DK164513B - PROCEDURE FOR MELT SPINNING POLYPROPYLENE FIBER - Google Patents
PROCEDURE FOR MELT SPINNING POLYPROPYLENE FIBER Download PDFInfo
- Publication number
- DK164513B DK164513B DK371184A DK371184A DK164513B DK 164513 B DK164513 B DK 164513B DK 371184 A DK371184 A DK 371184A DK 371184 A DK371184 A DK 371184A DK 164513 B DK164513 B DK 164513B
- Authority
- DK
- Denmark
- Prior art keywords
- polypropylene
- fibers
- weight
- stretching
- temperature
- Prior art date
Links
- -1 POLYPROPYLENE Polymers 0.000 title claims description 31
- 239000004743 Polypropylene Substances 0.000 title claims description 29
- 229920001155 polypropylene Polymers 0.000 title claims description 29
- 239000000835 fiber Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 19
- 238000002074 melt spinning Methods 0.000 title claims description 7
- 238000001125 extrusion Methods 0.000 claims description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 125000006289 hydroxybenzyl group Chemical group 0.000 claims 1
- 238000009987 spinning Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006379 extruded polypropylene Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000289 melt material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000004805 propylene group Chemical class [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Description
iin
DK 164513 BDK 164513 B
" Opfindelsen angår en fremgangsmåde til smeltespinding ' af polypropylenfibre, som fås efter strækning af smeltemassen under spindingen på en måde, som er i høj grad forbedret i sammenligning med, hvad der er kendt i den 5 eksisterende teknik.The invention relates to a process for melt spinning of polypropylene fibers obtained after stretching the melt during spinning in a manner which is greatly improved in comparison with what is known in the prior art.
Det er velkendt, at polypropylenfibre i mange år har haft mange anvendelsesområder, f.eks. ikke-vævede stoffer, tæpper, og beslægtede genstande.It is well known that polypropylene fibers have had many applications for many years, e.g. nonwoven fabrics, rugs, and related items.
Med den normale fremgangsmåde til fremstilling af 10 fibre indføres polypropylen i smeltestadiet i en spindedyse med et stort antal mundinger, normalt 2000-20.000. Polypropylen indføres i en sådan dyse, for at det kan få form som et garn, dvs. helheden bestående af alle filamenterne. Disse garner strækkes derpå kontinuerligt i den 15 faste fase i en ovn ved en temperatur på 90-160°C. De strækkeforhold, som normalt benyttes, ligger på 100-300%.With the normal process for producing 10 fibers, polypropylene is introduced into the melting stage in a spinning nozzle with a large number of orifices, usually 2000-20,000. Polypropylene is introduced into such a nozzle so that it can take the form of a yarn, ie. the whole consisting of all the filaments. These yarns are then continuously stretched in the solid phase in an oven at a temperature of 90-160 ° C. The stretching ratios normally used are 100-300%.
Det er også velkendt i teknikken, at et lavt strækkeforhold vil frembringe en fiber med høj residualforlængelse. Til opnåelse af den høje residualforlængelse sammen med en given 20 slutdiameter nødvendiggør det lave strækkeforhold, at der i ovnen indføres et garn med en finere begyndelsesdiameter.It is also well known in the art that a low stretch ratio will produce a high residual elongation fiber. In order to achieve the high residual elongation together with a given final diameter, the low stretching ratio necessitates the introduction of a yarn with a finer initial diameter.
Derfor må der foretages en mere betydelig strækning af smel tematerialet ved udløbet af spindedysen.Therefore, a more substantial stretching of the melt core material must be made at the exit of the spinning nozzle.
Strækkeligheden af den smeltemasse, som krydser disse 25 mundinger, afhænger navnlig af karakteren af polypropylen-garnet i smeltestadiet og navnlig af spredningen af molekylvægten af dette sidste. Desuden kan fibrene spindes opad eller nedad i overensstemmelse med den valgte proces eller også i overensstemmelse med den valgte smeltespindings-30 hastighed, idet de højeste hastigheder nås véd strækning nedad.The extensibility of the melt mass that crosses these 25 orifices depends in particular on the nature of the polypropylene yarn at the melting stage and in particular on the spread of the molecular weight of the latter. In addition, the fibers can be spun up or down according to the selected process or also according to the selected melt spinning speed, the highest speeds being reached by stretching downwards.
I øjeblikket har de polypropylener, som benyttes til fremstilling af fibre, ikke tilstrækkelig forlængelsesviskositet, hvilket vil sige, en sådan viskositet, at det 35 er muligt at danne et garn med smeltematerialet ved en høj hastighed, samt at det er muligt på passende måde at bringeAt present, the polypropylenes used in the manufacture of fibers do not have sufficient elongation viscosity, that is, such a viscosity that it is possible to form a yarn with the melt material at a high rate and that it is possible to suitably bring
DK 164513 BDK 164513 B
2 dette'-'garn til opnåelse af fibre på lf5 denier i tilfælde af strækning opad ved en hastighed på ca. 50 m pr. minut.2 this '-' yarn for obtaining fibers of lf5 denier in case of stretching upwards at a rate of approx. 50 m per minute.
I tilfælde af strækning nedad tillader de normale propylener ikke, at man når høje smeltespindehastigheder på 5 ca. 500 m/minut.In the case of downward stretching, the normal propylenes do not allow high melt spinning speeds of approx. 500 m / minute.
Til afhjælpning af disse ulemper har man allerede foreslået at indføre peroxider i polypropylenblandinger. Dette har imidlertid ikke ført til gunstige resultater i tilfælde af strækning opad, fordi viskositetetn af blandingen har 10 været for lav til at muliggøre dannelsen af et garn. Desuden bliver det materiale, som indeholder disse peroxider delvis nedbrudt, idet det typisk har et højt smelteflydeindeks og en meget lav viskositet, og disse egenskaber kan være uønskede til visse efterfølgende anvendelser.To remedy these disadvantages, it has already been proposed to introduce peroxides into polypropylene mixtures. However, this has not led to favorable results in the case of stretching upwards, because the viscosity of the mixture has been too low to allow the formation of a yarn. In addition, the material containing these peroxides is partially degraded, typically having a high melt flow index and a very low viscosity, and these properties may be undesirable for certain subsequent applications.
15 Der er derfor et behov for en fremgangsmåde til fremstilling af polypropylenfibre med særligt gode egenskaber i henseende til strækkelighed i smeltet tilstand.Therefore, there is a need for a process for producing polypropylene fibers having particularly good properties in terms of extensibility in the molten state.
Formålet med opfindelsen er at tilvejebringe en sådan fremgangsmåde.The object of the invention is to provide such a method.
20 Gennem den foreliggende opfindelse anvises der en fremgangsmåde til fremstilling af polypropylenfibre, som tillader en let extrudering af garner enten opad eller nedad, idet man opnår fibre med en bedre residualfor- længelse end den, som opnås med en kvalitet, som har samme 25 spindeegenskaber; normalt gælder, at jo mere peroxid- nedbrudt produktet er, desto bedre kan det spindes, men desto ringere er residualforlængelsen.The present invention provides a process for producing polypropylene fibers which allows easy extrusion of yarns either upwards or downwards, obtaining fibers with a better residual elongation than that obtained with a quality having the same spinning properties ; usually the more peroxide degraded the product, the better it can be spun, but the worse the residual elongation.
Ved fremgangsmåden ifølge opfindelsen kan der opnås polypropylenfibre med lav denier, normalt mellem 5 og 1 30 denief.By the process of the invention, low denier polypropylene fibers can be obtained, usually between 5 and 1 30 deniers.
Fremgangsmåden ifølge opfindelsen til fremstilling af polypropylenfibre med særligt gode egenskaber i henseende til strækkelighed i smeltet tilstand er ejendommelig ved det i krav l's kendetegnende del anførte.The process of the invention for producing polypropylene fibers having particularly good properties in terms of extensibility in the molten state is characterized by the characterizing part of claim 1.
35 Det skal for god ordens skyld bemærkes, at det fra DE35 It should be noted, for good measure, that from DE
fremlæggelsesskrift nr. 1.953.143 er kendt at stabiliserepresentation document No. 1,953,143 is known to stabilize
DK 164513BDK 164513B
3 polypropylen med tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)- ' -isocyanurat.3 polypropylene with tris- (3,5-di-tert.-butyl-4-hydroxy-benzyl) -isocyanurate.
Det polypropylen, som benyttes ved fremgangsmåden ifølge opfindelsen, er en krystallinsk polypropylen homo-5 polymer, som kan indeholde kernedannelsesmidler. Dette krystallinske polypropylen fås normalt ved polymerisation i nærværelse af en stereospecifik katalysator.The polypropylene used in the process of the invention is a crystalline polypropylene homopolymer which may contain nucleating agents. This crystalline polypropylene is usually obtained by polymerization in the presence of a stereospecific catalyst.
Det har overraskende vist sig, at hvis 1,3,5-tria-zin-2,3,6-(IH,3H,5H)-trioner-l,3,5-tris-3,5-bis (1,1-di-10 methylethyl)-4-hydroxyphenylmethyl, også kaldet tris--(3,5-di-tert.-buty1-4-hydroxyphenyl)-isocyanurat, indføres i en mængde på 0,01-0,5 vægt%, på basis af vægten af polypropylen, forbedres polymerens egenskaber i henseende til forlængelsesviskositet i høj grad, hvad enten stræk-15 ningen i smeltet tilstand af det extruderede polypropylen udføres opad eller nedad.Surprisingly, it has been found that if 1,3,5-triazin-2,3,6- (1H, 3H, 5H) -triones-1,3,5-tris-3,5-bis (1, 1-di-methylethyl) -4-hydroxyphenylmethyl, also called tris - (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, is introduced in an amount of 0.01-0.5% by weight , based on the weight of polypropylene, the properties of the polymer in terms of elongation viscosity are greatly improved, whether the molten state stretch of the extruded polypropylene is carried up or down.
Imidlertid har det vist sig, at de bedste resultater opnås, når forbindelsen benyttes i en mængde på 0,05-0,2 vægt%.However, it has been found that the best results are obtained when the compound is used in an amount of 0.05-0.2% by weight.
20 Når der benyttes mindre mængder end 0,01 vægt%, på basis af vægten af polypropylenet, opnås der ikke nogen virkning af betydning. Hvis man på den anden side benytter større mængder end 0,5 vægt%, opnås der ikke nogen yderligere fordel.When less than 0.01% by weight, based on the weight of the polypropylene, is used, no significant effect is obtained. On the other hand, if quantities greater than 0.5% by weight are used, no further benefit is obtained.
25 Ved strækning i smeltet tilstand af de extruderede garner opad opnår man dannelsen af fibre på 3 denier med en residual forlængelse liggende så højt som 250%, idet fibre på 1,5 denier stadig har en forlængelse på 100%. Dette resultat er helt uventet, hvis man tager i betragtning, at 30 det opnås med mundinger på en extruderingsdysé med et forhold mellem længde og diameter på 2, fordi man i tilfælde af normale blandinger, som extruderes fra den samme spindedyse, og som altså har det samme L/D-forhold, får mange brud på garnet ved en sådan strækning i smeltet 35 tilstand.By melting in the molten state of the extruded yarns upwards, the formation of fibers of 3 denier with a residual extension lying as high as 250% is obtained, with fibers of 1.5 denier still having an extension of 100%. This result is quite unexpected when one considers that it is obtained with orifices on an extrusion die having a length-to-diameter ratio of 2, because in the case of normal mixtures which are extruded from the same spinning nozzle and thus have at the same L / D ratio, many breakages of the yarn result in such a stretch in the molten state.
DK 164513 BDK 164513 B
4 "Skønt man ikke ønsker at lægge sig fast på nogen bestemt teori, antages det, at indføringen af en sådan forbindelse som tris-(3,5-di-tert.-butyl-4-hydroxyben-zyl)-isocyanurat, har en indflydelse på spredningen af 5 molekylvægten af polypropylenet. Desuden gør denne forbindelse det muligt at regulere spredningen ved hjælp af den temperatur, ved hvilken polymermaterialet, som skal behandles, indføres i spindedysen.4 "Although it is not desired to adhere to any particular theory, it is believed that the introduction of such a compound as tris- (3,5-di-tert.-butyl-4-hydroxybenzyl) -isocyanurate has a influences the spread of the molecular weight of the polypropylene, and furthermore, this compound makes it possible to regulate the spread by the temperature at which the polymeric material to be treated is introduced into the spinning nozzle.
Man har iagttaget, at fremgangsmåden ifølge op-10 findelsen kan udføres med godt resultat, hvis polymermaterialet extruderes i en spindedyse ved en temperatur på 220-280°C. Når polypropylensmeltemassen strækkes opad, udføres extruderingen ved en temperatur på 220-250°C, fortrinsvis 230-250°C, og når polypropylensmeltemassen 15 strækkes nedad, udføres extruderingen ved en temperatur på 220-280°C, fortrinsvis 230-260°C.It has been observed that the process according to the invention can be carried out successfully if the polymer material is extruded in a spinning nozzle at a temperature of 220-280 ° C. When the polypropylene melt is stretched upwards, the extrusion is carried out at a temperature of 220-250 ° C, preferably 230-250 ° C, and when the polypropylene melt mass is stretched downwards, the extrusion is performed at a temperature of 220-280 ° C, preferably 230-260 ° C.
Man benytter normalt lave temperaturer ved fremstilling af fibre med høj denier.Low temperatures are usually used in the production of high denier fibers.
Nedenstående eksempler illustrerer fremgangsmåden 20 ifølge opfindelsen.The following examples illustrate the method 20 of the invention.
Eksempel 1 0,15 vægtdele tris-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-isocyanurat indføres i 100 vægtdele polypropylen-homopolymer med et smelteflydeindeks på 25 g/10 min., 25 bestemt ved 230°C under et tryk på 2,16 kg i overensstemmelse med metoden ASTM D 1238.Example 1 0.15 parts by weight of tris (3,5-di-tert.-butyl-4-hydroxy-benzyl) isocyanurate is introduced into 100 parts by weight of polypropylene homopolymer with a melt flow index of 25 g / 10 min, determined at 230 ° C under a pressure of 2.16 kg according to the method ASTM D 1238.
Den fremkomne blanding indføres i en spindedyse ved en temperatur på 230°C. De fineste fibre, som opnås, har en denierværdi på 3, idet man benytter strækning opad ved en 30 hastighed på 50 m pr minut. Fibrene har en residual-forlængelse på 100%. L/D-forholdet for mundingerne i arket i dysen er 2.The resulting mixture is introduced into a spinning nozzle at a temperature of 230 ° C. The finest fibers obtained have a denier value of 3, using upward stretching at a speed of 50 m per minute. The fibers have a residual elongation of 100%. The L / D ratio of the orifices in the sheet of the nozzle is 2.
Til sammenligning extruderer man polypropylen indeholdende 0,05% af et normalt peroxid. Med dette 35 polypropylen er det ikke muligt ved strækning opad at opnå fibre på 3 denier.For comparison, polypropylene containing 0.05% of a normal peroxide is extruded. With this polypropylene, it is not possible to obtain fibers of 3 denier by stretching upwards.
DK 164513 BDK 164513 B
55
Eksémpel 2 0,05 vægtdele tris-(3,5-di-tert.-butyl-4-hydroxyben-zyl)-isocyanurat indføres i 100 vægtdele af det polypropylen, som benyttes i eksempel 1.Example 2 0.05 parts by weight of tris (3,5-di-tert.-butyl-4-hydroxybenzyl) isocyanurate is introduced into 100 parts by weight of the polypropylene used in Example 1.
5 Den fremkomne blanding indføres derefter i en spindedyse ved en temperatur på 250°C.The resulting mixture is then introduced into a spinning nozzle at a temperature of 250 ° C.
Der fremstilles fibre på 3 denier ved strækning opad ved en hastighed på 50 m pr. min. Disse fibre har en resi-dualforlængelse på 250%. Fibre på 1,5 denier har en resi-10 dualforlængelse på 100%.Three denier fibers are produced by stretching upwards at a rate of 50 m / s. mine. These fibers have a residual dual extension of 250%. 1.5 denier fibers have a 100% resi-10 dual extension.
I dette eksempel er det muligt at fremstille finere garner direkte ved smeltespinding. Dette tillader brugen af lavere strækkeforhold under passagen i den vandrette ovn.In this example, it is possible to produce finer yarns directly by melt spinning. This allows the use of lower stretching conditions during passage in the horizontal oven.
L/D forholdet for mundingerne i arket i dysen er 2.The L / D ratio of the orifices in the sheet of the nozzle is 2.
15 Man konstaterer 1 brud pr. time ved den benyttede spindedyse. Denne spindedyse har 180.000 mundinger.15 One break is found per hour at the spinning nozzle used. This spinning nozzle has 180,000 mouths.
Eksempel 3Example 3
Man fremstiller samme blanding som i eksempel 2.The same mixture is prepared as in Example 2.
Denne blanding extruderes derefter ved en temperatur 20 på 260°C i en arkdyse, som arbejder med strækning nedad.This mixture is then extruded at a temperature 20 of 260 ° C in a downwardly extending nozzle.
Der fremstilles fibre på 1,5 denier med en smelte-spindingshastighed på ca. 500 m pr. minut.1.5 denier fibers are produced with a melt spinning rate of approx. 500 m per minute.
Antallet af brud pr. time overstiger ikke 3 med den benyttede spindedyse. Denne spindedyse har 12.000 mundinger.The number of breaks per hour does not exceed 3 with the spinning nozzle used. This spinning nozzle has 12,000 mouths.
25 30 3525 30 35
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU84944A LU84944A1 (en) | 1983-08-02 | 1983-08-02 | PROCESS FOR PRODUCING POLYPROPYLENE FIBERS |
| LU84944 | 1983-08-02 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK371184D0 DK371184D0 (en) | 1984-07-31 |
| DK371184A DK371184A (en) | 1985-02-03 |
| DK164513B true DK164513B (en) | 1992-07-06 |
| DK164513C DK164513C (en) | 1993-08-02 |
Family
ID=19730129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK371184A DK164513C (en) | 1983-08-02 | 1984-07-31 | PROCEDURE FOR MELT SPINNING POLYPROPYLENE FIBER |
Country Status (10)
| Country | Link |
|---|---|
| BE (1) | BE900217A (en) |
| CA (1) | CA1230213A (en) |
| CH (1) | CH661274A5 (en) |
| DE (1) | DE3428068C2 (en) |
| DK (1) | DK164513C (en) |
| FR (1) | FR2550231B1 (en) |
| GB (1) | GB2144367B (en) |
| IT (1) | IT1180213B (en) |
| LU (1) | LU84944A1 (en) |
| NL (1) | NL192834C (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3531483A (en) * | 1968-10-25 | 1970-09-29 | Goodrich Co B F | Hydroxyphenylalkyleneyl isocyanurates |
| GB1380449A (en) * | 1972-05-12 | 1975-01-15 | Ici Ltd | Polypropylene composition |
| NZ186352A (en) * | 1977-02-07 | 1979-06-08 | Ici Ltd | Propylene polymer containing isocyanurate anti oxidant |
| US4185004A (en) * | 1977-04-27 | 1980-01-22 | Phillips Petroleum Company | Multi-component stabilizing system for pigmented polyolefins |
| FR2393829A1 (en) * | 1977-06-07 | 1979-01-05 | Solvay | PROCESS FOR THE EXTRUSION OF COMPOSITIONS BASED ON ALPHA-OLEFIN POLYMERS |
-
1983
- 1983-08-02 LU LU84944A patent/LU84944A1/en unknown
-
1984
- 1984-07-16 CH CH3446/84A patent/CH661274A5/en not_active IP Right Cessation
- 1984-07-18 GB GB08418245A patent/GB2144367B/en not_active Expired
- 1984-07-20 CA CA000459322A patent/CA1230213A/en not_active Expired
- 1984-07-25 BE BE0/213375A patent/BE900217A/en not_active IP Right Cessation
- 1984-07-30 DE DE3428068A patent/DE3428068C2/en not_active Expired - Fee Related
- 1984-07-31 DK DK371184A patent/DK164513C/en not_active IP Right Cessation
- 1984-08-01 NL NL8402407A patent/NL192834C/en not_active IP Right Cessation
- 1984-08-02 FR FR8412244A patent/FR2550231B1/en not_active Expired
- 1984-08-02 IT IT22199/84A patent/IT1180213B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DE3428068A1 (en) | 1985-02-21 |
| CA1230213A (en) | 1987-12-15 |
| GB2144367B (en) | 1986-11-05 |
| GB8418245D0 (en) | 1984-08-22 |
| GB2144367A (en) | 1985-03-06 |
| NL8402407A (en) | 1985-03-01 |
| LU84944A1 (en) | 1985-04-24 |
| BE900217A (en) | 1985-01-25 |
| NL192834C (en) | 1998-03-04 |
| CH661274A5 (en) | 1987-07-15 |
| NL192834B (en) | 1997-11-03 |
| IT1180213B (en) | 1987-09-23 |
| IT8422199A0 (en) | 1984-08-02 |
| DK371184D0 (en) | 1984-07-31 |
| DE3428068C2 (en) | 1993-09-30 |
| DK371184A (en) | 1985-02-03 |
| FR2550231A1 (en) | 1985-02-08 |
| FR2550231B1 (en) | 1987-06-05 |
| DK164513C (en) | 1993-08-02 |
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