature, and which indicates the slope of the KD line in its initial area, is less suitable for the characterization of high-strength fibers.
  • a conclusion about the entire working range of the threads is only possible from the initial module for drawn but not shrunk filaments. As can be seen for example from FIG. 1 curve b, the KD diagram changes in a characteristic way with shrunk filaments.
  • curve b After an initially identical increase in curves a and b, that is to say a corresponding initial module, curve b begins to flatten out from approximately 10 cNltex, which then increases again with high loads and high elongation values.
  • the elongation specification is the most important in a point on the KD diagram that is above the shrink saddle, but clearly below the elongation at break.
  • a stretching process as described in the following and which can only be carried out with spun fabric having a higher pre-orientation is essential for achieving the claimed filament properties.
  • Drawing processes are usually defined by specifying drawing conditions and drawing temperatures.
  • Maintaining a sufficient dwell time of threads on a heater is of particular importance for technical use, particularly in the case of high-titer filaments. What effect heat transfer can have shows z. B. Aleksandrijskij (Soviet. Contributions to fiber research and textile technology 1971, p. 521).
  • a dwell time of at least 0.5 seconds is required in order to obtain a constant shrinkage when fixing drawn filaments.
  • the dwell time should be at least 3 seconds (Pakshver, Khimicheskie Volokna, 1983, 1, pp. 59 - 61).
  • FIG. 4 shows the dependence of the shrinkage at 200 ° C. (S 200 ) on the drawing tension of a yarn with the final titer of 1100 dtex and a birefringence of 0.0025 (curve a). The same was done with a filament with a double refraction of 0.033 and a max. VV of 90% carried out, which was spun at a winding speed of 3000 m / min. The measured values gave the Curve b in FIG. 4.
  • drawing tensions are increased by reducing the temperature or by shortening the dwell time, not only is a higher thermal shrinkage obtained, but the number of capillary breaks also increases.
  • a lowering of the drawing tensions could only be achieved by further increasing the temperature, by slower driving or by lowering the drawing ratio.
  • a lowering of the draw ratio must be avoided due to the associated deterioration in the strength values.
  • a slower driving style and thus an increased dwell time in the stretching field will only be successful if the time for complete fixation with the faster driving style was too short. If this was sufficient, a further slowdown does not bring any further reduction in the drawing tension, but only worsens the strength of the thread.
  • FIG. 3 shows a schematic illustration of a preferred device for carrying out the method according to the invention.
  • the spun yarns Y are drawn off from the bobbins 1 plugged into the creel and fed to the roller mill 2 together as a family of threads.
  • This consists of 5 to 7 heatable rollers, the surface temperatures of which range from 75 to 100 ° C depending on the thread speed.
  • the thread sheet then passes through the heated furnace 3, which completely encloses the thread sheet, and then reaches the roller mill 4, which also has 5 to 7 rollers.
  • the speed of the roller mill 4 is higher by a factor of the stretching than that of the roller mill 2. From here, the threads either arrive directly at the winding 6 or they are previously guided over the roller mill 5, which generally has three rollers.
  • the furnace can be heated either in such a way that its walls are heated electrically or by means of a liquid heat transfer medium; at the same time, heated air can flow against the threads.
  • Another Version is the heating of the thread sheet with infrared radiators, which are installed in the oven.
  • Another possibility is heating by hot air, which flows across the thread sheet transverse to its direction of travel. If a relaxation process is subsequently connected to the stretching, only the roller mill 4 is heated to a correspondingly high temperature, the shrinkage approval then takes place between the roller mill 4 and the roller mill 5 or between the roller mill 4 and the winding 6. In the latter case, the shrinkage approval must be exact be adjustable between these two units.
  • the temperature, time and stress conditions of the thermal treatment determine the properties of the fabrics with regard to shrinkage and elongation. Even after this further thermal treatment, the materials according to the invention prove to be superior to those known hitherto.
  • the finished finished fabrics also have more favorable shrinking, stretching and elasticity properties than the previously known ones and exceed them in thermal and dimensional stability.
  • a shorter time of exposure to heat is possible in order to maintain the final properties of the finished materials. This means that the thermal aftertreatment of the textiles can take place under milder conditions with shorter residence times, which is also advantageous in terms of strength.
  • the yarns produced according to the invention are suitable both for use in threads for z. B. the production of tires, etc., which are thermally treated again in the latexing, and - with a re-axing stage downstream of the stretching stage - for the use of PVC-coated fabric, etc.
  • the following examples are intended to explain the process in detail. It can be seen that the filaments according to the invention are obtained only if the conditions of the process according to the invention are observed. Unless otherwise stated, percentages and parts are by weight.
  • the spun fabric used for the stretching tests described below was produced according to known technology as described below.
  • the polyethylene terephthalate granules used for Examples 1 to 7 and 12 to 14 showed a relative solution viscosity in dichloroacetic acid of 2.120.
  • a material with a relative solution viscosity of 1.990 and for Example 10 a material with a relative solution viscosity of 2.308 was used.
  • the relative solution viscosity was usually determined on solutions of 1.0 g of the polymer in 100 ml of dichloroacetic acid at 25 ° C. by measuring the transit times of the solution through a capillary viscometer and by determining the transit time of the pure solvent under the same conditions.
  • the polyethylene terephthalate granules used were melted using an extruder, fed to a spinning pump and spun using a spin pack.
  • the nozzle plate in the spin pack each had 100 holes with a diameter of 0.45 mm each.
  • the threads emerging from the spinnerets were reheated in the case of the raw materials with relative solution viscosity 2.120 and 2.308 by a device located below the spinneret plate, as described in German Patent 2 115 312, and then with air at 26 ° C. and a speed of Blown transversely at 0.5 m / sec.
  • Two such spun threads were fed together to a preparation device, provided with a spinning preparation and drawn off and spun on at the speeds indicated in the examples. Depending on the pre-orientation of the spun fabric, the threads were then drawn under different conditions and on different drawing systems and partially shrunk.
  • the stretching devices differed by the type of stretching furnace.
  • IR is understood to mean a heating channel in which the threads have been heated by ceramic infrared radiators
  • air is understood to mean an oven in which the threads are heated by hot air flowing transversely.
  • the specified temperatures refer to the temperatures of the sensors. In the “IR” oven the sensors were about 15 mm above the thread sheet, in the “Air” oven they were attached below the thread sheet and indicated the temperature of the heated air before this strikes the coulter.
  • Example 1 specifies the way of drawing a strand with low pre-orientation. The specified temperature could not be increased further, otherwise the thread would break.
  • Example 5 the same drawing conditions with regard to residence time and temperature as in Example 1 were used, but the feed yarn had a high degree of preorientation.
  • a comparison of the values compiled in the table below shows that, owing to the high degree of preorientation, the shrinkage is slightly lower and the stability quotient is slightly higher than in Example 1, the progress compared to the thread of Example 1, which is also well fixed, is not great.
  • the values of Example 4 show that by increasing the sensor temperature by 20 ° C., a thread with significantly reduced shrinkage could be obtained, which would surely meet all of the claims.
  • Example 6 the temperature of the heater was raised to that of example 4, but the residence time was halved by doubling the working speed. This measure led to a sharp increase in the drawing tension, the values for the shrinkage and stability quotient are clearly outside the claimed ranges.
  • This example shows how important it is to comply with the required drawing conditions, because otherwise, despite the high pre-orientation of the spun fabric which reduces the shrinkage, only a yarn is obtained which is even inferior to the classic threads or yarns in terms of thermal stability.
  • the drawing conditions according to the invention are applied to spun threads with high pre-orientation. However, the thread-forming substances used have different average molecular weights corresponding to different relative solution viscosities.
  • Example 14 shows that if the pre-orientation is increased by increasing the take-off speed to a birefringence, which is still below the claimed size of 0.025, an improvement in the thermal stability is achieved, since the drawing temperature has already been increased somewhat. However, the claimed ranges of the physical values of the yarns could not be reached.
  • Both Examples 11-13 used a cross-flow air stretching oven.
  • an inventive thread can only be obtained by increasing the drawing temperature, which this time could presumably also be the temperature of the thread at the end of the drawing field.
  • An increase in the drawing temperature in Example 11 to 250 ° C. led to the threads continuously tearing. Individual threads broke even at 245 ° C, but others showed a large number of capillary breaks.
  • Example 11 a slightly pre-oriented supply yarn was used that only had a birefringence of 0.0033.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP85110418A 1984-08-30 1985-08-20 Hochfestes Polyestergarn und Verfahren zu seiner Herstellung Expired EP0173221B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85110418T ATE49026T1 (de) 1984-08-30 1985-08-20 Hochfestes polyestergarn und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3431831 1984-08-30
DE19843431831 DE3431831A1 (de) 1984-08-30 1984-08-30 Hochfestes polyestergarn und verfahren zu seiner herstellung

Publications (3)

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EP0173221A2 EP0173221A2 (de) 1986-03-05
EP0173221A3 EP0173221A3 (en) 1986-05-28
EP0173221B1 true EP0173221B1 (de) 1989-12-27

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EP85110418A Expired EP0173221B1 (de) 1984-08-30 1985-08-20 Hochfestes Polyestergarn und Verfahren zu seiner Herstellung

Country Status (7)

Country Link
US (1) US4973657A (ja)
EP (1) EP0173221B1 (ja)
JP (2) JP2619356B2 (ja)
AT (1) ATE49026T1 (ja)
BR (1) BR8504163A (ja)
CA (1) CA1300360C (ja)
DE (2) DE3431831A1 (ja)

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EP0450607A2 (en) * 1990-04-06 1991-10-09 Asahi Kasei Kogyo Kabushiki Kaisha Polyester fiber and method of manufacturing same

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EP0526740B1 (de) * 1991-07-05 1998-03-25 Hoechst Aktiengesellschaft Hochfestes Polyestergarn und Verfahren zu seiner Herstellung
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EP0579083B1 (de) * 1992-07-10 1998-06-03 Hoechst Aktiengesellschaft Verfahren zum Verstrecken von erhitzten Garnen, damit erhältliche Polyesterfasern sowie deren Verwendung
DE4344691A1 (de) * 1993-12-27 1995-06-29 Hoechst Ag Hochfestes, schwer entflammbares Polyestergarn, Verfahren zu seiner Herstellung und seine Verwendung
CZ287583B6 (en) * 1994-12-23 2000-12-13 Akzo Nobel Nv Process for producing thread of continuous polyester fibers
US6471906B1 (en) 2000-07-10 2002-10-29 Arteva North America S.A.R.L. Ultra low-tension relax process and tension gate-apparatus
KR20120002498A (ko) * 2010-06-30 2012-01-05 코오롱인더스트리 주식회사 폴리에스테르 섬유 및 그의 제조방법
EP4363642A1 (de) 2021-06-28 2024-05-08 Indorama Ventures Fibers Germany GmbH Elektrisch leitfähiges garn

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JPS5846117A (ja) * 1981-09-14 1983-03-17 Teijin Ltd 熱安定性の優れたポリエステル繊維及びその製造法
JPS5898416A (ja) * 1981-11-30 1983-06-11 Asahi Chem Ind Co Ltd 高強度ポリエチレンテレフタレ−ト糸条
JPS5898419A (ja) * 1981-12-02 1983-06-11 Touyoubou Pet Koode Kk 熱寸法安定性および化学安定性にすぐれると同時に高強度を有するポリエステル繊維
ZA83849B (en) * 1982-02-22 1984-02-29 Goodyear Tire & Rubber Process for the production of high strength polyester yarn
JPS591713A (ja) * 1982-06-22 1984-01-07 Toray Ind Inc ポリエチレンテレフタレ−ト系繊維の製造方法
JPS595373A (ja) * 1982-07-02 1984-01-12 Casio Comput Co Ltd デ−タ転送方式
JPH0733610B2 (ja) * 1982-09-22 1995-04-12 東レ株式会社 ポリエステルタイヤコードの製法
JPS59211638A (ja) * 1983-05-11 1984-11-30 東レ株式会社 縫糸用ポリエステルフイラメント
JP3111086B2 (ja) * 1991-06-25 2000-11-20 マツダ株式会社 エンジンのクランクシャフトの軸受メタル組込方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0319940A1 (de) * 1987-12-09 1989-06-14 Hoechst Aktiengesellschaft Fahrzeugreifen
EP0450607A2 (en) * 1990-04-06 1991-10-09 Asahi Kasei Kogyo Kabushiki Kaisha Polyester fiber and method of manufacturing same
EP0450607B1 (en) * 1990-04-06 1997-08-06 Asahi Kasei Kogyo Kabushiki Kaisha Polyester fiber and method of manufacturing same

Also Published As

Publication number Publication date
CA1300360C (en) 1992-05-12
BR8504163A (pt) 1986-06-24
DE3431831A1 (de) 1986-03-13
DE3575000D1 (de) 1990-02-01
ATE49026T1 (de) 1990-01-15
JPH09170113A (ja) 1997-06-30
JP2854290B2 (ja) 1999-02-03
JP2619356B2 (ja) 1997-06-11
EP0173221A2 (de) 1986-03-05
JPS6163714A (ja) 1986-04-01
EP0173221A3 (en) 1986-05-28
US4973657A (en) 1990-11-27

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