EP0598536B1 - Fibres fortes discontinues de polyéthylène - Google Patents

Fibres fortes discontinues de polyéthylène Download PDF

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Publication number
EP0598536B1
EP0598536B1 EP19930308917 EP93308917A EP0598536B1 EP 0598536 B1 EP0598536 B1 EP 0598536B1 EP 19930308917 EP19930308917 EP 19930308917 EP 93308917 A EP93308917 A EP 93308917A EP 0598536 B1 EP0598536 B1 EP 0598536B1
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EP
European Patent Office
Prior art keywords
fibres
polyethylene
less
pulp
fibre
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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 - Lifetime
Application number
EP19930308917
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German (de)
English (en)
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EP0598536A2 (fr
EP0598536A3 (en
Inventor
Sylvie Cloutier
Lynne Marie Manuel
Vaclav George Zboril
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DuPont Canada Inc
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DuPont Canada Inc
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Publication date
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Publication of EP0598536A3 publication Critical patent/EP0598536A3/en
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Publication of EP0598536B1 publication Critical patent/EP0598536B1/fr
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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/11—Flash-spinning
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent

Definitions

  • the present invention relates to strong as-spun discontinuous polyethylene fibres, especially strong discontinuous plexifilamentary film-fibril strands formed directly from fibre-forming polyethylene.
  • Such as-spun discontinuous fibres may be formed in a flash spinning process.
  • discontinuous means that the strands have a length of not more than 100 mm.
  • duplexifilamentary film-fibril strands of polyethylene means strands which are characterized as a three dimensional integral network of a multitude of thin, ribbon-like film-like elements of random length and of a thickness in the range of about 1-20 ⁇ m, with an average thickness of less than about 10 ⁇ m, generally coextensively aligned with the longitudinal axis of the strand.
  • the film-fibril elements intermittently unite and separate at irregular intervals in various places throughout the length, width and thickness of the strand to form the three dimensional network.
  • Such strands are known, being described in further detail in Blades and White, US-A-3 081 519.
  • Blades and White describe a flash-spinning process for producing continuous plexifilamentary film-fibril strands from fibre-forming polymers.
  • a solution of polymer in a liquid that is a non-solvent for the polymer at or below its normal boiling point is extruded at a temperature above the normal boiling point of the liquid and at autogenous or higher pressure through a spinneret into a medium of lower temperature and substantially lower pressure.
  • This flash spinning causes the liquid to vaporize and form a continuous plexifilamentary film-fibril strand.
  • US-A-5 043 108 discloses flash spinning of a mixture of organic solvent, polyethylene and a non-solvent or spin aid, especially water or an alcohol, or mixtures thereof, in which the amount of water is less than the saturation limit of water in the organic solvent, to produce continuous as-spun fibres.
  • a process for the manufacture of a polyolefin pulp in which strands are formed and shredded is disclosed in US-A-5 093 060.
  • mechanical shredding tends to fuse the ends of the shredded filaments, even if the shredding is carried out under water. Fused ends make it difficult or impossible to open up the resultant web of fibres, as well as reducing fibre orientation and strength. For these reasons, processes that produce discontinuous fibres without requiring use of mechanical shredding means would be preferred.
  • the present invention provides fine, strong, as-spun discontinuous fibres formed from polyethylene, said fibres having a length of 1-25 mm, a fibre diameter of less than 30 ⁇ m and a handsheet zero span strength of greater than 29.4 N/15 mm (3 kg/15 mm).
  • the handsheet zero span strength is greater than 58.8 N/15 mm (6 kg/15 mm).
  • the present invention also provides a polyethylene pulp formed from as-spun discontinuous fibres having a surface area of greater than 4 m 2 /g, a Pulmac defect value of less than 3%, a handsheet zero span value of at least 29.4 N/15 mm (3 kg/15 mm) and with the fibres of the pulp having a Kajaani coarseness of less than 0.30 mg/m.
  • the pulp has a Pulmac defect value of less than 2%.
  • the fibre length in the pulp is less than 2 mm and with an average length in the range of 0.80-1.20 mm.
  • the fibres have a fineness such that the fibres have a Kajaani coarseness of less than 0.20 mg/m.
  • the pulp has a surface area in the range of 6-8 m 2 /g.
  • the polyethylene has a melt index of less than 15 dg/min, especially less than 7 dg/min and in particular less than 2 dg/min.
  • the fibre is in the form of plexifilamentary film-fibrils in a discontinuous form.
  • the average length of the fibre is in the range of 1-25 mm.
  • the fibres of the present invention have a handsheet zero span strength of greater than 29.4 N/15 mm (3 kg/15 mm) and especially greater than 58.8 N/15 mm (6 kg/15 mm).
  • the diameter of the fibre is less than 30 ⁇ m and more particularly less than 20 ⁇ m.
  • the fibres are referred to as "as-spun" fibres, which have "free” ends in contrast to the fused ends that tend to result from mechanical cutting of polyethylene fibres, especially at commercial rates.
  • the as-spun fibres are characterized by an absence of fused ends. This freeness of the fibres contributes to improved processing of the fibres, which usually includes a step of opening up of the fibres or separation of fibre bundles into individual fibres.
  • the fibres of the present invention are short fibres, in comparison to the fibres produced in the aforementioned Blades and White and Samuels processes.
  • the fibres of the present invention may be manufactured in a flash spinning process, particular examples of which are described in the aforementioned copending European patent application.
  • polyolefin is dissolved in an organic solvent.
  • the polyolefin may be in the form of pellets or powder, or other forms known in the art, having been previously polymerized from monomers.
  • the polyolefin is already dissolved in an organic solvent e.g. it is a solution of polymer in organic solvent from a process for the polymerization of monomers.
  • the polyethylene used in the present invention may be a high molecular weight homopolymer of ethylene or copolymer of ethylene and at least one C 4 -C 10 hydrocarbon alpha-olefin e.g. butene-1, hexene-1 and/or octene-1.
  • C 4 -C 10 hydrocarbon alpha-olefin e.g. butene-1, hexene-1 and/or octene-1.
  • a wide variety of such polymers, including by type of monomer(s) used, molecular weight, molecular weight distribution and other properties are commercially available.
  • the density is in the range of 0.930 to 0.965 g/cm 3 , especially in the range of 0.940 to 0.960 g/cm 3 .
  • the melt index of the polyolefin is preferably less than 15 dg/min i.e. in the range of from so-called "no-flow" e.g. less than about 0.01 dg/min, to 15 dg/min, especially in the range of 0.50 to 7.0 dg/min; melt index is measured by the method of ASTM D-1238 (condition E).
  • organic solvents may be used in the process, examples of which include pentane, hexane, cyclohexane, heptane, octane, methyl cyclohexane and hydrogenated naphtha, and related hydrocarbon solvents, and mixtures of solvents.
  • the polyethylene may contain additives e.g. antioxidants, ultra violet stabilizers, wetting agents, surfactants and other additives known for use in polyolefins, provided that the additives are capable of passing through the orifice used in the process and not otherwise adversely affecting the process.
  • additives e.g. antioxidants, ultra violet stabilizers, wetting agents, surfactants and other additives known for use in polyolefins, provided that the additives are capable of passing through the orifice used in the process and not otherwise adversely affecting the process.
  • the solution of polyethylene in organic solvent is at an elevated temperature and pressure, the solution being at a pressure that is at least the autogenous pressure and at a temperature sufficient to maintain the polyolefin in solution.
  • the solution also contains a non-solvent e.g. water, as a spinning aid, as described in the aforementioned patent of Samuels.
  • the spinning aid may contain wetting agents, surfactants or the like.
  • the temperature and pressure used, and the composition of the solution especially the percent of polymer in the solution, affect the properties of the film-fibril strands obtained on spinning and consequently the fibrous material subsequently formed in the process. For instance, the temperature, pressure and solution composition may be selected so that highly oriented fibres are obtained, such fibres being preferred.
  • the solution is fed through a feed section to a spinneret exit to form plexifilamentary film-fibril strands, the strands being formed as the polymer solution passes from the spinneret exit.
  • a mixture of steam and water is contacted with the solution passing from spinneret exit substantially simultaneously with the passage of the solution from the spinneret exit.
  • the mixture of steam and water may be fed as a stream to the tunnel or, preferably, a stream of hot high pressure water is flashed through an orifice into the tunnel, where the mixture of steam and water is formed.
  • the temperature and pressure of the stream are selected so as to produce the required ratio of steam to water in the tunnel.
  • the ratio of steam to water is in the range of 20:80 to 80:20 on a weight basis, especially in the range of 35:65 to 65:35.
  • the temperature of the inert fluid is 2-40°C lower than the melting point of the polymer.
  • the fibre may be converted to a polyethylene pulp, which has a variety of uses.
  • the pulp may be used as part of blends with cellulose for use in e.g. diapers, disposable wipes, feminine hygiene products and incontinence products, as a filler e.g. in polymers, cement and the like, thixotropic agent in paints and as synthetic paper.
  • fibres especially longer fibres with lengths in the range of about 5-25 mm may be used, without refining, to produce sheet structures using either wet-lay or air-lay sheet forming technologies.
  • Pulp may be obtained by feeding the fibres to a refining process that reduces the length of the fibres to less than 2 mm and with an average length in the range of 0.80-1.20 mm as well as opening up the fibre structure.
  • the fibres are fed to the refiner in the form of a slurry e.g. about 2% by weight, with polyvinyl alcohol added as surfactant; other surfactants may be used in combination with or instead of polyvinyl alcohol.
  • the fibres must be of a length of not more than about 10 mm, preferably with an average length of about 6 mm in order to produce an acceptable slurry.
  • the refining process may be carried out in a pulp and paper-type refiner. Suitable refiners include single disk, twin-flow and conical refiners.
  • Synthetic pulp is synthetic fibre having a very short length.
  • the fibre in the pulp preferably has an length of less than 2 mm, an average length in the range of 0.8-1.2 mm, and preferably about 1 mm.
  • the fibre in the pulp has a surface area of greater than 4 m 2 /g, especially than 6 m 2 /g and in particular in the range of 6-8 m 2 /g.
  • Pulp fibres have a handsheet zero span value of at least 29.4 N/15 mm (3 kg/15 mm), especially at least 49 N/15 mm (5 kg/15 mm). In use, it is preferred that the pulp have a low percentage of long fibres and a low percentage of agglomerates.
  • Fineness of the fibres may be characterized using, a coarseness test viz. the Kajaani test. As used herein "fine fibres" have a coarseness of less than 0.3 mg/m and preferably less than 0.2 mg/m.
  • Fibrous material was manufactured using semi-works scale apparatus equipped with a spinneret and die having a venturi tunnel, such a tunnel being shown in Fig. 1 of the aforementioned EP-A-0 597 658.
  • the solution of polymer fed to the spinneret was a solution of ethylene/butene-1 copolymer dissolved in cyclohexane and containing 7% (w/w) of water as a spin aid. Water was introduced at high temperature and pressure into the zone immediately adjacent the spinneret so that a mixture of steam and water contacted the fibres exiting from the spinneret.
  • the product was in the form of a slurry of fibres in water at a 0.5% consistency (w/w).
  • the fibre slurry was conveyed, using a water-driven venturi, through a large smooth pipe to a vessel where live steam was injected to boil off residual traces of cyclohexane.
  • the slurry, free of solvent, was further conveyed, using a water-driven venturi, through a large smooth pipe to a belt filter press where water was removed.
  • the product was collected in the form of a loose cake with an approximately 50% solids content.
  • polymers of low melt index i.e. high molecular weight
  • the fibres were all strongly oriented, with linear shrinkages slightly above 10.
  • Fibre length was in the range of 18-25 mm for Runs 1 and 2, in which the melt index was 0.28 and 0.33 dg/min respectively.
  • the polymer melt index was higher viz. 0.43 dg/min
  • the fibre length was shorter, generally below 10 mm.
  • Handsheet zero span strength was 61.7 N/15 mm (6.3 kg/15 mm) at a polymer density of 0.937 g/cm 3 (Run 1), 79.4 N/15 mm (8.1 kg/15 mm) at a polymer density of 0.942 g/cm 3 (Run 2) and 81.9 N/15 mm (9.0 kg/15 mm) at a polymer density of 0.958 g/cm 3 (Run 3).
  • the fibres of this example were strong and discontinuous, with combinations of the unique properties described herein.
  • Example I The procedure of Example I was repeated using polymers of differing melt index. Polymers having a melt indices in the range of 0.79 to 7.6 dg/min were spun into fibres.
  • Polymer melt index (or polymer molecular weight) had an effect on both the fibre length and fibre strength. All the fibres were strong and discontinuous, with the unique combination of properties described herein.
  • the individual fibres lengths ranged from 2 to 8 mm. In contrast, for the polymer of highest melt index (7.6 dg/min, in Run 8), the individual fibre lengths ranged from 1 to 3 mm. Fibres with the lengths reported in this Example are short enough to be dispersed into a slurry in a well agitated vessel, preferably a pulper, and refined to pulp length. In contrast, some of the fibres obtained in Example 1 had lengths of up to 25 mm, which would be expected to cause entanglement problems in a pulping and refining process.
  • Polymers with lower melt index give fibres with higher strength, as measured by handsheet zero span, than fibres with higher melt index.
  • the polymer with a melt index of 0.79 dg/min had a handsheet zero span of 83.3 N/15 mm (8.5 kg/15 mm) (Run 4), whereas the polymer with a melt index of 7.6 dg/min had a handsheet zero span of less than half that value (Run 8).
  • the polymer had the same density and a melt index of 0.42 dg/min; the handsheet zero span was 89.8 N/15 mm (9.0 kg/15 mm).
  • Example I The procedure of Example I was repeated, with the fibres obtained being refined to a pulp length viz. approximately 1 mm.
  • Refining was conducted by first dispersing the fibres in water in an agitated tank, at a fibre consistency of 1.5-2%.
  • a surfactant polyvinyl alcohol, 2% by weight of fibres
  • Two different single disk refiners were used, with a 30 cm plate diameter in Runs 9 and 10 and with a one metre plate diameter in Run 11.
  • the plate gap setting was between 0.05 and 0.15 mm, with the larger gap settings being used on the smaller refiner.
  • the samples were refined until the average fibre length was 1 mm.
  • This Example compares the properties of refined fibres (pulp) to the unrefined fibres. Most applications of the fibres are expected to be in the form of pulp. In addition, certain fibre properties cannot be measured on unrefined fibres.
  • the fibre samples were obtained by spinning high density polymers with varying melt indices viz. from 0.78 to 7.5 dg/min.
  • the handsheet zero span for unrefined fibres was 73.5 N/15 mm (7.5 kg/15 mm) and the individual fibre lengths ranged between 6 and 12 mm.
  • the handsheet zero span was 35.3 N/15 mm (3.6 kg/15 mm) and the individual fibres lengths ranged between 1 and 3 mm.
  • the fibres were refined to an average length of 1 mm viz. 0.97 mm for Run 9, 1.02 mm for Run 10 and 0.98 mm for Run 11.
  • the Pulmac defect test which measures long fibres and agglomerates, gave results of less than 2% for the fibres of all three runs.
  • the Clark 14 mesh test which measures the proportion of long fibres, was also less than 2% for all three runs.
  • Fibre strength as measured by the handsheet zero span test was lower for the refined fibres than for the unrefined fibres.
  • the handsheet zero span decreased from 73.5 N/15 mm (7.5 kg/15) mm before refining to 55.9 N/15 mm (5.7 kg/15 mm) after refining.
  • the decrease was from 35.3 to 30.4 N/15 mm (3.6 to 3.1 kg/15 mm). Nonetheless, fibre strength was still acceptable.
  • Fibre size and surface area are typically measured only on refined fibres, because refining opens up the fibre structure.
  • Average fibre coarseness as measured by the Kajaani method increased with increasing melt index, from 0.171 mg/m in Run 9 to 0.260 in Run 11. This shows that finer, more oriented fibres may be obtained with lower melt index polymers.
  • Surface area measured by nitrogen adsorption was between 6 and 7 m 2 /g for all three runs.

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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)
  • Artificial Filaments (AREA)
  • Paper (AREA)
  • Nonwoven Fabrics (AREA)
  • Laminated Bodies (AREA)

Claims (19)

  1. Fibres fines, résistantes, discontinues telles que filées formées de polyéthylène, lesdites fibres ayant une longueur de 1-25 mm, un diamètre de la fibre de moins de 30 microns et une résistance à écartement zéro d'une feuille d'une main de plus de 29,4 N/15 mm (3 kg/15 mm) en utilisant le processus de TAPPI 205 om.
  2. Les fibres de la revendication 1 dans lesquelles la résistance à l'écartement zéro d'une feuille d'une main est plus grande que 58,8 (N/15 mn) (6 kg/15 mn).
  3. Les fibres de la revendication 1 ou de la revendication 2 dans lesquelles le polyéthylène a un indice de fusion de moins de 15 dg/mn.
  4. Les fibres de la revendication 3 dans lesquelles l'indice de fusion polyéthylène est inférieur à 7 dg/mn.
  5. Les fibres de la revendication 3 dans lesquelles l'indice de fusion du polyéthylène est inférieur à 2 dg/mn.
  6. Les fibres selon l'une quelconque des revendications 1-5 dans lesquelles le polyéthylène est un homopolymère de fort poids moléculaire d'éthylène ou un copolymère d'éthylène et d'au moins une hydrocarbure d'alpha-oléfine C4-C10.
  7. Les fibres de la revendication 6 dans lesquelles le polyéthylène est un copolymère et l'alpha-oléfine est sélectionnée parmi le butène-1, l'hexène-1 et l'octène-1, et leurs mélanges.
  8. Les fibres de la revendication 6 dans lesquelles la densité du polyéthylène est comprise entre 0,930 et 0,965 g/cm3.
  9. Les fibres de la revendication 8 dans lesquelles l'indice de fusion de la polyoléfine est inférieur à 15 dg/mn.
  10. Une pâte de polyéthylène formée de fibres selon l'une quelconque des revendications 1 à 9, les fibres dans la pâte ayant une aire superficielle de plus de 4 m2/g, une valeur de défaut Pulmac de moins de 3%, une valeur à écartement zéro d'une feuille d'une main de 29,4 N/15 mn (3 kg/15 mn) en utilisant le processus de TAPPI 205 om et avec les fibres de la pâte ayant une rugosité de Kajaani de moins de 0,30 mg/m.
  11. Pâte de polyéthylène de la revendication 10 dans laquelle la valeur du défaut Pulmac est inférieure à 2%.
  12. Pâte de polyéthylène de la revendication 10 ou de la revendication 11 dans laquelle la longueur de la fibre est inférieure à 2 mm et avec une longueur moyenne comprise entre 0,80 et 1,20 mm.
  13. Pâte de polyéthylène selon l'une quelconque des revendications 10-12 dans laquelle la pâte a une aire superficielle comprise entre 6 et 8 m2/g.
  14. Pâte de polyéthylène selon l'une quelconque des revendications 10-13 dans laquelle les fibres ont une finesse telle que les fibres ont une rugosité de Kajaani de moins de 0,20 mg/m.
  15. Feuille de polyéthylène formée de la pâte selon l'une quelconque des revendications 10 à 14.
  16. Feuille de polyéthylène formée de fibres fortes discontinues selon l'une quelconque des revendications 1-9.
  17. Feuille de la revendication 16 dans laquelle les fibres ont des longueurs comprises entre 5 et 25 mm.
  18. Feuille de la revendication 16 ou de la revendication 17 qui est une feuille mise à plat à l'air.
  19. Feuille de la revendication 16 ou de la revendication 17 qui est une feuille mise à plat à l'état humide.
EP19930308917 1992-11-10 1993-11-09 Fibres fortes discontinues de polyéthylène Expired - Lifetime EP0598536B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9223562 1992-11-10
GB929223562A GB9223562D0 (en) 1992-11-10 1992-11-10 Strong discontinuous polyethylene fibres

Publications (3)

Publication Number Publication Date
EP0598536A2 EP0598536A2 (fr) 1994-05-25
EP0598536A3 EP0598536A3 (en) 1994-09-14
EP0598536B1 true EP0598536B1 (fr) 1998-06-24

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EP19930308917 Expired - Lifetime EP0598536B1 (fr) 1992-11-10 1993-11-09 Fibres fortes discontinues de polyéthylène

Country Status (6)

Country Link
EP (1) EP0598536B1 (fr)
JP (1) JPH06212512A (fr)
CA (1) CA2102568C (fr)
DE (1) DE69319306T2 (fr)
ES (1) ES2119865T3 (fr)
GB (1) GB9223562D0 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10252200B2 (en) 2016-02-17 2019-04-09 Hollingsworth & Vose Company Filter media including a filtration layer comprising synthetic fibers
US11014030B2 (en) 2016-02-17 2021-05-25 Hollingsworth & Vose Company Filter media including flame retardant fibers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9313352D0 (en) * 1993-06-29 1993-08-11 Du Pont Canada Absorbent structure of blends of cellulosic and polyethylene plup
JP2008266832A (ja) * 2007-04-20 2008-11-06 Mitsui Chemicals Inc 繊維、それを含む圧着シール用シート及び圧着シート
WO2020234090A1 (fr) * 2019-05-23 2020-11-26 Oerlikon Textile Gmbh & Co. Kg Procédé de filage à chaud et dispositif de filage à chaud pour la fabrication de fibres discontinues synthétiques

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3081519A (en) * 1962-01-31 1963-03-19 Fibrillated strand
CA1255065A (fr) * 1984-02-17 1989-06-06 Lawrence H. Sawyer Fibres de polymere d'olefine
US5043108A (en) * 1989-08-22 1991-08-27 E. I. Du Pont De Nemours And Company Process for preparing polyethylene plexifilamentary film-fibril strands
US5093060A (en) * 1991-02-25 1992-03-03 E. I. Du Pont De Nemours And Company Coupled spinning and dewatering process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10252200B2 (en) 2016-02-17 2019-04-09 Hollingsworth & Vose Company Filter media including a filtration layer comprising synthetic fibers
US11014030B2 (en) 2016-02-17 2021-05-25 Hollingsworth & Vose Company Filter media including flame retardant fibers
US11123668B2 (en) 2016-02-17 2021-09-21 Hollingsworth & Vose Company Filter media including a filtration layer comprising synthetic fibers
US11738295B2 (en) 2016-02-17 2023-08-29 Hollingsworth & Vose Company Filter media including flame retardant fibers

Also Published As

Publication number Publication date
EP0598536A2 (fr) 1994-05-25
EP0598536A3 (en) 1994-09-14
DE69319306D1 (de) 1998-07-30
CA2102568A1 (fr) 1994-05-11
DE69319306T2 (de) 1998-12-24
ES2119865T3 (es) 1998-10-16
JPH06212512A (ja) 1994-08-02
CA2102568C (fr) 2003-10-14
GB9223562D0 (en) 1992-12-23

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