WO1998011282A1 - Meltblown ionomer microfibers and non-woven webs made therefrom for gas filters - Google Patents

Meltblown ionomer microfibers and non-woven webs made therefrom for gas filters Download PDF

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Publication number
WO1998011282A1
WO1998011282A1 PCT/US1997/015641 US9715641W WO9811282A1 WO 1998011282 A1 WO1998011282 A1 WO 1998011282A1 US 9715641 W US9715641 W US 9715641W WO 9811282 A1 WO9811282 A1 WO 9811282A1
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WO
WIPO (PCT)
Prior art keywords
microfibers
web
meth
ionomer
filter
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.)
Ceased
Application number
PCT/US1997/015641
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English (en)
French (fr)
Inventor
Richard Tien-Hua Chou
Patrick Stephen Ireland
Charles John Molnar
Hyun Sung Lim
Hyunkook Shin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
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EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to EP97939814A priority Critical patent/EP0925390B1/en
Priority to DE69704366T priority patent/DE69704366T2/de
Priority to JP10513711A priority patent/JP2001500201A/ja
Priority to CA002264948A priority patent/CA2264948A1/en
Publication of WO1998011282A1 publication Critical patent/WO1998011282A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/16Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B01D39/163Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin sintered or bonded
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/098Melt spinning methods with simultaneous stretching
    • D01D5/0985Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30Monocomponent 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
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282Addition polymers
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282Addition polymers
    • D04H1/4291Olefin series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825Composite fibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838Ultrafine fibres, e.g. microfibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/0216Bicomponent or multicomponent fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604Arrangement of the fibres in the filtering material
    • B01D2239/0622Melt-blown
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604Arrangement of the fibres in the filtering material
    • B01D2239/0627Spun-bonded
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/0604Arrangement of the fibres in the filtering material
    • B01D2239/064The fibres being mixed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/06Filter cloth, e.g. knitted, woven non-woven; self-supported material
    • B01D2239/065More than one layer present in the filtering material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12Special parameters characterising the filtering material
    • B01D2239/1233Fibre diameter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/12Special parameters characterising the filtering material
    • B01D2239/1291Other parameters
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/903Microfiber, less than 100 micron diameter
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S55/00Gas separation
    • Y10S55/45Woven filter mediums
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904Staple length fiber
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2929Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2964Artificial fiber or filament
    • Y10T428/2967Synthetic resin or polymer

Definitions

  • the invention relates to microfibers made from ethylene/carboxylic acid ionomers, the fibers being meltspun, particularly using the 'meltblown' process.
  • the microfibers in the form of a web material can be efficient gas filters without being electretized.
  • the materials, however, may also be electretized.
  • Non-woven materials are well known and widely used in a variety of applications including apparel, adhesives. sorbents and filters. These materials are made from matted, entangled non-bonded, but also melt-bonded fibers. When the matting is very tight, the non- woven material may be thought of as fabric-like. Such non-wovens may be useful, for instance, for apparel. When the matting is relatively loose and open it may considered, and is often referred to as, a 'web'. The form of a web may be thick or thin and the fibers entangled and/or bonded with varying degrees of openness, and with variations in the degree of bonding.
  • non-woven materials vary widely, from tough to relatively weak, flexible to stiff, highly porous to having low porosity, with highly absorptive or less absorptive capacity, yet may even have barrier characteristics, especially to liquids.
  • the nature of non-wovens depends on (i) what material is used to make the fibers (ii) the nature of the fibers - which will depend on the process used to make them, and (iii) how the fibers are bonded together. It may be fair to say that the variation in the type and applications of non-wovens is as great or greater than that of woven materials.
  • a major market for non-wovens is in the filtration market, for gases and liquids.
  • Gas filtration involves removing particulate matter, usually solid such as dust, but also liquid particles, from a gas, particularly air.
  • Typical markets include heating ventilating and air conditioning (HVAC).
  • HVAC heating ventilating and air conditioning
  • Demanding markets such as pharmaceuticals, microelectronics and biotechnology use highly efficient or ultra efficient particulate air filters (HEPA and UFPA).
  • HEPA and UFPA highly efficient or ultra efficient particulate air filters
  • the filter may require high flux (i.e., high gas throughput) requiring high permeability, and/or require a high level of particle removal, and/or require removal of specific size particles.
  • flux often quantified and measured in terms of the 'pressure drop' across the web, and the 'filtration efficiency' are conjugate quantities.
  • the 'architecture' of a filter web depends on the fiber diameters, and the distribution of the diameters, how the fibers are entangled/bonded together, the density of web, its uniformity, and the thickness and weight per unit area. These architectural features are a major factor in filter efficiency, the flux, and the size particles which they remove. To filter out small particles, it is necessary to have fine fibers and small passages throughout the web, with no large channels (somewhat comparable to a finer mesh in a woven filter). Webs made of 'microfibers' as opposed to fibers of the size of normal textile fibers are used for filtering fine particles in the 0.1 to about 20 micron region.
  • Microfibers of synthetic thermoplastic polymers are commonly meltspun, particularly by a process known as the 'meltblown' process, though certain other processes can produce microfibers such as fibrillating film.
  • the meltblown process has been succinctly defined as 'a one-step process in which high- velocity air blows a molten thermoplastic resin from an extruder die tip, onto a conveyor or take-up screen, to form a fine-fibered self-bonding web'.
  • a meltblowing apparatus suitable for the production of microfibers was described in Report No. 4364 of the Naval Research Laboratories, published May 25, 1954, entitled 'Manufacture of Super Fine Organic Fibers', by Van Wente et al.
  • microfibers from synthetic polymers, and the nature of the resulting web produced in the meltblown process depends on the melt rheological and crystallizing or, more generally, solidifying. characteristics of the polymer.
  • Other technologies that, in a broader sense, could be considered meltblown, or more generally meltspun processes, and can produce microfibers include electrostatic melt-spinning, flash spinning and centrifugal spinning.
  • the appropriate web architecture is a necessary factor but may not be the only factor in determining efficiency.
  • Another major factor is the electrostatic nature of the surface of the polymer fibers. This is significantly dependent on the chemical nature of the polymer composition, the molecular conformation within the fiber, and the surface nature of the fibers made from it.
  • filter microfibers are subjected to a surface treatment to increase their electrostatic charge or polar nature. So-called 'insulating' polymers, those with high resistivity, are 'electretized' which is sometimes said to mean 'electrified to possess permanent dielectric polarization' or 'electrified to make an electret' or to possess an 'electret surface'.
  • a deliberately produced electret surface on filter web microfibers may be produced at different stages of forming the filter.
  • a material may be treated even before fiber formation, such as a sheet before fibrillation. Fibers may be treated during or after their formation, or the treatment may be carried out during or after the actual web formation Such treatment is conventionally done by a procedure involving rubbing or corona charge treatment.
  • Other techniques for providing electret enhancement are described in U.S. Patent No 4,375,718 (Wadsworth); No. 4,588,537 (Klaase) and No. 4,592,815 (Nakao).
  • electrets are often referred to as having a 'permanent dielectric polarization', which leads to or is associated with a surface charge, in fact to a greater or lesser degree, the electrostatic charge or permanence of surface polar nature, whatever its precise nature, decays with time.
  • the usefulness of electret enhanced filtering is of course dependent on how permanent the electret nature is, in relation to the time span for use of the filter.
  • Non-polar polymers such as polyethylene and polypropylene are indicated to produce stable electrets, but of relatively low electrostatic charging capacity, while polar polymers are indicated to have high initial electet capacity, but relatively rapid decay, particularly under humid conditions.
  • U.S. Pat. No. 4,789,504 discloses microfibers which are able to be more permanently electretized than prior art materials.
  • the materials used to make the fibers consist of polymers which include polypropylene, polyethylene, polyester, polyamide, poly( vinyl chloride), poly(methyl methacrylate) etc., containing 100 ppm or more, preferably 200 to 2000 ppm, in terms of the metal, of a fatty acid salt such as an aluminum, magnesium or zinc salts of palmitic, stearic or oleic acid.
  • Electretizing generally requires extra steps and use of special equipment after or during making of the fibers or webs. There is a need for materials which can be made into filter webs without the need to post-charge or deliberately electretize, yet which have comparable or better efficiency/flux. At the same time, if such materials can be electretized to produce filters with even greater efficiency, then the materials serve yet an added need.
  • the invention depends on the recognition that ethylene/carboxylic acid ionomers appear to be uniquely suitable for microfibers for filters, particularly since it is not necessary to deliberately post-charge or electretize the fibers or fiber webs, though they may additionally benefit from a deliberate electretizing process.
  • the fibers have high static retention of any existing or deliberate specifically induced static charge which makes them excellent gas filters either without electretizing, as well as with an electretizing step.
  • the invention comprises meltspun, particularly meltblown microfibers for filter webs the fibers made from a copolymer comprising: a copolymer of ethylene, 5 to 25 weight percent of (meth)acrylic acid, and optionally, though less preferably, up to 40 weight percent of an alkyl (meth)acrylate whose alkyl groups have from 1 to 8 carbon atoms, having from 5 to 70 percent of the acid groups neutralized with a metal ion, particularly zinc, sodium, lithium or magnesium ions, or mixtures of these, the copolymer having a melt index of from 5 to 1000 g/10 minutes.
  • a copolymer comprising: a copolymer of ethylene, 5 to 25 weight percent of (meth)acrylic acid, and optionally, though less preferably, up to 40 weight percent of an alkyl (meth)acrylate whose alkyl groups have from 1 to 8 carbon atoms, having from 5 to 70 percent of the acid groups neutralized with a metal ion, particularly zinc, sodium,
  • a further aspect of the invention are non-electretized filter webs made from the above fibers. Yet another aspect are electretized filter webs made from the above fibers. Yet a further aspect of the invention are microfibers and webs of those microfibers where the material used to make the fibers is a blend of the above ionomer and another polymer, where the ionomer is at least 10 weight percent of the blend composition.
  • copolymer means a 'direct' near- random copolymer, (as distinct from a graft copolymer) polymerized from two or more comonomers, and thus includes dipolymers, terpolymers etc.
  • Microfibers as the term is used in this application means fibers having an average diameter of less than about 30 microns.
  • the copolymers used to make the microfibers of this invention are ionomers. Many ionomers are well known commercially.
  • the ionomers of this invention are metal ion neutralized copolymers of ethylene with acrylic or methacrylic acid or both. The option of either or both of these acids will be designated by the shorthand term '(meth)acrylic acid'.
  • Ionomers of this type are sold under the tradename of Surlyn ® ionomer resins, by E. I. du Pont de Nemours and Company, as well as other companies.
  • the ionomer copolymers of the invention contain 5 to 25 weight percent, preferably 8 to 20 weight percent (meth)acrylic acid, most preferably 8 to 15 weight percent.
  • they may contain up to 40 weight percent of a 'softening' monomer which is an alkyl acrylate with a 1 to 8 carbon alkyl group.
  • the ionomer is a dipolymer with no softening monomer.
  • the carboxylic acid groups are partially neutralized; from 5 to 70 percent, preferably 25 to 60 percent of the acid groups being neutralized with metal ions, preferably of sodium, zinc, lithium or magnesium (or mixtures of these), most preferably sodium or zinc. Ions which produce more hydrophilic ionomers such as potassium are less preferred unless the degree of neutralization is at a relatively low level.
  • Non-neutralized acid copolymers are less suitable for making the microfibers of this invention.
  • Acid copolymers and their preparation are described in U.S. Patent No. 4,351 ,931 (Armitage), and ionomers and their preparation from acid copolymers are described in U.S. Patent No. 3,264,272 (Rees).
  • 'Soft' ionomers containing alkyl acrylates are described in U.S. Patent No. 4,690,981 (Statz).
  • Preparation of acid copolymers containing higher levels of acid are advantageously prepared by a modified method, referred to as 'cosolvent technology' which is described in U.S. Patent No. 5,028,674 (Hatch et al.). All four above patents are hereby incorporated by reference.
  • meltblowing apparatus suitable for preparation of the microfibers of the present invention is described in the Naval Research Laboratories Report 4364, discussed in the Related Art Section. Further descriptions of meltblowing apparatus also suitable for the present microfibers have been more recently given in the TAPPI Journal, 78, 185, 1995 by Sanjiv R. Malkan, and by L.C. Wadworth et al. in 'Melt Blown Technology Today', Miller Freeman, 1989.
  • the apparatus consists of an extruder, a metering pump, a die assembly and web formation and winding equipment.
  • the distinct feature is the die assembly, consisting of a polymer feed distribution system, a die nosepiece and air manifolds.
  • the air manifolds supply the high-velocity hot air at temperatures between about 400 and 600 °F through slots in the die nosepiece.
  • the high-velocity hot air streams attenuate (thin divide) the polymer streams to form microfibers.
  • the hot air stream containing the microfibers progresses towards a collector screen, it draws in a large amount of surrounding air that cools and solidifies the fibers.
  • the solidified fibers subsequently get laid randomly onto the collecting screen, forming a self-bonded non-woven web.
  • U.S. Patent 3,825,380 (Harding et al.) describes a die with specific nose configuration, for production of non-woven mat. This patent is also hereby incorporated by reference.
  • water jets are desirable to facilitate microfiber cooling, producing a more uniform web, without overly fused bond areas.
  • the microfibers of this invention have an average diameter in the range of 0.5 to 30 microns, preferably 0.5 to 10 microns and most preferably 1 to 5 microns. Fibers in the broad range, but preferably in the narrow range are of a suitable diameter for removing particles in the 0.1 to 20 micron size, the size of particle removed by the fiber webs of this invention.
  • Non- woven filter webs of this invention, produced from the microfibers, have a weight of between 0.5 and 10 ozJsquare yard, preferably between 0.7 and 3 oz./square yard. The web thickness should be between 5 and 30 mils.
  • microfiber filter webs of this invention may be used as part of a filter structure, and may be laminated with a layer of a different (generally spunbonded) web, or can be in the form of a three-layer sandwich in which the meltspun, particularly meltblown microfiber web forms the core, while the different spunbonded web forms the outer layer.
  • Spunbonded non-woven webs and its fibers of the type useful for such sandwich structures can be made by any convenient process, for example by melt-spinning the polymer as described in U.S. Patent Nos. 3,821,062 (Henderson), 3,563,838 (Edward) and 3,338,992
  • the different spunbonded web fibers of the sandwich should have a diameter of at least 20 microns and thus is considerably higher than the preferred microfiber diameter of 1 to 5 microns used for the core web.
  • the different spunbonded layer provides mechanical strength and integrity, while the core layer provides the desired microporosity and filter properties.
  • the filter webs need not be deliberately electretized to be highly efficient filters. That is not to say that the webs can not benefit further from a specific post-charging/electretizing step. In brief preliminary experiments discussed below, on a less than optimum ionomer web, post-charging/ electretization was found to improve filtering efficiency, just as it is known to do for other microfibers.
  • the ionomers of the invention can have a melt index (MI) anywhere between about 5 and 1000 g/10 minutes. However, because a moderately fluid melt is desirable for meltblowing, the MI should preferably be between 30 and 400 g/10 minutes more preferably between 60 and 350 g/10 minutes and most preferably between 150 and 350g/10 min. The more fluid, the easier it is to produce fine microfibers, but too high an MI may detract from fiber strength, and may lead to excessive fiber bonding. It is also important to have the polymer solidify with adequate bonding of fibers, but not too much 'coalescence' by excess fusing, which produces areas where the fibers lose their fibrous identity. For this reason, generally, the more rapid the crystallization and higher melting point, the better.
  • MI melt index
  • Ionomers have low softening temperatures, and in this regard require special care in meltblowing a satisfactory web. Dipolymers are preferred to terpolymers because they crystallize more readily. Other means which can raise melt temperature of the ionomer, such as polymerizing at a temperature lower than about 200°C may help also. However, standard ionomers prepared at between 220°C and 270°C and pressures between 23,000 and 25,000 psi, according to the Rees patent noted above, are entirely suitable. Nevertheless, it has been found highly advantageous to cool the microfibers as quickly as possible with water, to prevent excess bonding.
  • Ionomer microfibers produce highly efficient filter webs. This efficiency may also be utilized in mixed fiber webs also containing fibers other than ionomers.
  • Ionomers whether deliberately post-charged or not, in the form of film or sheets may also find applications as the electrostatic element in electro- acoustical devices such as microphones, headphones and speakers, generators and recorders.
  • Microfiber webs of ionomer resins, (either experimental or commercial grades), as well as webs of two grades of HDPE and LLDPE were prepared. Webs were also made of blends of ionomer resins and polypropylene and blends of ionomer resins and polyethylene.
  • the meltblown webs were made in a 20 inch meltblowing line consisting of a 2 inch screw extruder and metering pump to control the polymer throughput per die hole in the range of 0.3 to 2 grams/minute.
  • the 20 inch horizontal die had 25 holes per inch and 0.0145 inch diameter holes.
  • a furnace for heating the air, and an air compressor with a maximum capacity of 650 sq.ft. /minute was used to attenuate the fibers from the die-tip to a moving drum collector. Except for a first, preliminary series of scouting tests, high-pressure water jets were introduced 2 to 3 inches from the die to enhance fiber cooling for the ionomer resin webs, before collecting on the drum. The die to collector distance was maintained, for most webs, at 11 inches. Conditions to make what is believed to be close to optimum fiber diameter are shown in Table 1.
  • Pore size distribution (minimum, maximum and mean) of the web was measured using a Coulter Porometer, as described in ASTM F-316-86.
  • the filtration efficiency was measured with polystyrene spheres of nominal sizes of 0.6, 1, 2 and 3 microns in diameter, at the 30 cm/sec face velocity. Pressure drop across the filter media is reported in inches of water.
  • the test is a modified ASTM 1215 filter efficiency test in that four different particle sizes were tested simultaneously. A first preliminary scouting series of tests utilized an ionomer resin filter web made, as noted above, without water cooling.
  • the first series also included ionomer web which had been specifically deliberately electrostatically post-charged for comparison with commercial electretized polypropylene.
  • filtration efficiency for 0.1 micron particles was the same order for the ionomer resin as for the polypropylene both for the charged and non-charged web samples, though somewhat higher for the polypropylene.
  • Uncharged the values were 32 versus 41 for polypropylene and charged 87 versus 98 for the polypropylene.
  • LLDPE was very much poorer than either. While these data relate to less than optimum webs, they indicate that ionomer resin, like polypropylene resin, can benefit from deliberate post- charging. However, the actual values obtained, as indicated above, do not represent significant numbers in terms of the efficiency possible with the material, in view of the non-optimum web structure.
  • the second series produced an ionomer web which gave far superior results to the first series ionomer webs.
  • the webs were generally microscopically comparable in appearance.
  • the polycarbonate and the PP-electret were both commercial webs, and presumed to have been produced under reasonably optimum conditions.
  • Web thickness is noted if measured, but is not particularly critical, the critical criterion of the filter being efficiency as a function of pressure drop. The results indicate that the ionomer which was not deliberately charged is equal to or even superior to the commercial polypropylene electret, for particles from 0.6 to 3.0 microns diameter.
  • the non post-charged ionomer sample with comparable web base weight of 2 oz./square yard is superior to the charged polypropylene sample.
  • the polypropylene sample had a greater pressure drop (0.33 versus 0.23). Since efficiency and pressure drop are largely conjugate characteristics of a filter, the non-charged ionomer shows superior performance.
  • PP in Table 1 was a commercial non-electretized web.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Filtering Materials (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
PCT/US1997/015641 1996-09-12 1997-09-05 Meltblown ionomer microfibers and non-woven webs made therefrom for gas filters Ceased WO1998011282A1 (en)

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EP97939814A EP0925390B1 (en) 1996-09-12 1997-09-05 Meltblown ionomer microfibers and non-woven webs made therefrom for gas filters
DE69704366T DE69704366T2 (de) 1996-09-12 1997-09-05 Schmelzgeblasene mikrofasern aus ionomeren und daraus hergestellte vliesstoffe für gasfilter
JP10513711A JP2001500201A (ja) 1996-09-12 1997-09-05 溶融吹きつけしたイオノマーの微小繊維およびそれから作られたガスフィルタ用の不織ウェブ
CA002264948A CA2264948A1 (en) 1996-09-12 1997-09-05 Meltblown ionomer microfibers and non-woven webs made therefrom for gas filters

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US08/712,743 1996-09-12
US08/712,743 US5817415A (en) 1996-09-12 1996-09-12 Meltblown ionomer microfibers and non-woven webs made therefrom for gas filters

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US6372004B1 (en) 1999-07-08 2002-04-16 Airflo Europe N.V. High efficiency depth filter and methods of forming the same
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EP0960645A3 (en) * 1998-05-11 2000-02-02 Airflo Europe N.V. Vacuum cleaner bag or filter, and method of filtering a gas
US6171369B1 (en) 1998-05-11 2001-01-09 Airflo Europe, N.V. Vacuum cleaner bag construction and method of operation
US6183536B1 (en) 1998-05-11 2001-02-06 Airflo Europe, N.V. Enhanced performance vacuum cleaner bag and method of operation
US6372004B1 (en) 1999-07-08 2002-04-16 Airflo Europe N.V. High efficiency depth filter and methods of forming the same
JP2003511577A (ja) * 1999-10-08 2003-03-25 スリーエム イノベイティブ プロパティズ カンパニー フリー繊維および極性液体による不織繊維エレクトレットウェブを製造するための方法および装置
US7094270B2 (en) 2001-03-02 2006-08-22 Airflo Europe N.V. Composite filter and method of making the same

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US5882519A (en) 1999-03-16
EP0925390B1 (en) 2001-03-21
DE69704366T2 (de) 2001-10-31
US5780153A (en) 1998-07-14
JP2001500201A (ja) 2001-01-09
DE69704366D1 (de) 2001-04-26
EP0925390A1 (en) 1999-06-30
US5817415A (en) 1998-10-06
CA2264948A1 (en) 1998-03-19

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