DK157286B - Ansigtsmaske samt fremgangsmaade til fremstilling af et fiberbaneelektreret til brug som filterlag i ansigtsmasken - Google Patents
Ansigtsmaske samt fremgangsmaade til fremstilling af et fiberbaneelektreret til brug som filterlag i ansigtsmasken Download PDFInfo
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- DK157286B DK157286B DK045179AA DK45179A DK157286B DK 157286 B DK157286 B DK 157286B DK 045179A A DK045179A A DK 045179AA DK 45179 A DK45179 A DK 45179A DK 157286 B DK157286 B DK 157286B
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- Prior art keywords
- fibers
- fiber
- stream
- charge
- face mask
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- 206010016654 Fibrosis Diseases 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
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- 239000004698 Polyethylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 231100001261 hazardous Toxicity 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
- H01G7/021—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric
- H01G7/023—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
- A41D13/1107—Protective face masks, e.g. for surgical use, or for use in foul atmospheres characterised by their shape
- A41D13/1138—Protective face masks, e.g. for surgical use, or for use in foul atmospheres characterised by their shape with a cup configuration
- A41D13/1146—Protective face masks, e.g. for surgical use, or for use in foul atmospheres characterised by their shape with a cup configuration obtained by moulding
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62B—DEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
- A62B23/00—Filters for breathing-protection purposes
- A62B23/02—Filters for breathing-protection purposes for respirators
- A62B23/025—Filters for breathing-protection purposes for respirators the filter having substantially the shape of a mask
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
- B03C3/28—Plant or installations without electricity supply, e.g. using electrets
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-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
- D04H1/54—Non-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
- D04H1/56—Non-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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
- D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0435—Electret
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S55/00—Gas separation
- Y10S55/35—Respirators and register filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S55/00—Gas separation
- Y10S55/39—Electrets separator
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Textile Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Emergency Management (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Physical Education & Sports Medicine (AREA)
- Business, Economics & Management (AREA)
- Filtering Materials (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
- Nonwoven Fabrics (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Electrostatic Separation (AREA)
- Semiconductor Lasers (AREA)
- Led Devices (AREA)
Description
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Den foreliggende opfindelse angâr en ansigtsmaske med en koplignende del indrettet til at passe over mund og næse pâ en person, nâr denne bærer masken, og indeholdende et filterlag, samt en fremgangsmâde til fremstilling af et 5 fiberbaneelektret til brug som filterlag i ansigtsmasken ifolge opfindelsen.
Ansigtsmasken ifolge opfindelsen er ejendommelig ved, at filterlaget omfatter mindst ét lag indeholdende smelteblæste fibre med en gennemsnitsdiameter pâ under 10 10 jum og en længde pâ 10 cm eller derover, hvilke fibre bestâr af et hydrofobt materiale med en specifik modstand pâ mindst 1014 ohm-centimeter og bærer deri indlejrede elektriske ladninger, der har en halvlevetid pâ mindst én uge ved stuetemperatur og i omgivelser med 100%'s relativ fugtighed.
15 For en ansigtsmaske med en koplignende del indrettet til at passe over mund og næse pâ en person, nâr denne bærer masken, opnâs ifolge opfindelsen en forbedret filtreringsevne af varig natur ved, at der i ansigtsmasken inkorporeres mindst ét lag indeholdende smelteblæste fibre med en gen-20 nemsnitsdiameter pâ under 10 μια og en længde pâ 10 cm eller derover, hvilke fibre bestâr af et hydrofobt materiale med en specifik modstand pâ mindst 1014 ohm-centimeter og bærer deri indlejrede elektriske ladninger, der har en halvlevetid pâ mindst én uge ved stuetemperatur og i omgivelser med 25 100%'s relativ fugtighed. Fra en gasstrom, der passerer gennem ansigtsmasken ifolge opfindelsen, fjerner denne en hojere procentdel af partikler, der fores med luftstrommen, end kendte masker og en sâdan forbedret ydeevne opnâs, selv om masken udsættes for ældning, som det forekommer i omgi-30 velser med hoj fugtighed.
En tidlig fremgangsmâde til dannelse af fibrose elek-treter omtales i USA patentskrift nr. 2.740.184 og omfatter anbringelse af termoplastiske trâde, filamenter, stoffer eller ark i et elektrostatisk felt tilvejebragt mellem pa-35 rallelle elektroder anbragt med ringe afstand imellem. Det fibrose materiale opvarmes for at blodgore det og afkoles 2
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derefter i naerværelse af feltet, hvorefter der indferes "mère eller mindre" permanente ladninger i fibrene.
USA patentskrift nr. 3.571.679 bemærker, at der ved denne metode bestâr den ulempe, at det er vanskeligt at 5 indf0re en nogenlunde h0j permanent ladning i et fibrdst materiale, der behandles, fordi anvendelse af store spaen-dinger ved de opladede elektoder forârsager bunddannelse gennem de âbne porer i det fibr0se væv. Det foreslâs derfor at dække de opladede elektroder med et dârligt ledende ark 10 for at fordele den anvendte h0je spænding og dæmpe eventuelt dielektrisk nedbrydning gennem det fibrdse materiale.
Denne metode med dækkede elektroder kritiseres i et senere USA patentskrift nr. 3.998.916, fordi der kræves for langt et tidsrum til opladning af det fibrdse materiale til 15 en dnskelig opladet tilstand. For at undgâ denne ulempe foresâs en noget indviklet to-trinsmetode, ved hvilken der fdrst fremstilles en film, der- lades elektrisk, og filmen derefter fibrilleres ved at passere over ruller forsynet med nâle og samles i flere lag til dannelse af et fibrdst 20 materiale.
Denne tillid til filmdannelse ved fiberfremstilling er et led i et historisk forldb, hvor teknikken er gâet frem fra fremstilling af forholdsvis tykke vokselektreter til tyndere film ved anvendelse af polymère materialer og 25 metoder, der omfatter adskillige justeringer under processen, herunder f.eks. kontrol af filmens temperatur under opladning, kontrol af afstanden mellem ladeapparatet og filmen og kontrol af ladetidsrummet. I USA patentskrift nr. 3.998.916 (se ogsâ "The Use of Polymers for Electrets", J.
30 Van Turnhout, Journal of Electrostatics, bd. 1 (1975), side 147-163) opnâs elektrisk ladning af filmen ved at opvarme filmen til nær dens smeltepunkt, strække den over en buet plade og spr0jte den med positive eller négative ladninger fra et antal tynde metaltrâde anbragt over den buede plade.
35 I USA patentskrift nr. 3.644.605 holdes en tynd polymerfilm over en dielektrisk plade med samme udstrækning og bombar- 3
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deres med en elektronstrâle. I NASA Technical Report R-457 (december 1975) sendes en spray eller tâge af dielektrisk væske gennem coronaafladningen fra en b0rsteelektrode eller fra et gitter af smalle metaltrâde og samles derefter pâ et 5 dielektrisk ark, hvor de smâ drâber storkner som en film.
Selv om dannelsen af et fibrest materiale ved hjælp af indskudt dannelse af en film udnytter kendskabet til filmopladningsteknikken, er det en tidsrovende og kostbar metode. Desuden kan der med denne teknik kun opnâs begrænsede 10 fiberstorrelser.
Sâdanne ulemper er afhjulpet med den hidtil ukendte fremgangsmâde til fremstilling af et fiberbaneelektret til brug som filterlag i ansigtsmasken ifolge opfindelsen, hvil-ken fremgangsmâde er ejendommelig ved 15 1) ekstrudering af et smeltet fiberdannende materiale med en specifik modstand pâ mindst ÎO·1-^ ohm-cm gennem flere âbninger ind i en gasstrdm med stor hastighed, hvor den ekstruderede væske udtyndes til dannelse af en str0m af fibre, 20 2) bombardering af fiberstremmen med elektrisk ladede partikler, efterhânden som fibrene kommer ud af âbningerne, og 3) samling af fibrene til et lag i et omrâde, der er tilstrækkelig langt fra âbningerne, til at fibrene er afk0let 25 til en fast fibres formfast form.
Nâr fibrene er k0let af til en fast fibres tilstand, der kan holde formen, viser de sig at medfere en vedvarende elektrisk ladning. Det samlede materiale eller den samlede mâtte kan anvendes direkte bortset fra, at det som regel 30 skal tilrettes eller udskæres efter mâl.
De betingelser, hvorunder fremgangsmâden ifelge op-findelsen skal udferes, stâr i skarp modsætning til de kon-trollerede betingelser, der ved tidligere metoder har været mulige til dannelse af filmelektreter: fibrene bevæger sig 35 med ekstremt h0je hastigheder, de blæses med turbulens af en gasstr0m med stor hastighed, og de omsluttes og disper- 4
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gérés i store kvantiteter fortyndede luft med stor hastighed. Desuden indtræder de elektrisk ladede partikler i fiber-strommen og tilbageholdes i effektive mængder i de smel-teblæste fibre. Injicering af partiklerne i fiberstr0mmen 5 indtræffer nodvendigvis i den lille brokdel af et sekund (mindre end 1/1000 sekund), nâr fibrene bâde er nær de elektrisk ladede partiklers kilde og befinder sig i smeltet eller næsten smeltet tilstand. Efter denne injicering st0rk-ner fibrene yderst hurtigt og fryser derved de elektriske 10 ladninger ind i fibrene, hvor de tilvejebringer en samlet fibermasse med en vedvarende elektrisk ladning.
Den vedvarende ladning i fibermaterialerne adskiller sig fra den midlertidige ladning, der er blevet etableret i andre fiberprodukter f0r i tiden, ofte soin en hjælp til 15 fremstilling af produktet. Der er sâledes blevet etableret ladninger for at understotte overtrækning af fibrene med en væske med modsat ladning (se USA patentskrift nr. 2.491.889), eller for at forbedre fordelingen og adskillelsen af fibrene eller trække dem mod en kollektor, hvorved der fâs en mere 20 ensartet fibermâtte (se USA patentskrifterne 2.466.906, 2.810.426, 3.824.052 og 3.003.304 samt vedrorende sâdanne fiberstrenge, se USA patentskrifterne nr. 3.490.115 og 3.456.156).
De ladninger, der etableres under disse fremstil-25 lingsprocesser, er af natur kun midlertidige. Sâledes kan det fiberdannende materiale hâve utilstrækkelig specifik modstand, eller der kan være for meget ledende oplosnings-middel til stede i de dannede fibre til, at der kan opret-holdes en permanent ladning. Eller ladningen kan være eta-30 bleret, efter at fibrene er blevet dannet, sâledes at der kun er etableret en overfladeladning. Eller ladebetingel-serne, sâsom den anvendte spænding, kan være utilstrækkelige til at udvikle en permanent ladning. Eller ladningen kan være neutraliseret efter samling af fibrene. Hvis der er 35 nogen rest af en sâdan midlertidig ladning tilbage efter fremstillingen af fibermâtter if0lge de ovenfor anf0rte 5
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patentskrifter, forsvinder denne hurtigt under opbevaring aller brug.
I modsætning hertil besidder de fibermaterialer, der fremstilles ved fremgangsmâden ifelge opfindelsen, en ved-5 varende eller "permanent" ladning. Nâr sâdanne fibermaterialer opbevares under gængse betingelser, kan de bibeholde en effektiv ladning i mange âr. Under fremskyndet afprdvning, sâsom ved opbevaring i omgivelser med stuetemperatur og 100% relativ fugtighed, har ladningen af fibermaterialerne 10 en halvlevetid pâ mindst én uge og fortrinsvis pâ 1/2 eller et helt âr. Med en sâ vedvarende ladning kan fibrene og fibermaterialerne med rette kaldes elektreter, og udtrykkene "fiberelektreter", "fibermaterialeelektreter" eller det mere almindelige "fibros elektret" vil blive anvendt ved 15 beskrivelsen af dem.
For mange elektreter af fibrost materiale kan der fâs en pâlidelig angivelse af ladningens st0rrelse ved at mâle overfladespændingen i materialet med et elektrostatisk isosonde voltmeter. sâdan en mâling er imidlertid mindre 20 nojagtig, hvis materialet omfatter en blanding af modsat ladede fibre. Et materiale med blandet ladning er alligevel nyttigt, f.eks. til for0gelse af filteregenskaberne, men nettoladningen, der mâles pâ mater ialet, vil ikke være et udtryk for ladningens fulde st0rrelse. For elektreter af 25 fibrpst materiale, der bærer en vedvarende ladning med kun det ene fortegn, mâles ladningen i reglen som mindst 10“^ coulomb pr. gram smelteblæste fibre. For elektreter af fi-brost materiale, der omfatter bâde positivt og negativt ladede fibre, vil nettoladningen i reglen være mindst 10-9 30 coulombs pr. gram smelteblæste fibre. En angivelse af elek-trisk ladning kan ogsâ fâs ved andre pr0ver, sâsom pâforele af farvepulver pâ materialet, men ikke nedvendigvis ved mâlinger, der giver numerisk bestemte kvantiteter.
De smelteblæste ladede fibre, der fremstilles som 35 angivet ovenfor, kan afpasses, sâ at de fâr en 0nsket fiber-diameter. Til mange formâl har fibrene mikrofiberst0rrelser, 6
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(dvs. en st0rrelse, der bedst betragtes under mikroskop), og til nogle anvendelser gælder det, at jo mindre diameteren er jo bedre. Mikrofibrene kan sâledes i gennemsnit være mindre end 25, 10 eller endog 1 mikrometer i diameter.
5 Man ved, at fibre i mikrost0rrelse kan hâve flere nyttige egenskaber, herunder forbedring af filtrering i visse henseender, og kombinationen af fibre i mïkrost0rrelse med en permanent elektrisk ladning giver elektreter af fi-br0st materiale fremstillet ved fremgangsmâden if0lge opfin-10 delsen enestâende filtreringsegenskaber.
Elektreterne af fibr0st materiale anvendes i ansigts-masken if0lge opfindelsen, der er ejendommelig ved, at fil-terlaget omfatter mindst ét lag indeholdende smelteblæste fibre med en gennemsnitsdiameter pâ under 10 jum og en længde 15 pâ 10 cm eller derover, hvilke fibre bestâr af et hydrofobt materiale med en specifik modstand pâ mindst 1014 ohm-cen-timeter og bærer deri indlejrede elektriske ladninger, der har en halvlevetid pâ mindst én uge ved stuetemperatur og i omgivelser med 100%'s relativ fugtighed. En særlig udformning 20 for ansigtsmasken if0lge opfindelsen er den skâlformede ansigtsmaske, der er vist. i fig. 3Anvendelse af elektreter af fibr0st materiale i ansigtsmasker til erstatning af materiale af smelteblæste mikrofibre, der blev anvendt i tid-ligere masker af den viste type, kan forbedre filtereffek-25 tiviteten med en faktor pâ to eller mere. Masker if0lge opfindelsen af den i fig. 3 viste type kan fremstilles bil-ligt, og deres lave pris og store effektivitet giver et bredt anvendelsesomrâde, der ikke kan opnâs med andre kendte ansigtsmasker.
30 Opfindelsen belyses i det f0lgende nærmere ved hjælp af tegningen pâ hvilken fig. 1 er en skematisk fremstilling af et repræsen-tativt apparat til dannelse af en elektret af fibr0st materiale, 7
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fig. 2 er et opret snit langt linien 2-2 i fig, 1 og omfatter et skematisk stromdiagram til en kilde af elektrisk ladede partikler i apparatet i fig. 1, fig. 3 og 4 viser en repræsentativ ansigtsmaske, der 5 inkorporerer en elektret af fibr0st materiale, idet fig. 3 viser anvendelsen af masken og fig. 4 et snit langs linien 4-4 i fig. 3, fig. 5 er en skematisk fremstilling af et apparat til afprovning af filteregenskaberne hos en elektret af 10 fibermateriale fremstillet ved fremgangsmâden ifplge opfindelsen, og fig. 6 viser kurver for partikelgennemtrængning (or-dinaten) som funktion af partikelst0rrele (abscissen) i elektreter af fibrost materiale fremstillet ved fremgangs-15 mâden if0lge opfindelsen og hermed sammenligneligt ikke-ladet materiale.
Fig. 1 og 2 viser et repræsentativt apparat 10 til fremstilling af elektreter af fibrost materiale ved fremgangsmâden if0lge opfindelsen. En del af dette apparat kan 20 være et konventionelt smelte-blæsningsapparat som beskrevet i Report No. 4364 fra U.S. Naval Research Laboratories, udgivet 25. maj 1954 med titlen "Manufacture of Super Fine Organic Fibers" af V.A. Wente, C.D. Boon og E.L. Fluharty.
Et sâdant fiber-blæsningsapparat omfatter en dyse il, der 25 er udformet med en række smalle âbninger 12 ved siden af hinanden til ekstrudering af smeltet materiale og med spalter 13 pâ hver side af rækken af âbninger, hvorigennem en gas, i reglen luft, blæses med stor hastighed. Gasstrommen trækker det ekstruderede materiale til fibre, afkoler fibrene til 30 stbrknet form og forer fibrene til en kollektor 14 som en fiberstrom 15. Den i fig. 1 viste kollektor 14 omfatter en fint perforeret skærm udformet som en tromle eller cylinder, men kollektoren kan ogsâ hâve andre udformninger sâsom en flad skærm eller et lukket bælte, der korer pâ valser. Et 35 gasudsugningsapparat kan være anbragt bag skærmen for at lette anbringelsen af fibrene og fjernelsen af gas. Strommen 8
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15 af blæste fibre afsættes pâ kollektoren som en tilfældig filtret saxranenhængende masse, der kan hândteres som en mâtte 16, der kan afvikles fra kollektoren og opvikles i en op-bevaringsrulle 17.
5 Til bombardering med elektrisk ladede partikler pâ de smelteblæste fibre er der anbragt en eller flere kilder for sâdanne partikler op til dyseâbningerne 12. I apparatet i fig. 1 og 2 er der anvendt to kilder 18 og 19, en pâ hver side af fiberstrommen 15. Hver kilde omfatter en elektrisk 10 leder 20 eller 21 fforbundet med en hojspændingskilde 22 og anbragt inden i en metalskal 23 eller 24, som er forbundet til jord gennem en modstand 25. Som vist i fig. 2 kan lederne monteres i isolatorer 26 og 27. Nâr der sendes strom gennem lederen med en spænding, der er hdj nok (i reglen 15 kilovolt 15 eller mere), dannes der en korona omkring lederen, og luften eller anden gas omkring lederen ioniseres. De elektrisk ladede ioner eller partikler slynges ind i fiberstrdmmen af en kombination af aerodynamiske og elektrostatiske kræfter, der virker pâ de ladede partikler. Strdmmen af ladede par-20 tikler kan understdttes af en ventilator eller ved hjælp af spænding pâ skallerne 23 og 24, der slynger partiklerne bort. I stedet for en cylindrisk skal eller ror kan der pâ hver side af lederen anbringes flade metalplader eller et hvilket som helst andet arrangement, der etablerer den 0n-25 skede spændingsgradient mellem elektroden og det omgivende skjold. André kilder for elektrisk ladede partikler er elektronstrâler og bestrâlingskilder sâsom rdntgenkanoner.
Kilderne 18 og 19 for elektrisk ladede partikler er anbragt tæt ved læben pâ dysen 11, hvor fibrene er i smeltet 30 eller næsten smeltet tilstand. Under sâdanne betingelser er mobiliteten af de frie ladningsbærere i fibrene stor, og indforelsen af en ladning i fibrene lettes. Jo tættere de elektrisk ladede partiklers kilde er ved dysens læbe, jo mere smeltede er fibrene, og jo lettere er det at indfçire 35 ladningen.
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Efterhânden som fibrene storkner og afkoles, bliver de bombarderede ladninger indefrosset i fibrene, og fibrene bliver vedvarende ladet (opvarmning af fibrene vil fjerne ladningen). I overensstemmelse med gængs terminologi for 5 elektreter, kaldes denne ladning en homo-ladning, og den har samme tegn som den spænding, der er pâfort lederne. Der kan anvendes enten en positiv eller en negativ ladning pâ de elektrisk ladede partiklers kilde, og der kan anvendes kilder for modsat ladede partikler samtidig og pâ hver side 10 af fiberstrommen.
En statisk ladning pâ fibrenes overflade (der kan være med modsat tegn i forhold til dem, hvormed der bombar-deres) kan ogsâ udvikles under fremstilling af et materiale som det her omhandlede. Imidlertid vil en sâdan ladning 15 hurtigt nedbrydes pâ samme mâde, som en statisk ladning nedbrydes, nâr den er pâfdrt pâ et færdigt fibermateriale.
Temperaturen af gassen rundt om fibrene har en tendens til hurtigt at falde, efterhânden som afstanden fra dyseâb-ningen 0ges. Ved f.eks. betingelserne som beskrevet i ek-20 sempel 1, hvor luftens temperatur ved dyseâbningen er ca.
290°C, vil temperaturen være ca. 190°C 1,25 cm fra dysen, ca. 150°C 2,5 cm fra dysen, ca. 120°C 3,75 cm fra dysen og ca. 95°C 5 cm fra dysen. De ladninger, hvormed der bombar-deres pâ de smeltede eller næsten smeltede fibre nær dyse-25 læben, bliver hurtigt indefrosset i fibrene.
Der kan anvendes en lang række polymère materialer med dielektriske egenskaber, der tillader elektrisk ladede partikler at forblive i fibrene, uden at ladningen forsvin-der. Polypropylen, der har en specifik modstand pâ ca. 10·*·6 30 ohm-cm, er særlig anvendelig. André polymère sâsom polycar-bonater og polyhalogencarboner, der kan smelteblæses og har passende specifikmodstand under de forventede betingelser i omgivelserne, kan ogsâ anvendes. De anvendelige polymer-materialer har en specifik modstand pâ mindst 1014 ohm-cm 35 og hindrer absorption af fugtighed i mængder, der umuliggcr ladningens onskede halvlevetid. Pigmenter, farvestoffer, 10
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fyldstoffer og andre additiver kan blandes i det polymère materiale, forudsat at de ikke eliminerer de nodvendige egenskaber, f.eks. modstand.
Diameteren af de fremstillede blæste fibre varierer 5 med sâdanne paramétré som storrelsen af dyseâbningen, det polymère materiales viskositet og luftstr0mmens hastighed. Blæste mikrofibre betragtes i reglen som diskontinuerlige, skont forholdet mellem deres længde og diameter nærmer sig det uendelige, for at der kan fremstilles anvendelige mate-10 rialer. Nogle arbejdere skonner, at fiberlængderne er op til 10 cm eller mere.
Den fiberdannende procès kan ændres, sa at der kan indfdres andre fibre eller partikler i materialet. Sâledes beskriver USA patentskrift nr. 3.971.373 et apparat og en 15 fremgangsmâde til indf0ring af faste partikler i et blæst fibermateriale. En lang række partikler er anvendelige især til filtrering og rensning; eksemplerne omfatter aktiveret kul, aluminium, natriumbicarbonat og S0lv, der fjerner en komponent fra en væske ved adsorption, kemisk reaktion eller 20 amalgamering, og sâdanne findelte katalytiske midler som hopcalcit, der katalyserer omdannelse af en farlig gas til uskadelig form. Partiklerne kan variere i st0rrelse, mindst fra 5 mikrometer til 5 mm i gennemsnitlig diameter. Til respiratorer har partiklerne i reglen en gennemsnitlig dia-25 meter pâ mindre en 1 mm.
Præformede fibre kan ogsâ indf0res i et blæst fibermateriale under dannelsen af materialet, se f.eks. USA patentskrift nr. 3.016.599 og USA patentskrift nr. 4.118.531. Sâledes kan der sættes stapelfibre, herunder krympede sta-30 pelfibre, til en str0m af smelteblæste fibre (nâr det drejer sig om krympede stapelfibre, ved at opsamle de krympede fibre fra et materiale ved hjælp af en rivevalse) til dan-nelse af et mere âbent eller porost materiale med formindsket trykfald, men gode filtreringsegenskaber.
35 Mange andre tilsætninger eller ændringer i den grund- liggende smelteblæseproces er mulige. Sâledes kan de smel- 11
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teblæste fibre opsamles i et monster af kompakte omrâder og omrâder med lav massefylde, se USA patentskrift nr. 4.042.740. Ligeledes kan opsamlet materiale af smelteblæste fibre videreforarbejdes, f.eks. ved ituskæring, til dannelse 5 af fibre, der kan indgâ i andre produkter, ved at sammen-trykkes i et monster, se USA patentskrift nr. 2.464.301, ved spr0jtning eller ved pâ anden mâde at tilsætte ingredi-enser til materialet, ved at laminere materialet pâ andre materialer eller produkter i arkform eller ved at tilpasse 10 eller tilskære materialet.
Fig. 3 og 4 viser en passende udformning og konstruk-tion af ansigtsmasker, hvortil der kan anvendes elektreter af fibrost materiale. En maske 28 omfatter en i reglen skâl-formet del 29, der er udformet til at passe over mund og 15 næste pâ et menneske, og en strop 30 til fastholdelse af masken. Kanten pâ masken har en tendens til at passe temmelig stramt til ansigtets konturer og afgrænser sâledes tilgangen af luft til maskens bærer, dvs. det meste af den luft, der indândes af maskens bærer, skal passere gennem masken. Den 20 skâlformede del kan omfatte et indre ikke-vævet materiale af luftlagte fibre 31, to lag 32 og 33 af fibrôst elektret-materiale og et udvendigt ikke-vævet materiale 34 af luftlagte fibre.
Opfindelsen vil i det folgende blive yderligere belyst 25 ved hjælp af eksempler. Der anvendes to forskellige priver i eksemplerne til afprevning af det fremstillede materiales filtreringsevne, én, der anvender dioctylphthalatdrâber (DOP-pr0ve), og en anden, der anvender siliciumoxidstov til en pr0ve fastlagt af National Institute for Occupational 30 Safety and Health (NIOSH-siliciumoxidst0vpr0ve), og begge er beskrevet detaljeret i U.S. Fédéral Register, Title 30, part 11.
Eksempel 1-8 35 Der fremstilles blæste mikrofibre af polypropylen- ® e .
harpiks (Hercules "Profax 6330") pâ et apparat som vist i 12
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fig. 1. Betingelserne i eksemplerne 1, 2, 4-6 og 8 er f0l-gende: dysen er 50 cm bred. Temperaturen i henholdsvis smelten i dysen, i selve dysen og i den luft, der uddrives fra dysen, er 346°C, 370°C og 400°C. Lufttrykket ved dysen 5 er 0,43 kg/cm2, og polypropylenet ekstruderes med en ha-stighed pâ 6,8 kg i timen. Dyselæben befinder sig 60 cm fra kollektoren; afstanden 35 i fig. 1 fra dyselæben til lederne er 3 cm, og afstanden 36 mellem midterlinien 37 i fiber-stremmen og lederne 20 eller 21 er 2,5 cm. Der pâf0res en 10 spænding pâ 15 kilovolt pâ hver af lederne 20 og 21, og en spænding pâ 3 kilovolt pâf0res skjoldene 23 og 24. I eksemplerne 3 og 7 er aile betingelser de samme med undtagelse af, at smeltens temperatur er 360°C, lufttemperaturen er 370°C og lufttrykket 0,5 kg/cm2. Materialet fremstilles i 15 varierende tykkelser og med varierende vægt som anfert i tabel I. De fleste af eksemplerne omfatter et positivt ladet materiale (angivet ved et + i tabellen nedenfor og frem-stillet ved at pâf0res en positiv spænding pâ begge elek-troderne 20 og 21 i fig. 1) , et negativt ladet materiale 20 (-) og et ikke-ladet materiale (C) som sammenligning. Tryk- fald (ΔΡ) og partikelgennemtrængning (%P) mâlt med DOP-pr0ver anfdrt i tabel I nedenfor.
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Tabel I
Eks. Basisvægt ΔΡ P
nr. (g/m2) (mm vand) (%) 5 1 + 0,29 0,6 61 1 - 0,30 0,6 60 1 C 0,32 0,8 83 2 + 0,25 0,9 51 10 2 - 0,25 0,7 65 2 C 0,25 0,7 80 3 + 0,26 0,9 54 3 - 0,26 0,9 58 15 3 C 0,28 1,0 78 4 + 0,33 1,1 44 4 - 0,33 1,2 53 4 C 0,32 1,1 70 20 5 - 0,45 0,8 61 5 C 0,45 0,7 81 6 + 0,52 1,1 46 25 6 - 0,52 1,3 52 6 C 0,52 1,3 73 7 + 0,52 1,1 44 7 - 0,52 1,2 53 30 7 C 0,52 1,1 70 1 - 0,65 2,1 32 8 C 0,65 2,1 55
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14
Eksempel 9-12
Masker som dem, der er vist i fig. 3 og 4, fremstilles af materiale fra eksemplerne 1-, 1+, 2+ og 3+. Resultaterne af NIOSH-siliciumoxidst0vpr0ven er anf0rt i tabel II.
5
Tabel II
Indledende Slut- Slut- Partikel-
Eks. inhalering inhalering ekshalering gennemtrængning 10 nr. (mm vand) (mm vand) (mm vand) (mg) 9 7,9 13,9 9,3 1,39 10 8,1 14,7 10,0 0,66 11 11,6 16,6 16,4 0,19 15 12 12,0 17,8 13,8 0,23
Ladningsnedbrvdninqsprover
Nedbrydningen af ladningen pâ det fibr0se elektret-materiale if0lge eksempel 6+ i et vist tidsrum afpr0ves ved 20 at opbevare pr0ver af materialet i polyethylenbeholdere ved normale stuebetingelser. Ladningsnedbrydningen bestemmes ved at mâle overfladespændingen med et Monroe elektrostatisk isosondevoltmeter og anvende forholdet mellem ladning og overfladespænding (Q=CV, hvor Q er ladning, C er kapacitet, 25 og V er overfladespænding) til at beregne den effektive overfladeladningstæthed. Tabel III viser forholdet mellem den indledende overfladeladning og overfladeladningen mâlt med forskellige intervaller.
30 Tabel III
Forholdsmæssiq overfladeladning bibeholdt under opbevarinq
Eks. nr. 100 daqe 200 daqe 325 daqe 6+ 0,96 0,94 0,94 35
Desuden foretages der mâlinger af nedbrydningen af ladningen pâ pr0ver af materiale if0lge eksempel 6+ og 6 C
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efter opbevaring i en ekssikkator ved 20°C og 100% relativ fugtighed. Pr0verne anbringes i ekssikkatoren 120 dage efter fremstilling. Den forholdsmæssige mængde overfladeladning, der er bibeholdt pâ forskellige tidspunkter, er vist i tabel 5 IV.
Tabel IV
Forholdsmæssiq overfladeladning bibeholdt under onbevarina 10 Eks.
nr. 5 dage 10 dage 25 dage 100 dage 180 dage 6 + 0,99 0,98 0,97 6 C 0,35 0,15 0,1 15 üd over prever med hensyn til nedbrydning af overfladeladning mâles ændringen i partikelgennemtrængning gennem et materiale ifdlge eksempel 6 + efter forskellige opbevar-ingstidsrum i omgivelser med 100% relativ fugtighed, og 20 resultaterne er vist i tabel V. Mâlingerne foretages med et apparat 39 vist i fig. 5. Luft, der kommer ind i et aero-soltransportror 40 med en diameter pâ 7,6 cm, passerer gennem et absolut filter 41 for at sikre, at den oprindelige par-tikelkoncentration holdes pâ et minimum. Den aérosol, der 25 skal afprdves, injiceres med strdmmen i det absolutte filter ved et indldb 42 og sendes gennem en sektion 43, hvor aero-solen, om n0dvendigt, kan neutraliseres ved hjælp af en krypton- 8 5 bestrâlingskilde. Den aérosol, der skal afpreves, ®r rogfældet siliciumoxidst0v som beskrevet i NIOSH's silici-30 umoxidst0vpr0ve.
Mængden, der udsendes fra aerosolkilden, overvâges med et aerosolphotometer 44, der er monteret pâ transport-r0ret. Aerosolphotometeret anvender en fotodiode 45 til at mâle den fremadrettede lysspredning fra partikler, der pas-35 serer gennem strâlen fra en heliumneonlaser 46. Mængden af udsendt lys star i forhold til aerosolkoncentrationen, hvis stdrrelsesfordelingen i aerosolindholdet er konstant hele 16
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tiden. En prove af aerosolen udtages fra hovedaerosolstrdmmen gennem en kanal 47 og sendes gennem provefiltreringsmediet 48. Med passende ventilindstilling overvâges storrelsen og koncentrationen af de partikler, der skal undersoges, mellem 5 0,15 og 3 mikrometer mod strommen og med strommen i filtre- ringsmediet ved hjælp af et Particle Measuring System ASAS-200 Aérosol Spectrometer, der er forbundet til en kanal 49.
Der foretages stadige mâlinger af trykfaldet gennem filteret (med en trykmâler 50), dugpunktstemperaturen (som mâlt i en 10 kanal 51) og luftens temperatur. De data, der fâs med dette proveinstrument, muliggor en beskrivelse af filtergennem-trængning som en funktion af partikelstorrelse frem for pâ massebasis.
Typiske gennemtrængningsresultater pâ et apparat som 15 vist i fig. 5 for materialer ifolge eksempel 3 (firkanter), 6 + (cirkler) og 6 C (udfyldte prikker) er vist i fig. 6.
En top pâ partikelgennemtrængningskurven forekommer i par-tikelstorrelsesintervallet 0,3-0,6 mikrometer, hvor hverken diffusion eller inertiafsætning er særlig effektive. Det 20 fremgâr imidlertid, at det fibrose elektretmateriale frem-stillet ved fremgangsmâden ifolge opfindelsen giver forbed-ring for aile partikelstorrelser.
Som anfort ovenfor viser tabel V gennemtrængningsresultater i det i fig. 5 viste apparat, efter at provemate-25 rialerne har været udsat for omgivelser med 100% relativ fugtighed i forskellige tidsrum. De i tabel V anforte re-sultater er kumulativ partikelgennemtrængning mâlt med partikler mindre end en given diameter (0,3 mikrometer, 1 mikrometer og 3 mikrometer) ; dvs. at det résultat, der er 30 anfort i kolonnen med overskriften "3 jum'1 er den procentdel partikler op til 3 mikrometer s storrelse, der trængte gennem provematerialet; resultatet anfort i kolonnen med overskriften "1 μη" er den procentdel partikler med op til 1 mikrometer s storrelse, der trænger igennem etc.
Tabel V
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17
Kumulativ massegennemtrængning i % ved forskelllae partikelstflrrelser 5 Antal dage i 100% relativ fugtighed 0,3 μιη l μια 3 μη 0 0,012 0,24 2,4 1 0,019 0,30 3,3 10 7 0,008 0,34 3,0 30 0,009 0,24 1,7 180 0,008 0,29 2,6
Claims (6)
1. Ansigtsmaske med en koplignende del indrettet til at passe over mund og næse pâ en per son, nâr denne bærer 5 masken, og indeholdende et filterlag, kendetegnet ved, at filterlaget omfatter mindst et lag indeholdende smelteblæste fibre med en gennemsnitsdiameter pâ under 10 μια og en længde pâ 10 cm eller derover, hvilke fibre bestâr af et hydrofobt materiale med en specifik modstand pâ mindst 10 1014 ohm-centimeter og bærer deri indlejrede elektriske ladninger, der har en halvlevetid pâ mindst én uge ved stuetemperatur og i omgivelser med 100%'s relativ fugtighed.
2. Ansigtsmaske ifolge krav 1, kendetegnet 15 ved, at de smelteblæste fibre bestâr af polypropylen.
3. Ansigtsmaske if0lge krav 1 eller 2, kendetegnet ved, at det nævnte lag yderligere omfatter sta-pelfibre anbragt imellem de smelteblæste fibre. 20
4. Fremgangsmâde til fremstilling af et fiberbane-elektret til brug som filterlag i ansigtsmasken ifolge krav 1, kendetegnet ved 1. ekstrudering af et smeltet fiberdannende materiale 25 med en specifik modstand pâ mindst 1014 ohm-cm gennem flere âbninger ind i en gasstr0m med stor hastighed, hvor den ekstruderede væske udtyndes til dannelse af en str0m af fibre, 2. bombardering af fiberstrommen med elektrisk ladede 30 partikler, efterhânden som fibrene kommer ud af âbningerne, og 3. samling af fibrene til et lag i et omrâde, der er tilstrækkelig langt fra âbningerne, til at fibrene er afkolet til en fast fibr0s formfast form. 35 DK 157286 B
5. Fremgangsmâde if0lge krav 4,kendetegnet ved, at stapelfibre indf0res i fiberstrommen, efter at stro-mmen er blevet bombarderet med ladede partikler.
6. Fremgangsmâde if0lge krav 4 eller 5, kende- t e g n e t ved, at partikler indfores i fiberstrommen, efter at str0mmen er blevet bombarderet med ladede partikler.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/875,614 US4215682A (en) | 1978-02-06 | 1978-02-06 | Melt-blown fibrous electrets |
US87561478 | 1978-02-06 |
Publications (3)
Publication Number | Publication Date |
---|---|
DK45179A DK45179A (da) | 1979-08-07 |
DK157286B true DK157286B (da) | 1989-12-04 |
DK157286C DK157286C (da) | 1990-05-07 |
Family
ID=25366080
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK045179A DK157286C (da) | 1978-02-06 | 1979-02-02 | Ansigtsmaske samt fremgangsmaade til fremstilling af et fiberbaneelektreret til brug som filterlag i ansigtsmasken |
Country Status (16)
Country | Link |
---|---|
US (1) | US4215682A (da) |
JP (2) | JPS59124B2 (da) |
AT (1) | AT380126B (da) |
AU (1) | AU507773B2 (da) |
BR (1) | BR7900546A (da) |
CA (1) | CA1122546A (da) |
CH (1) | CH642277A5 (da) |
DE (1) | DE2904170A1 (da) |
DK (1) | DK157286C (da) |
ES (1) | ES477436A1 (da) |
FR (1) | FR2416535A1 (da) |
GB (1) | GB2015253B (da) |
IT (1) | IT1116822B (da) |
NL (1) | NL7900855A (da) |
NO (1) | NO151092C (da) |
SE (1) | SE444893B (da) |
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- 1979-01-30 BR BR7900546A patent/BR7900546A/pt unknown
- 1979-02-02 SE SE7900929A patent/SE444893B/sv not_active IP Right Cessation
- 1979-02-02 DK DK045179A patent/DK157286C/da active
- 1979-02-02 NL NL7900855A patent/NL7900855A/xx not_active Application Discontinuation
- 1979-02-02 NO NO790347A patent/NO151092C/no unknown
- 1979-02-03 ES ES477436A patent/ES477436A1/es not_active Expired
- 1979-02-05 CH CH111479A patent/CH642277A5/de not_active IP Right Cessation
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- 1979-02-05 FR FR7902842A patent/FR2416535A1/fr active Granted
- 1979-02-05 IT IT47886/79A patent/IT1116822B/it active
- 1979-02-05 JP JP54012144A patent/JPS59124B2/ja not_active Expired
- 1979-02-05 AU AU43912/79A patent/AU507773B2/en not_active Ceased
- 1979-02-05 DE DE19792904170 patent/DE2904170A1/de not_active Ceased
- 1979-02-05 AT AT0082779A patent/AT380126B/de not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
---|---|
NO151092C (no) | 1985-02-06 |
ATA82779A (de) | 1985-08-15 |
NO790347L (no) | 1979-08-07 |
FR2416535B1 (da) | 1984-02-03 |
NO151092B (no) | 1984-10-29 |
AU507773B2 (en) | 1980-02-28 |
AU4391279A (en) | 1979-09-06 |
CH642277A5 (de) | 1984-04-13 |
AT380126B (de) | 1986-04-10 |
DK157286C (da) | 1990-05-07 |
GB2015253B (en) | 1982-08-25 |
IT7947886A0 (it) | 1979-02-05 |
ES477436A1 (es) | 1980-09-01 |
JPS62290477A (ja) | 1987-12-17 |
SE444893B (sv) | 1986-05-20 |
NL7900855A (nl) | 1979-08-08 |
GB2015253A (en) | 1979-09-05 |
JPS54113900A (en) | 1979-09-05 |
CA1122546A (en) | 1982-04-27 |
DE2904170A1 (de) | 1979-08-09 |
IT1116822B (it) | 1986-02-10 |
JPH027671B2 (da) | 1990-02-20 |
SE7900929L (sv) | 1979-08-07 |
US4215682A (en) | 1980-08-05 |
JPS59124B2 (ja) | 1984-01-05 |
DK45179A (da) | 1979-08-07 |
BR7900546A (pt) | 1979-09-11 |
FR2416535A1 (fr) | 1979-08-31 |
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