DK169728B1 - Fremgangsmåde til frigørelse af cellulosebaserede fibre fra hinanden i vand og støbemasse til plastisk formning af celluloseholdige fiberprodukter - Google Patents
Fremgangsmåde til frigørelse af cellulosebaserede fibre fra hinanden i vand og støbemasse til plastisk formning af celluloseholdige fiberprodukter Download PDFInfo
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- DK169728B1 DK169728B1 DK011793A DK11793A DK169728B1 DK 169728 B1 DK169728 B1 DK 169728B1 DK 011793 A DK011793 A DK 011793A DK 11793 A DK11793 A DK 11793A DK 169728 B1 DK169728 B1 DK 169728B1
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- fibers
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/30—Defibrating by other means
- D21B1/32—Defibrating by other means of waste paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
- D21H23/06—Controlling the addition
- D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
- D21H23/16—Addition before or during pulp beating or refining
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/30—Defibrating by other means
- D21B1/34—Kneading or mixing; Pulpers
- D21B1/342—Mixing apparatus
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/0018—Devices for dispensing fibres in a fluid
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/14—Secondary fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
Description
DK 169728 B1
Opfindelsen angår frigørelse af cellulosebaserede fibre ved kraftig mekanisk bearbejdelse efter tilsætning af hydrokolloid og ved tørstofindhold op til 80%. Bearbejdelsen resulterer i en støbemasse, som er egnet til plastisk 5 formning af celluloseholdige fiberprodukter.
Ved kendt produktion af papir og pap foretages først en behandling af fiberråvaren ved, at fibrene dispergeres i vand i en såkaldt pulper ved meget lavt tørstofindhold på 10 kun nogle få procent. Resten, normalt mere end 95%, er vand.
Pulpere af speciel udførelse er beskrevet i de europæiske patentansøgninger 126.632 og 189.379. I disse udtrykkes stolthed over at kunne arbejde med tørstofindhold på lidt over 20%. 15 I papirindustrien er det alment antaget, at de nævnte store vandmængder er nødvendige for, at fibrene effektivt kan blødgøres, udvides, og således nemmere frigøres fra hinanden ved hjælp af den dispergerende virkning fra pulperens propel.
20
Det meget lave tørstofindhold, som bruges ved traditionel opløsning af fiberråvaren og også ved selve formningen af papir, har gjort papirfabrikkerne til store, tunge og dyre produktionsenheder, som må producere dag og nat hele året 25 for at forrente de store investeringer. De store vandmængder skal siden fjernes fra fibrene. Det giver miljøproblemer på grund af det høje vandforbrug, og mest på grund af, at en del af fibrene og de anvendte kemikalier løber ud med afløbsvandet og altså forurener dette.
30
Opfindelsen har løst problemerne med en ny fremgangsmåde til frigørelse af cellulosebaserede fibre i vand og kendetegnes ved, at frigørelsen foretages ved et højt tørstofindhold på op til 80% og efter tilsætning af en eller flere hydro-35 kolloider under kraftig mekanisk bearbejdelse.
OK 169728 B1 2
Selv om opfinderen ikke vil være bundet til nogen bestemt teori for mekanismen, som ligger bag opfindelsen, så antages det, at hydrokolloiden har en dobbelt funktion under disper-geringen. For det første giver den blandingen en høj 5 viskositet, således at røreorganets bevægelse bringes ud i massen til de enkelte fibre og river disse fra hinanden.
For det andet er der en kemisk affinitet mellem hydroxyl-grupperne på fibrene og på hydrokolloiden, således at kolloiden trænger ind mellem fibrene, overtrækker disse og 10 forhindrer dem derved i at reassociere.
Dispergeringen udføres i en specielt kraftig blander, med fordel i en æltemakine, f.eks. i en såkaldt kneter, med mulighed for opvarmning.
15
Opfindelsen er mest tiltænkt som fortrin til nye formemetoder for pap og papir, som baserer sig på plastisk formning ved ekstrudering, sprøjtestøbning, bestrygning, presning eller valsning. En god støbemasse til sådant brug skal ikke kun have 20 perfekt dispergerede fibre. Det er også påkrævet, at massen indeholder så meget hydrokolloid, at vandet er fuldstændigt bundet, nærmere bestemt ved at frit vand ikke kan ses på støbemassens overflade, når den er presset ud gennem et ekstrudermundstykke. Dersom frit (glinsende) vand kan ses på 25 tråden, som kommer ud af ekstrudermundstykket, går der erfaringsmæssigt kun kort tid før mundstykket er tilstoppet af fibre, som har mistet vand og hydrokolloid. Fuldstændig binding af vandet er også en fordel ved tilberedningen af støbemassen.
30 Støbemassen kan tilberedes og bruges ved forskellige temperaturer. Høj temperatur er specielt interessant, da man derved kan dispergere fibrene ved endnu højere tørstofindhold end ved almindelige temperaturer. Den Øvre grænse for temperaturen er ca. 200 °C, da cellulose og hydrokolloid så begynder 35 at misfarves og nedbrydes.
Det har vist sig, at støbemassen tåler at blive udsat for de høje tryk, som optræder under æltningen og også i ekstrudere ved formning af støbemassen.
DK 169728 B1 3
Produktion af celluloseholdige fiberprodukter kan forenkles ved/ at frigørelsen af fibrene og formningen af fiberprodukterne udføres som en sammenhængende proces, f.eks. ved at massen først æltes ved høj temperatur i 5 begyndelsen af en kogeekstruder og derefter, evt. efter nedkøling, formes i mundstykket ud fra ekstruderen eller ved at presses ind i et sprøjtestøbeværktøj.
De fibre, som med fordel kan bruges til opfindelsen, 10 er fibre af cellulose, halvkemisk masse, træmasse eller genbrugspapir.
Hydrokolloider, som kan bruges, er bl.a. stivelse, stivelsesderivat, dextrin, polyvinylalkohol, cellulose-15 derivater som carboxymetylcellulose eller hydroxyetyl-cellulose, animalsk protein som kasein, vegetabilsk protein fra f.eks. soya, plantelim som guar gum eller johannesbrødmel, alginat, syntetiske hydrokolloider som f.eks. polyacrylamid eller mel fra kornsorter som hvede, 20 havre, rug, byg etc. eller fra knolde som f.eks. kartofler eller tapioca.
Mængden af hydrokolloid, som behøves til fuldstændig vandbinding, afhænger af, hvor meget vand der indgår i massen, 25 og endnu mere af, hvor god vandbinding kolloiden giver.
Med billig hydrokolloid som f.eks. mel er kolloidmængden omtrent 4 - 20 % af vandmængden, og med supereffektiv kolloid som f.eks. polyacrylamid er det nok med omtrent 0,4 - 2 % af vandmængden.
30
Det er specielt interessant at anvende billig hydrokolloid, som må opvarmes for at gelatinere f.eks. almindelig nativ stivelse. Denne kan tilsættes i ugel-atineret form og bringes til gelatinering, efter at den 35 er blandet med fibrene og vandet, ved at tilføre varme eller ved at energien fra æltningen afgiver den nødvedige varme. Når stivelsen gelatinerer, bemærkes dette DK 169728 B1 4 tydeligt, ved at blandingen forvandles fra en inhomogen masse til en dejagtig pasta.
Både frigørelsen af fibrene og formningen af fiberpro-5 dukterne udføres nemmest ved rimeligt tørstofindhold på omkring 50 %. Efter formningen kommer imidlertid en tørring, og denne er mere omstændelig jo lavere tørstofindholdet er. Det er derfor fordelagtigt at udføre frigørelsen ved lavere tørstofindhold end formningen.
10 Eksempelvis således at frigørelsen af fibrene startes ved varm æltning ved 40 % tørstofindhold. Under denne bearbejdelse fordamper vand fra æltemaskinen, og fibrene opnår perfekt fiberfordeling, når tørstoffet er kommet op til 55 %. Pastaen bearbejdes videre i æltemaskinen 15 med varmetilførsel til tørstofindholdet er kommet op på 75 %. Selve formningen behøver så lidt højere tryk ved 75 % tørstof , end ved 55 %, men denne ulempe og ulempen med den ekstra fordampning bliver mere end opvejet af nemmere sluttørring.
20
Hydrokolloiderne har en tendens til at gøre støbemassen klæbrig og derved forårsage driftsforstyrrelser. Denne klæbrighed kan reduceres ved at tilsætte hjælpestoffer som voks eller latex-emulsioner. Klæbrigheden reduceres 25 også, ved at højne tørstofindholdet, f.eks. som beskrevet i forrige afsnit. Derved får støbemassen reduceret adhæsion til andet materiale og mere kohæsion i sig selv. Tilsætning af voks med rigtigt valgt smeltepunkt kan også højne formningshastigheden, da pastaen stivner hur-30 tigere ved afkøling f.eks. i et sprøjtestøbeværktøj.
Nedenfor beskrives en del forsøg, som er udført for at fastsætte de betingelser, der behøves, for at støbemassen efter sammenpresning til tyndt ark og nøje efter-35 syn skal fremtræde som helt homogen uden forekomst af fiberbundter.
DK 169728 B1 5
De fire første forsøg udførtes i en laboratoriemixer af typen Brabender Plasti-Corder PI 2000. Dette er en mixer, som giver meget kraftig æltning, og som kan opvarmes'. Apparatet er beregnet til at efterligne den bearbejdelse, 5 der foregår inde i de ekstrudere, som bruges i plastindustrien. Blanderen består af to tykke propelformede skovle, som roterer med lille afstand til hinanden og til blande-kammerets vægge, omtrent som i en gearpumpe. Omdrejningshastigheden ved de forsøg, som nu skal beskrives, var 30 10 omdrejninger pr. minut. Mixertemperaturen var i alle forsøg indstillet på 105 oc. Blandingens temperatur og drejningsmomentet til skovlene blev automatisk udskrevet på et diagram.
15 Til alle forsøgene blev der brugt en præblanding af 115 g ikke-trykt avispapir fugtet med 260 ml vand. Disse to grundkomponenter var blandet sammen i en almindelig køkkenblander med blandeklo af typen Braun KM 32. Denne bearbejdelse var ikke tilstrækkelig til at finfordele 20 fibrene, så præblandingen forelå som små stykker papir gennemblødt af vand.
Forsøg 1 var et kontrolforsøg uden hydrokolloid. Forsøget viste klart, at mixeren ikke formåede at omdanne massen 25 til en pasta. De store kræfter i mixeren resulterede i stedet i, at vand blev presset ud af massen med en sådan kraft, at vandstråler sprøjtede ud af maskinen. Drejningsmomentet kom hurtigt op til niveauer over 3 Nm, og det var ikke muligt at opnå en homogen fiber fordeling.
30
Forsøg 2 blev udført på samme måde som forsøg 1, men med den forskel at 30 g nativ majsstivelse var tilsat blandingen. Stivelsen gelatinerede hurtigt i mixeren, hvorved massen omdannedes til en pasta, og drejningsmomentet var 35 i begyndelsen kun 0,5 Nm. Æltningen fortsatte i 7'min-?. . . utter, og derved steg koncentrationen, da vand fordampede. Efter 7 minutter var drejningsmomentet kommet op DK 169728 B1 6 til 3 Nm, hvilket ved hastigheden på 30 omdrejninger pr. minut erfaringsmæssigt er noget af det højeste, som kan håndteres ved sprøjtestøbning af plast. Da pastaen blev taget ud af maskinen, viste den sig at være forholdsvis 5 homogen, og tørstofindholdet blev målt til 45 %.
Forsøg 3 blev udført på samme måde som forsøg 2, men med den forskel at majstivelsesmængden var fordoblet til 60 g. Forløbet i mixeren var det samme, men pastaen blev 10 mere klæbrig og havde en tendens til at klistre sig til blandekammerets inderside. Drejningsmomentet var i begyndelsen 0,5 Nm og var efter 6 minutter nået til 3 Nm. Mixeren blev så stoppet, og prøven taget ud. Den var perfekt homogen, og tørstofindholdet var 52 %.
15
Forsøg 4 blev udført som forsøg 3, men i tillæg til de 60 g majsstivelse blev der også tilsat 8 g stearinsyre. Stearinen viste sig at give to positive effekter. For det første forsvandt klæbrigheden, og dessuden kunne man 20 opnå højere tørstofindhold, inden drejningsmomentet kom op til 3 Nm. Sidstnævnte antageligt på grund af at smeltet stearin gør pastaen mere letflydende. Prøven -frigav damp i mixeren i hele 10 minutter, inden drejningsmomentet kom op til 3 Nm, og da prøven derefter 25 blev taget ud, viste den et tørstofindhold på 58 %.
Fiberfordelingen var perfekt.
Forsøg 5 Blev udført for at fastlægge betydningen af kraftig æltning. Forsøg 4 blev gentaget, men i køkken-30 blanderen Braun KM 32 i stedet for i Brabendermixeren. Prøven blev vekselvis varmet til 95 °C i mikrobølgeovn og blandet i køkkenblanderen. Selv om denne behandling blev udført i hurtig rækkefølge og gentaget mange gange, var det umuligt at opnå god homogenisering, hvorfor dét 35 må konstateres, at kraftig mekanisk bearbejdelse er nødvendig til udøvelse af opfindelsen.
DK 169728 B1 7
Forsøg 6 blev udført direkte i en dobbeltsnekkeekstruder beregnet til plast af typen Berstorf EO 7618/86.
Blandingen var større end til forsøgene ovenfor, men blandingsforholdet var nogenlunde det samme som ved 5 forsøgene 4 og 5, nemlig 115 g ikke-trykt avispapir fugtet med 260 ml vand og tilsat 60 g majsstivelse samt 13 g stearinsyre. Temperaturen i ekstruderen blev indstillet på 95 °C. Ekstruderen forvandlede den inhomogene blanding effektivt til en homogen pasta, som kom ud af 10 ekstruderens mundstykke i form af en tråd på 1 mm i diameter. Fiberfordelingen var perfekt.
Der skete en forsampning af vand fra den varme pastatråd, da den forlod mundstykket. Ved at lade pastaen· passere gentagne gange gennem ekstruderen, var det 15 muligt, at komme op i tørstofindhold til 80 %, inden pastaen blev så hård og sprød ved 95 °C, at den havde mistet sin formbarhed.
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Claims (11)
1. Fremgangsmåde til frigørelse af cellulosebaserede fibre fra hinanden i vand, kendetegnet ved, at frigørelsen foretages ved et højt tørstofindhold på op til 80 % efter tilsætning af en eller flere hydrokolloider under kraftig mekanisk bearbejdelse.
2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at mængden af hydrokolloid er så stor, at vandet bindes fuldstændigt.
3. Fremgangsmåde ifølge krav 1 eller 2, kendetegnet ved, at frigørelsen udføres ved temperaturer op til ca. 200 °C.
4. Fremgangsmåde ifølge kravene 1-3, kendetegnet ved, at frigørelsen udføres ved så høje tryk som· der kan danne sig i ekstrudere.
5. Fremgangsmåde ifølge kravene 1-4, kendetegnet ved, at frigørelsen danner første del af en sammenhængende produktion, hvor massen først æltes i begyndelsen af en ekstruder for så direkte at formes i ekstrudermundstykket eller i et sprø j te støbeværktøj.
6. Fremgangsmåde ifølge kravene 1-5, kendetegnet ved, at de anvendte cellulosebaserede fibre er fibre fra cellulose, halvkemisk masse, træmasse eller genbrugspapir. DK 169728 B1 9
7. Fremgangsmåde ifølge kravene 1-6, kendetegnet ved, at hydrokolloiden består af stivelse.
8. Fremgangsmåde ifølge kravene 1-7, kendetegnet ved, at hydrokolloiden tilsættes i ugelatineret form og bringes til gelatinering ved at tilføre energi til . blandingen.
9. Fremgangsmåde ifølge et eller flere af kravene 1-8, kendetegnet ved, at blandingens vandindhold reduceres ved fordampning under frigørelsen og/eller mellem frigørelse og formning.
10. Fremgangsmåde ifølge et eller flere af kravene 1-9, kendetegnet ved, at voks eller latex tilsættes for at forbedre formbarheden.
11. Støbemasse egnet til plastisk formning af cellulose-holdige fiberprodukter, kendetegnet ved, at massen er fremstillet ved fremgangsmåden ifølge et eller flere af kravene 1-10.
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK011793A DK169728B1 (da) | 1993-02-02 | 1993-02-02 | Fremgangsmåde til frigørelse af cellulosebaserede fibre fra hinanden i vand og støbemasse til plastisk formning af celluloseholdige fiberprodukter |
JP51753794A JP3308273B2 (ja) | 1993-02-02 | 1994-01-27 | セルロースベース繊維を水中で分散させる方法 |
AT94905009T ATE160829T1 (de) | 1993-02-02 | 1994-01-27 | Verfahren zur trennung cellulosehaltigen fasern in wasser |
EP94905009A EP0683831B1 (en) | 1993-02-02 | 1994-01-27 | A method to separate cellulose based fibers from each other in water |
DE69407170T DE69407170T2 (de) | 1993-02-02 | 1994-01-27 | Verfahren zur trennung cellulosehaltigen fasern in wasser |
PCT/DK1994/000045 WO1994018384A1 (en) | 1993-02-02 | 1994-01-27 | A method to separate cellulose based fibers from each other in water and a moulding composition for plastic forming of cellulose containing fiber products |
CA002153982A CA2153982A1 (en) | 1993-02-02 | 1994-01-27 | A method to separate fibres from each other in water and a moulding composition for plastic forming of fibre products |
PL94310084A PL310084A1 (en) | 1993-02-02 | 1994-01-27 | Method of separating cellulose fibre in water and moulding compound for plastic forming of cellulose containing fibrous products |
US08/500,890 US5849155A (en) | 1993-02-02 | 1994-01-27 | Method for dispersing cellulose based fibers in water |
HU9502284A HU215550B (hu) | 1993-02-02 | 1994-01-27 | Eljárás szálas keverék előállítására cellulózalapú szálak diszpergálásával vízben, és annak formázására |
NO952674A NO307895B1 (no) | 1993-02-02 | 1995-07-06 | FremgangsmÕte for Õ dispergere fibre i vann samt tilsvarende fremgangsmÕte med etterfølgende formgivning av den resulterende blandingen uten signifikant avrenning av vann |
FI953654A FI116906B (fi) | 1993-02-02 | 1995-08-02 | Menetelmä selluloosapohjaisten kuitujen erottamiseksi toisistaan vedessä sekä valumassa selluloosaa sisältävien kuitutuotteiden plastiseen muovaukseen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK11793 | 1993-02-02 | ||
DK011793A DK169728B1 (da) | 1993-02-02 | 1993-02-02 | Fremgangsmåde til frigørelse af cellulosebaserede fibre fra hinanden i vand og støbemasse til plastisk formning af celluloseholdige fiberprodukter |
Publications (3)
Publication Number | Publication Date |
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DK11793D0 DK11793D0 (da) | 1993-02-02 |
DK11793A DK11793A (da) | 1994-08-03 |
DK169728B1 true DK169728B1 (da) | 1995-01-23 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DK011793A DK169728B1 (da) | 1993-02-02 | 1993-02-02 | Fremgangsmåde til frigørelse af cellulosebaserede fibre fra hinanden i vand og støbemasse til plastisk formning af celluloseholdige fiberprodukter |
Country Status (12)
Country | Link |
---|---|
US (1) | US5849155A (da) |
EP (1) | EP0683831B1 (da) |
JP (1) | JP3308273B2 (da) |
AT (1) | ATE160829T1 (da) |
CA (1) | CA2153982A1 (da) |
DE (1) | DE69407170T2 (da) |
DK (1) | DK169728B1 (da) |
FI (1) | FI116906B (da) |
HU (1) | HU215550B (da) |
NO (1) | NO307895B1 (da) |
PL (1) | PL310084A1 (da) |
WO (1) | WO1994018384A1 (da) |
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DE4402284A1 (de) * | 1994-01-27 | 1995-08-03 | Ibn Gmbh Dresden | Verfahren zur Herstellung von geformten, recyclingfähigen Verpackungen unter Verwendung von Altpapier |
ES2113279B1 (es) * | 1994-11-07 | 1999-07-16 | Molina Juan Moreno | Proceso y moldeado de papel y carton reciclado para la fabricacion de bovedillas. |
EP0752444B1 (en) * | 1995-07-03 | 2003-05-21 | Sony Corporation | Method of manufacturing molded pulp product |
US6479164B1 (en) | 1996-02-05 | 2002-11-12 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | Method for preparing composite materials from renewable raw materials |
EP0936245B1 (en) * | 1998-02-12 | 2004-06-02 | Daiho Industrial Co., Ltd | Molding compound for articles including a cellulose fiber and a method for molding the same |
AUPQ468299A0 (en) * | 1999-12-15 | 2000-01-20 | James Hardie Research Pty Limited | Method and apparatus for extruding cementitious articles |
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-
1993
- 1993-02-02 DK DK011793A patent/DK169728B1/da not_active IP Right Cessation
-
1994
- 1994-01-27 AT AT94905009T patent/ATE160829T1/de not_active IP Right Cessation
- 1994-01-27 US US08/500,890 patent/US5849155A/en not_active Expired - Fee Related
- 1994-01-27 PL PL94310084A patent/PL310084A1/xx unknown
- 1994-01-27 HU HU9502284A patent/HU215550B/hu not_active IP Right Cessation
- 1994-01-27 DE DE69407170T patent/DE69407170T2/de not_active Expired - Fee Related
- 1994-01-27 JP JP51753794A patent/JP3308273B2/ja not_active Expired - Fee Related
- 1994-01-27 WO PCT/DK1994/000045 patent/WO1994018384A1/en active IP Right Grant
- 1994-01-27 EP EP94905009A patent/EP0683831B1/en not_active Expired - Lifetime
- 1994-01-27 CA CA002153982A patent/CA2153982A1/en not_active Abandoned
-
1995
- 1995-07-06 NO NO952674A patent/NO307895B1/no unknown
- 1995-08-02 FI FI953654A patent/FI116906B/fi not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP0683831A1 (en) | 1995-11-29 |
NO307895B1 (no) | 2000-06-13 |
FI953654A (fi) | 1995-08-02 |
DK11793A (da) | 1994-08-03 |
EP0683831B1 (en) | 1997-12-03 |
HU215550B (hu) | 1999-01-28 |
JPH08506386A (ja) | 1996-07-09 |
DE69407170D1 (de) | 1998-01-15 |
WO1994018384A1 (en) | 1994-08-18 |
CA2153982A1 (en) | 1994-08-18 |
ATE160829T1 (de) | 1997-12-15 |
DE69407170T2 (de) | 1998-07-02 |
FI116906B (fi) | 2006-03-31 |
FI953654A0 (fi) | 1995-08-02 |
HU9502284D0 (en) | 1995-09-28 |
HUT72822A (en) | 1996-05-28 |
NO952674L (no) | 1995-07-06 |
JP3308273B2 (ja) | 2002-07-29 |
PL310084A1 (en) | 1995-11-27 |
US5849155A (en) | 1998-12-15 |
DK11793D0 (da) | 1993-02-02 |
NO952674D0 (no) | 1995-07-06 |
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A0 | Application filed | ||
B1 | Patent granted (law 1993) | ||
PBP | Patent lapsed |
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