IE860905L - Water-dispersible synthetic fiber - Google Patents

Water-dispersible synthetic fiber

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Publication number
IE860905L
IE860905L IE860905A IE90586A IE860905L IE 860905 L IE860905 L IE 860905L IE 860905 A IE860905 A IE 860905A IE 90586 A IE90586 A IE 90586A IE 860905 L IE860905 L IE 860905L
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IE
Ireland
Prior art keywords
fiber
water
dispersible
polyester
filaments
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Application number
IE860905A
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IE57359B1 (en
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Du Pont
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Publication of IE860905L publication Critical patent/IE860905L/en
Publication of IE57359B1 publication Critical patent/IE57359B1/en

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Classifications

    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/20Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/24Polyesters

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Water-dispersible polyester fiber of cruciform cross-section to promote dispersibility, and so better uniformity, more opacity, good permeability and an attractive flannel-like hand to the resulting wet-laid fabrics.

Description

This invention concerns new water-dispersible synthetic polymer fiber, particularly of poly(ethylene terephthalate), and its preparation.
There has been increased interest in recent years in water-dispersible synthetic fiber, especially of polyester. Such water-dispersible fiber is used in various non-woven applications, including paper-making and wet-laid non-woven fabrics, sometimes as part of a blend, often with large amounts of wood pulp, or fiberglass, but also in applications requiring only polyester fiber, i.e., unblended with other fiber. This use, and the requirements therefor, are entirely different from, previous more conventional use as tow or staple fiber for conversion into textile yarns for eventual use in woven or knitted fabrics, because of the need to disperse this fiber in water instead of to convert the fiber into yarns e.g., by processes such as carding, e.g. in the cotton system. It is this requirement for water-dispersibility that distinguishes the field of the invention from previous, more conventional polyester staple fiber.
Host such water-dispersible polyester fiber is of poly(ethylene terephthalate), and is prepared in essentially the same general way as conventional textile polyester staple fiber, except that most water-dispersible polyester fiber is not crimped, whereas any polyester staple fiber for use in textile yarns is generally crimped while in the form of tow, before conversion into staple fiber. Thus, water-dispersible polyester fiber has generally been prepared by melt-spinning the polyester into filaments, combining the filaments to form a tow, drawing, applying-a suitable coating to impart 5 water-dispersible properties, generally in the same way as a finish is applied to a tow of conventional textile filaments, and then, generally without any crimping (or with imparting only some mild wavy undulations in some cases to provide extra bulk and a three-dimensional 10 matrix), converting the tow into staple. Some prior polyester staple fiber has been prepared in uncrimped form, e.g. for use as flock in pile fabrics, but for such use, water-dispersibility has not been required.
Polyester fibers are naturally hydrophobic, so it 15 is necessary to apply to the polyester a suitable coating, as disclosed by Ring et al. in U.S. Patent No. 4,007,083, Hawkins in U.S. Patent Nos. 4,137,181, 4,179,543 and 4,294,883, and Viscose Suisse in British Patent No. 958,350, to overcome the inherent hydrophobic character of 20 the polyester fiber without creating foam or causing the fibers to flocculate. It is this coating that has distinguished water-dispersible polyester fiber from more conventional polyester staple fiber, rather than any inherent characteristic feature of the polyester itself, 25 or of its shape, such as the cross-section. Heretofore, so far as is known, the cross-section of all commercial water-dispersible polyester fiber has been round. Indeed the cross-section of most commercial polyester staple fiber has generally been round, because this has been 30 preferred.
Although, hitherto, most synthetic polymeric water-dispersible fiber has been formed of polyester, being inexpensive and plentiful, increasing amounts of polyolefins and polyamides are beginning to be used for 35 water-dispersible fibers, and so the invention is not limited only to polyesters, but covers other synthetic polymers.
Accordingly, the present invention provides a synthetic polymer fiber rendered water-dispersible by a coating promoting water-dispersibility, wherein the fibers are of cruciform cross-section.
A cruciform cross-section has been used heretofore for other polyester fibers, as described herein. Other than the cross-section, the water-dispersible fiber of the invention may be essentially similar to prior water-dispersible polyester or other synthetic polymer fibers, although the advantages described hereinafter may provide the opportunity for additional modifications. The invention will be described hereinafter with special reference to polyester fiber, although it will be recognized that other synthetic polymers, such as polyamides and polyolefins, may also be used.
The fibers of the invention may be made conveniently by melt-spinning and drawing polyester filaments of appropriate denier per filament (dpf), and applying thereto a suitable coating to impart water-dispersible characteristics. The filaments are then generally cut into staple of whatever length is desired "for the end-use contemplated. - 3a - ^ The present invention further provides a process for preparing polyester fiber rendered water-dispersible by a coating promoting water-dispersibility, by melt-spinning the polyester into filaments, drawing the tow and cutting the filaments, wherein the polyester is spun into filaments of cruciform cross-section, the filaments are coated with a segmented synthetic copolyester of poly(ethylene terephthalate) repeat units and poly(oxyalkylene) groups derived from a poly(oxyalkylene) 10 glycol having an average molecular weight in the range of 300 to 6,000, and cut to fibers of cut length from 5 to 90 mm.
The use of a cruciform cross-section for the water-dispersible fiber of the invention has, surprisingly, been 15 found to promote dispersibility, in comparison with a round cross-section, and this imparts to the resulting wet-laid fibers better uniformity, more opacity, good permeability, and an attractive flannel-like hand as will J be seen in the Example.
Figure 1 shows a cruciform cross-section for stylized fiber according to the invention.
Figure 2 shows a typical spinneret orifice for spinning filaments of the invention.
As indicated above, a cruciform cross-section has already been used for more conventional polyester staple fiber, that has been spun into filaments and drawn, cut, converted into spun yarn, and used in woven or knitted fabrics. Such fiber had the water-dispersible characteristics required for this invention. Similarly, polyester filaments having a cruciform cross-section are already known from Lehmicke U.S. Pat. No. 2,945,739, which discloses a process for melt-spinning polyami.de and polyester filaments of, inter alia cruciform cross-section, and woven and knitted fabrics from staple fibers, and from Jamieson U.S. Pat. No. 3,249,669, which discloses a process for making a multifilament yarn of polyester filaments of various cross-sections, including a cruciform cross-section. Oriented polyester filaments of non-round cross-section have also been described by Frankfort et al. in U. S. Pat. Nos. 4,134,882 and 4,195,051, having been prepared by spinning at a very high speed (6,000 ypm(5486 nyfain)), which high speeds could also be used to prepare oriented polyester filaments of cruciform cross-section as a substrate for applying thereto a suitable coating to impart water-dispersible characteristics, and thereby obtain water-dispersible fiber according to the invention. None of this art concerns the field of the present invention. However, the polyester filamentary substrates for making the water-dispersible fiber of the invention may be prepared by the techniques described therein, or by appropriate modifications of these or other known techniques of making polyester filaments of non-round cross-section.
The prior art references disclose parameters for a cruciform cross-section and Figure 1 is essentially as shown therein.
The preparation of the polyester staple fiber is otherwise conventional, involving the steps of melt-spinning polymer into filaments, collecting the filaments into a tow, drawing the tow, and applying a 5 suitable coating to impart water-dispersible characteristics. If low shrinkage is desired, the drawn filaments are generally annealed.
Selection of an appropriate coating to promote water-dispersibility is important, and more of such 10 coating is generally required than for comparable weights of fiber of round cross-section of similar dpf, because of the larger surface area of the periphery of the cruciform cross-section. It is especially important to provide good boundary lubrication properties. For this reason, an ^5 ethoxylated coating is preferred.
Suitable coatings are disclosed in Hawkins, U.S. Pat. Nos. 4,137,181, 4,179,543 and 4;>294,883 or a synthetic copolyester of poly(ethylene terephthalate) units and poly(oxyalkylene) of groups derived from a 20 poly(oxyalkylene) glycol having an average molecular weight in the range of 300 to 6,000, as disclosed, e.g. in Mclntyre, et al. U.S. Pat. Nos. 3,416,952, 3,557,039 and 3,619,269, referred to therein; other useful segmented copolyesters are disclosed in Raynolds U.S. Patent No. 25 3,981,807.
Such polyester fiber is generally prepared first in the form of a continuous filamentary uncrimped tow or, if extra bulk is required, and a more three-dimensional matrix, the filaments may be provided with mild wave-like 30 undulations by a mild crimping-type process, and the uncrimped or mildly wave-like filaments are cut to the desired cut length, i.e. to form the water-dispersible fiber, which is generally sold in the form of bales, or other packages of cut fiber. Suitable cut lengths are generally from about 5 to about 90 mm (1/4 to 3 inches), generally up to 60 mm (2-1/2 inches), and of 5 length/diameter (L/D) ratio from about 100:1 to about 2000:1, preferably about 150:1 to about 2000:1, it being an advantage of the invention that good performance has been obtainable with preferred water-dispersible fiber of the invention with an L/D ratio higher than we have 10 considered satisfactory with prior art water-dispersible polyester fiber. For instance, machine manufacturers have generally recommended that the L/D ratio not exceed 500:1, and many operators have considered even this figure unrealistically high. A suitable denier per filament is 15 generally from about 0.5 to about 20 (about 0.55 to about 22 dtex). The coating is generally present in amount about 0.04 to about 1.0% of the weight of fiber (0WF%), it being an advantage that smaller amounts may generally be used than we have considered satisfactory according to the prior art. 20 There is also provided a process for preparing such water-dispersible polyester fiber, comprising the steps of melt-spinning the polyester into filaments of cruciform cross-section, forming a tow of such filaments, drawing, and then coating the filaments in the tow with 25 such synthetic copolyester, and, at an appropriate time, converting such coated filaments into staple fiber.
The coating is preferably cured on the filaments by heating the coated filaments, or the resulting staple fiber, if desired, to a temperature of about 100° to about 30 190° C to improve durability.
The invention is further illustrated in the following Example, in which all parts and percentages are by weight, unless otherwise indicated, and OWF is (solids) "of weight of fiber". Reference is made to several 35 measurements of yarn properties, such as tensile properties (tenacity and elongation at break), which are measured according to the methods described in Frankfort et al. U.S. Patent Application No. 4,134,882. It will be understood that other conditions can be used e.g., other designs of orifice, such as are shown in the art.
Example The following fibers, Fiber A, a comparison of round cross-section, and Fiber N, a fiber of the invention of cruciform cross-section, were both spun from poly(ethylene terephthalate) of intrinsic viscosity 0.64, containing 0.3% Ti02 as a delusterant.
Fiber A was spun at 1600 ypm (1463 m/min) into filaments with conventional radial air quenching using a 900 hole spinneret, with round holes 0.015 inches (0.381 mm) in diameter and capillary length of 0.030 inches (0.762 mm), a 270°C block, and polymer throughput 68.2 pounds/hour (30.9 kg/hour). Denier per filament was 3.67 (4.04 dtex). Fiber A was then oriented by running over a set of feed rolls at 29.3 ypm (26.8 m/min), followed by a set of draw rolls at 80.0 ypm (73.15 m/min), and delivered to a conveyor by puller rolls at 80.1 ypm (73.24 m/min). Between feed roll sections the filaments were treated in a 45°C water bath. Between feed and draw rolls the rope was sprayed with water at 98°C. Between draw and puller rolls a commercial water-dispersible coating (50/50 mixture of potassium salt of mono and diacid phosphate esters of lauryl alcohol/tallow alcohol ethoxylated with 25 moles of ethylene oxide) was applied. The filaments were then relaxed free in an oven at 150°C for 6 minutes.
Fiber N was produced in a similar manner to Fiber A except that 625 filaments of 3.22 dpf (3.54 dtex pf) and cruciform cross-section were spun through capillaries as shown in Figure 2, with block temperature 273°C, and throughput 42.9 pounds/hour (19.5 kg/hour). Roll speeds for the orientation were feed rolls 32.1 ypm (29.4 m/min), draw rolls 80.2 ypm (73.3 m/min) and puller rolls 79.2 ypm (72.4 m/min), and a somewhat higher level of water-dispersible coating was used to offset approximately 57% higher surface area of the cruciform cross-section.
The properties of the drawn coated filaments are compared in Table 1.
TABLE 1 Sample A N • Cross-Section dpf (dtex pf) coating OWF (%) Boil-off shrinkage (%) Dry heat shrinkage (196"Ci (%) Tenacity at Break (g/d) Round Cruciform 1.47 (1.62) 1.56 (1.72) 0.4 1.0 2.45 4.5 (4.10) 42 0.93 (0.85) 0.44 0 3.6 4.8 Elongation at break (%) Tenacity at 2% elongation (g/d) (g/dtex) (4.37) 26 (g/dtex) 0.93 (0.85) - 8a - i Both types were cut to form water-dispersible fiber of 1/4, 3/8, 1/2 and 3/4 inch (6.35 mm, 9.53 mm, 12.70 mm, and 19.05 mm) cut lengths and were tested on an inclined wire Fourdrinier machine. Fibers were dispersed for three 5 minutes in a small pulper at 0.75% consistency (kg. fiber per 100 kg. slurry, or furnish). The cylindrical pulper was approximately 3 feet (0.91 m) in diameter by 6 feet (1.83 m) deep. Fibers were then mixed with unrefined sulphite pulp to form a 50% polyester blend and diluted to 10 0.1% consistency in a 10 cubic meter stock tank. This stock was further diluted in the headbox of the machine to 0.0143% consistency and formed into a 0.5 meter wide wet lay nonwoven fabric at 20 meters/minute. A spray of an acrylic binder, Acronyl 240D was spray applied at the end 15 of the Fourdrinier wire. The fabric was then cured in a through air drier at 150°. Finished fabric weight averaged 40 grams/square meter.
Dispersion quality can be judged by the uniformity of the fabric produced from a given sample. As cut length 20 increases, the uniformity of the fabric can generally be expected to suffer significantly. However, great advantages can result from using a longer fiber because the fabric tear strength increases, for example. In practice, therefore, a fabric producer will generally wish 5 to use the longest fiber that will meet his uniformity standards. Thus, a longer fiber with improved, or c equivalent uniformity would be preferred.
The dispersion quality of fabrics from Fibers A £ and N were rated as they were produced on the machine by 10 observing the fabrics as the water drained from them on the Fourdrinier wires. Results of this comparison are in Table 2 and indicate good dispersion for the cruciform in spite of its 57% greater surface area.
TABLE 2 Dispersion description 1 5 Round Cruciform Cut Length item A item N good dispersion few log defects good dispersion fair fabric cover (opacity) normal dispersion very good dispersion 1/4 inch good dispersion (6.35 mm) few log defects 3/8 inch some log defects (9.53 mm) general quality not so good as 1/4 inch (6.35 mm) 1/2 inch fairly good dispersion (12.70 mm) 3/4 inch dispersion definitely (19.05 mm) poor, cover lower Standard physical properties were measured for the set of fabrics at Herty Foundation, Savannah; GA.
Compared each time to Fiber A as 100%, Fiber N had the following average properties: Air Permeability, Gurley 112% Opacity, ISO 2471 111% Bulk, TAPPI T410 om-83 and T411 om-83 118% Tensile Strength, TAPPI T494 om-81 100% Tensile Stretch, TAPPI T494 om-81 85% Tear Strength, TAPPI T414 om-82 104% On balance, Fibers exhibited advantages in the important areas of higher permeability, opacity, bulk and 10 tear strength compared to the control at equivalent tensile strength with a small reduction in stretch. The cover advantage is important because less fiber can be used for a nonwoven fabric with similar performance characteristics, thereby saving materials cost. The 15 fabrics of Fiber Nalso have an attractive flannel-like hand.
When used with the appropriate water-dispersible coating in appropriate amount, the cruciform cross-section fiber of the invention has given a fabric with 20 surprisingly good dispersion uniformity, and the properties indicated.
From theoretical considerations, water-dispersible fibers of conventional round cross-section would have been expected to give more uniform dispersions, and, therefore, 25 more uniform wet-laid fabrics. This is because the surface energy required to disperse a fiber (or other articles) is given by: Energy - (Surface Tension) X (Dispersed surface area - Undispersed surface area). 30 The undispersed fiber exists in logs or clumps of many hundreds of fibers, most of which are on the inside of the logs. Therefore the undispersed surface area is negligible compared to the dispersed area, and the energy term can be expressed approximately as: Energy » (Surface Tension) X (Number of fibers) X (Surface area of a fiber).
This energy term describes both the energy required to disperse the fiber, and the free energy 5 driving force for reagglomeration. Therefore, for any given coating, and fiber dpf, fibers with lower area would be expected to provide a more uniform dispersion, hence more uniform fabric. The minimum surface area per unit weight for a given fiber occurs when the cross-section is 10 round, which would be expected, therefore, to be preferred.
Surprisingly, however, these cruciform fibers, in spite of about 60% greater surface area gave more uniform fabrics. Without limiting the invention to any theory, 15 this may result from the fiber's hydrodynamic shape, Which may more effectively use the energy available in the mixer shear field. ^ V V \ 4 s - 12 "

Claims (16)

1. A synthetic polymer fiber rendered water-dispersible by a coating promoting water-dispersibility, wherein the fibers are of cruciform cross-section. ^ 5
2. A water-dispersible fiber as claimed in claim 1, of cut length from 5 to 90 mm, and wherein the length/diameter ratio is from 100:1 to 2000:1.
3. A water-dispersible fiber as claimed in claims 1 or 2, wherein the denier is from 0.5 to 20. 10
4. A water-dispersible fiber as claimed in any of claims 1 to 3, in the form of a package of cut fiber.
5. Polymer fibers of claim 1, in the form of a continuous filamentary uncrimped tow.
6. A fiber as claimed in any of preceding claims, 15 wherein the synthetic polymer is polyester.
7. A polyester fiber according to claim 6, consisting essentially of poly(ethylene terephthalate).
8. A polyester fiber as claimed in claim 7, wherein the fiber is an essentially uncrimped poly(ethylene 20 terephthalate) fiber, of cut length 5 to 90 mm, of length/diameter ratio 100:1 to 2000:1, and of denier 0.5 *;to 20, and an ethoxylated water-dispersing coating is t present in amount 0.04 to 1.0% of the total weight of the fiber.;25
9. A polyester fiber according to claim 7, coated with a;- 1-3 -;water-dispersing coating consisting essentially of a segmented copolyester of poly(ethylene terephthalate);repeat units and poly(oxyalkylene) groups derived from a poly(oxyalkylene) glycol having an average molecular 5 weight in the range of 300 to 6,000. f;
10. A process for preparing polyester fiber rendered water-dispersible by a coating promoting water-dispersibility, by melt-spinning the polyester into filaments, drawing the tow and cutting the filaments,;10 wherein the polyester is spun into filaments of cruciform cross-section, the filaments are coated with a segmented synthetic copolyester of poly(ethylene terephthalate);repeat units and poly(oxyalkylene) groups derived from a poly(oxyalkylene) glycol having an average molecular 15 weight in the range of 300 to 6,000, and cut to fibers pf cut length from 5 to 90 mm.;
11. A process as claimed in claim 10, wherein the filaments are coated with the copolyester in amount 0.04 to 1.0% of their weight.;20
12. A process as claimed in claims 10 or 11, wherein the coating is cured on the filaments by heating the coated filaments to a temperature of 100°C to 190°C. * I
13. A process for preparing water-dispersible polyester fiber substantially as described with reference to the 25 Example. - 14 -
14. Water-dispersible polyester fibers whenever prepared by a process as claimed in any one of claims 10 to 13.
15. Water-dispersible synthetic polymer fibers •<4 substantially as described with reference to and as shown ) 5 in Figure 1 of the accompanying drawings.
16. Apparatus for producing water-dispersible synthetic polymer fibers substantially as described with reference to and as shown in Figure 2 of the accompanying drawings. MACLACHLAN & DONALDSON Applicants1 Agents 47 Merrion Square DUBLIN 2 t I 4
IE905/86A 1985-04-09 1986-04-08 New water-dispersible synthetic fiber IE57359B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US72134685A 1985-04-09 1985-04-09

Publications (2)

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IE860905L true IE860905L (en) 1986-10-09
IE57359B1 IE57359B1 (en) 1992-08-12

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IE905/86A IE57359B1 (en) 1985-04-09 1986-04-08 New water-dispersible synthetic fiber

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EP (1) EP0198401B1 (en)
JP (1) JPS62502484A (en)
KR (1) KR880002441B1 (en)
CN (1) CN1005734B (en)
AT (1) ATE44787T1 (en)
CA (1) CA1280266C (en)
DE (1) DE3664503D1 (en)
ES (1) ES8800998A1 (en)
FI (1) FI80078C (en)
IE (1) IE57359B1 (en)
WO (1) WO1986006112A1 (en)

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US4731239A (en) * 1983-01-10 1988-03-15 Gordon Robert T Method for enhancing NMR imaging; and diagnostic use
US5057368A (en) * 1989-12-21 1991-10-15 Allied-Signal Filaments having trilobal or quadrilobal cross-sections
JP3056862B2 (en) * 1991-12-27 2000-06-26 日産自動車株式会社 New sound absorbing material
US6250948B1 (en) * 2000-01-31 2001-06-26 Avava Technology Corp. Cylindrical front access connector
CN100462492C (en) * 2006-01-20 2009-02-18 泉州海天轻纺有限公司 Textile with ultraviolet resistant , hygroscopic and perspiratory function, and its preparation method
JP2017145527A (en) * 2016-02-17 2017-08-24 日本製紙株式会社 Wall paper

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US2945739A (en) 1955-06-23 1960-07-19 Du Pont Process of melt spinning
US3156085A (en) * 1959-09-24 1964-11-10 Du Pont Continuous composite polyester filament yarn
GB958350A (en) 1963-02-18 1964-05-21 Ass Elect Ind Improvements in and relating to electric incandescent lamps
GB1088984A (en) 1963-06-05 1967-10-25 Ici Ltd Modifying treatment of shaped articles derived from polyesters
DE1635684A1 (en) * 1963-07-24 1969-10-16 Glanzstoff Ag Process for the production of textile surface structures with a felt-like character
US3249669A (en) 1964-03-16 1966-05-03 Du Pont Process for making composite polyester filaments
US3625754A (en) * 1970-02-02 1971-12-07 Beaunit Corp Surface-modified polyester article
US3702260A (en) * 1971-01-18 1972-11-07 Beaunit Corp Coated polyester fiberfill
DE2105681C3 (en) * 1971-02-08 1975-10-02 Bayer Ag, 5090 Leverkusen Process for the production of aqueous fiber suspensions
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US4294883A (en) 1976-08-19 1981-10-13 Hoechst Fibers Industries, Div. Of American Hoechst Corporation Staple fiber, finish therefor and process for use of same
US4179543A (en) 1976-08-19 1979-12-18 Hoechst Fibers Industries, Division Of American Hoechst Corporation Staple fiber, finish therefor and process for use of same
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JPS5685436A (en) * 1979-12-12 1981-07-11 Toray Industries Synthetic staple fiber mixture having animal wool like feeling and animal wool like yarn
JPS5881609A (en) * 1981-11-04 1983-05-17 Nippon Ester Co Ltd Melt spinning method of ultrafine modified cross section yarn

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Publication number Publication date
ES553822A0 (en) 1987-12-01
CN86102459A (en) 1986-10-08
CN1005734B (en) 1989-11-08
KR880700116A (en) 1988-02-15
DE3664503D1 (en) 1989-08-24
EP0198401A1 (en) 1986-10-22
FI864687A (en) 1986-11-18
ES8800998A1 (en) 1987-12-01
FI80078B (en) 1989-12-29
FI80078C (en) 1990-04-10
ATE44787T1 (en) 1989-08-15
JPS62502484A (en) 1987-09-24
IE57359B1 (en) 1992-08-12
JPH0331804B2 (en) 1991-05-08
FI864687A0 (en) 1986-11-18
CA1280266C (en) 1991-02-19
KR880002441B1 (en) 1988-11-12
EP0198401B1 (en) 1989-07-19
WO1986006112A1 (en) 1986-10-23

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