EP0351397A2 - Use of a polyamide-polyamine-epichlor hydrine precondensate as an impregnation agent for paper - Google Patents
Use of a polyamide-polyamine-epichlor hydrine precondensate as an impregnation agent for paper Download PDFInfo
- Publication number
- EP0351397A2 EP0351397A2 EP89890186A EP89890186A EP0351397A2 EP 0351397 A2 EP0351397 A2 EP 0351397A2 EP 89890186 A EP89890186 A EP 89890186A EP 89890186 A EP89890186 A EP 89890186A EP 0351397 A2 EP0351397 A2 EP 0351397A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper
- precondensate
- polyamine
- polyamide
- epichlorohydrin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
Description
Es ist bekannt, zur Oberflächenbehandlung von Papier, insbesondere von Rohpapieren für die Wellpappenfabrikation, vorwiegend Stärke in gelöster Form einzusetzen, um auf diesem Wege die geforderten Festigkeitseigenschaften zu erreichen. Der Einsatz erfolgt dabei bei der Papierherstellung vor der Nach-Trockenpartie in der Leimpresse.It is known to primarily use starch in dissolved form for the surface treatment of paper, in particular raw paper for the manufacture of corrugated cardboard, in order to achieve the required strength properties in this way. It is used in paper production before the after-dryer section in the size press.
Durch die DE-OS 29 51 507 wurde es bekannt, in Papierleimstoffen ein kationisches Harz als Reaktionsprodukt von Epichlorhydrin mit einem Polymer der Gruppe eines Aminopolyamids, das aus einer Dicarbonsäure und einem Polyalkylenpolyamin mit zwei primären Amingruppen und wenigstens einer sekundären oder tertiären Aminogruppe besteht, einzusetzen.From DE-OS 29 51 507 it has become known to use a cationic resin in paper sizes as a reaction product of epichlorohydrin with a polymer from the group of an aminopolyamide, which consists of a dicarboxylic acid and a polyalkylene polyamine with two primary amine groups and at least one secondary or tertiary amino group .
Durch die US-PS 4 336 835 wurde eine härtbare wässerige Lösung eines duroplastischen Harzes bekannt, welche einen relativ hohen Feststoffanteil besitzt und eine verbesserte Naßfestigkeit von Papier erzielen läßt. Die Lösung wird dabei durch Umsetzung einer aliphatischen Dicarbonsäure mit einem Polyalkylen-Polyamin zwecks Bildung eines Polyamid-Polyamins hergestellt, welches danach mit Epichlorhydrin umgesetzt wird. Die erste Reaktion wird dabei bei einem molaren Verhältnis zwischen aliphatischer Dicarbonsäure und Polyalkylen-Polyamin von 1 : 1,0 bis 1,2 ausgeführt, bis eine Viskosität der 50%igen wässerigen Lösung bei 25°C an Polyamid-Polyamin von 400 bis 1000 cps erreicht wird, und die zweite Umsetzung, bei der Epichlorhydrin in einem Ausmaß von 1,6 bis 1,7 Mol pro Mol des Polyamid sekundären Amins eingesetzt wird, wird solange fortgesetzt, bis die Viskosität der 15%igen Lösung des sich ergebenden Produktes einen Wert von 30 bis 150 cps bei 25°C erreicht.A curable aqueous solution of a thermosetting resin has become known from US Pat. No. 4,336,835, which has a relatively high solids content and allows improved wet strength of paper to be achieved. The solution is prepared by reacting an aliphatic dicarboxylic acid with a polyalkylene polyamine to form a polyamide polyamine, which is then reacted with epichlorohydrin. The first reaction is carried out at a molar ratio between aliphatic dicarboxylic acid and polyalkylene polyamine of 1: 1.0 to 1.2 until a viscosity of the 50% strength aqueous solution at 25 ° C. of polyamide polyamine of 400 to 1000 cps is reached, and the second reaction, in which epichlorohydrin is used in an amount of 1.6 to 1.7 moles per mole of the polyamide secondary amine, is continued until the viscosity of the 15% solution of the resulting product becomes a value 30 to 150 cps at 25 ° C.
Als aliphatische Dicarbonsäure wird u.a. Adipinsäure empfohlen und als Polyalkylen-Polyamin Triäthylentetramin.As an aliphatic dicarboxylic acid, i.a. Adipic acid recommended and as polyalkylene-polyamine triethylene tetramine.
Zur Steigerung der Festigkeitseigenschaften wurde auch bereits empfohlen, Kombinationen von Naßfestmitteln mit Kunststoffdispersionen einzusetzen. Alle diese Mittel haben jedoch bei ihrer Verwendung den Nachteil, daß Feststoffgehalte von höchstens 10 % in der Leimpresse zur Anwendung kommen konnten, da sonst das erforderliche Fließverhalten der Imprägnierflüssigkeit nicht erreicht werden konnte.To increase the strength properties, combinations of wet strength agents have already been recommended use with plastic dispersions. However, all of these agents have the disadvantage, when used, that solids contents of at most 10% could be used in the size press, since otherwise the required flow behavior of the impregnation liquid could not be achieved.
Nun kann durch Einsatz von Sulfitablauge in der Leimpresse ein wesentlich höherer Feststoffgehalt erreicht werden. Versuche, anstelle von Stärke andere Substanzen einzusetzen, scheiterten jedoch an der hohen Wasserlöslichkeit der in der Sulfitablauge enthaltenen Ligninsulfonate. Die hohe Wasserlöslichkeit führte nämlich bei der Verarbeitung des Wellpappenrohpapieres an den Riffelwalzen der Wellpappenanlage zu klebrigen Ablagerungen, was Abrißfolgen nach sich zog.A much higher solids content can now be achieved by using sulfite waste liquor in the size press. Attempts to use other substances instead of starch failed due to the high water solubility of the lignin sulfonates contained in the sulfite waste liquor. The high water solubility in the processing of the corrugated base paper led to sticky deposits on the corrugated rollers of the corrugated board plant, which resulted in tearing consequences.
Überraschenderweise wurde nun gefunden, daß die vorerwähnten Probleme dadurch einer Lösung zugeführt werden können, daß Polyamid-Polyamin-Epichlorhydrin-Vorkondensat, dessen Kondensationsgrad bei 500 liegt und einem Aktivgehalt von 12 % entspricht, im Gemisch mit Ligninsulfonsäure, gegebenenfalls als Calciumsalz der Sulfonsäure, als Zusatz zur Imprägnierflüssigkeit für die Oberflächenbehandlung von Papier, insbesondere von Wellpapperohpapier, verwendet wird. Durch die vorstehend erwähnte erfindungsgemäße Maßnahme als Zusatz zur Imprägnierflüssigkeit konnte eine ausreichende Quellfestausrüstung und eine Steigerung der Festigkeitswerte des Papiers, insbesondere des CMT-Wertes (DIN 53143) erzielt werden. Die Chlorkomponente des Vorkondensats läßt hinsichtlich Umweltbelastung keine Schwierigkeiten erwarten, weil Chlor mit dem in der Sulfitablauge enthaltenen Calzium zu CaCl₂ reagiert und kein freies Chlor oder Salzsäure gebildet wird.Surprisingly, it has now been found that the aforementioned problems can be solved by a solution that polyamide-polyamine-epichlorohydrin precondensate, the degree of condensation of which is 500 and corresponds to an active content of 12%, in a mixture with lignosulfonic acid, optionally as the calcium salt of sulfonic acid, as Additive to the impregnation liquid for the surface treatment of paper, in particular corrugated raw paper, is used. With the measure according to the invention mentioned above as an additive to the impregnation liquid, it was possible to achieve adequate swelling resistance and an increase in the strength values of the paper, in particular the CMT value (DIN 53143). The chlorine component of the pre-condensate does not pose any difficulties with regard to environmental pollution, because chlorine reacts with the calcium contained in the sulfite waste liquor to form CaCl₂ and no free chlorine or hydrochloric acid is formed.
Das Imprägniermittel, enthaltend Sulfitablauge, ist erfindungsgemäß dadurch gekennzeichnet, daß es 75 - 95 Gew.-% Sulfitablauge, bevorzugt mit einem Feststoffgehalt von ca. 50 %, im Gemisch mit 0 - 20 Gew.-% Stärke und mindestens 5 Gew.-% eines Polyamid-Polyamin-Epichlorhydrin (PPE)-Vorkondensats, bezogen auf Sulfitablauge, ge gegebenenfalls mit Amino-Sulfo-Carboxymethylcellulose in einer Menge von 0,1 %, bezogen auf den Gesamtansatz (Sulfitablauge und PPE Harz), als Kondensationskatalysator, enthält. Bei Verwendung des erfindungsgemäß zusammengesetzten Imprägniermittels auf der Papiermaschine konnte offenbar durch Vernetzung der Ligninsulfonsäuren mit dem genannten Vorkondensat und den Hexosen und Pentosen eine Erhöhung der Festigkeitswerte, insbesondere des CMT-Wertes, erzielt werden.According to the invention, the impregnating agent containing sulfite waste liquor is characterized in that it contains 75-95% by weight sulfite waste liquor, preferably with a solids content of approx. 50%, in a mixture with 0-20% by weight starch and at least 5% by weight. a polyamide-polyamine-epichlorohydrin (PPE) precondensate, based on sulfite waste liquor, ge optionally with amino-sulfo-carboxymethyl cellulose in an amount of 0.1%, based on the total batch (sulfite waste liquor and PPE resin), as a condensation catalyst. When using the impregnating agent composed according to the invention on the paper machine, it was evidently possible to achieve an increase in the strength values, in particular the CMT value, by crosslinking the lignosulfonic acids with the precondensate mentioned and the hexoses and pentoses.
In weiterer Ausgestaltung der Erfindung wird vorgesehen, daß das Polyamid-Polyamin-Epichlorhydrin-Vorkondensat aus den Grundstoffen Adipinsäure, Triäthylentetramin und Epichlorhydrin so aufgebaut ist, daß ein mittleres Molekulargewicht von 20000 bei einem Chlorgehalt von 16 - 18 %, bevorzugt 17 %, einer Kondensationstemperatur von 180°C und einer Reaktionszeit von 45 min resultiert.In a further embodiment of the invention it is provided that the polyamide-polyamine-epichlorohydrin precondensate is made up of the basic materials adipic acid, triethylenetetramine and epichlorohydrin in such a way that an average molecular weight of 20,000 with a chlorine content of 16-18%, preferably 17%, of a condensation temperature of 180 ° C and a reaction time of 45 min results.
Mit sinkendem Stärkeanteil im erfindungsgemäßen Imprägniermittel kann die Papiermaschinengeschwindigkeit erhöht werden. Dies ist vor allem möglich, weil bei höherem Feststoffgehalt eine geringere Wassermenge in der Trockenpartie zu verdampfen ist.As the proportion of starch in the impregnating agent according to the invention decreases, the paper machine speed can be increased. This is possible above all because with a higher solids content, a smaller amount of water has to be evaporated in the dryer section.
Bei Anwendung des erfindungsgemäßen Imprägniermittels können Stoffqualitäten für die Wellenlage der Wellpappe erzielt werden, deren Festigkeitsniveau jenes von Fluting (d.i. eine Wellenlage, deren Hauptanteil Primärfasern sind, wodurch auch ohne chemische Zusätze eine hinreichende Steifigkeit erzielt wird) übersteigt, wenn hochwertigere Altpapierrohstoffe eingesetzt werden.When using the impregnating agent according to the invention, material qualities can be achieved for the corrugated cardboard corrugation, the strength level of which exceeds that of fluting (i.e. a corrugation, the main part of which is primary fibers, as a result of which sufficient rigidity is achieved even without chemical additives) if higher-quality waste paper raw materials are used.
Bevorzugt wird eine Imprägnierflüssigkeit eingesetzt, die aus 75 % Sulfitablauge (bei einem Feststoffgehalt von ca. 50 %), 20 % Stärke und 5 % Polyamid-Polyamin-Epichlorhydrin-Vorkondensat, bezogen auf die Sulfitablauge, 12 % akt., besteht. Als Kondensationskatalysator kann AminoSulfo-Carboxymethylcellulose in einer Menge von 0,1 %, bezogen auf den Gesamtansatz (Sulfitablauge und PPE Harz), Verwendung finden.An impregnation liquid is preferably used which consists of 75% sulfite waste liquor (with a solids content of approx. 50%), 20% starch and 5% polyamide-polyamine-epichlorohydrin precondensate, based on the sulfite waste liquor, 12% act. AminoSulfo-Carboxymethylcellulose can be used as a condensation catalyst in an amount of 0.1%, based on the total batch (sulfite waste liquor and PPE resin).
Eine solche Imprägnierflüssigkeit wird in einem Ver fahren bevorzugt eingesetzt, bei dem erfindungsgemäß das Imprägniermittel auf einen Feststoffgehalt von ca. 27 Gew.-%, bevorzugt mit Wasser, verdünnt wird und danach in an sich bekannter Weise in der Leimpresse vor der Nach-Trockenpartie der Papiermaschine eingesetzt wird.Such an impregnation liquid is in a ver are preferably used, in which, according to the invention, the impregnating agent is diluted to a solids content of about 27% by weight, preferably with water, and is then used in a manner known per se in the size press before the after-dryer section of the paper machine.
Die Zusammensetzung der Sulfitablauge kann dabei wie folgt definiert werden: 65 % Calciumligninsulfonat, S-Gehalt 5 %, Molekülmasse ca. 80.000, 35 % Kohlenhydrate mit folgendem Spektrum: 43 % Manose, 30 % Glucose, 22 % Xylose, 5 % Galactose. Die Kohlenhydrate liegen in kurzkettig polymerer Form im Sinne von Oligosacchariden vor.The composition of the sulfite waste liquor can be defined as follows: 65% calcium lignin sulfonate, S content 5%, molecular weight approx. 80,000, 35% carbohydrates with the following spectrum: 43% manose, 30% glucose, 22% xylose, 5% galactose. The carbohydrates are in short-chain polymer form in the sense of oligosaccharides.
Aktivsubstanz 75 %
Bei Anwendung des erfindungsgemäßen Verfahrens kann die Leimpressenflotte von 8,5 %, wie sie bei Stärke möglich ist, bzw. von 14,5 %, wie sie bei einer Mischung von Stärke und Ligninsulfonat im Ausmaß von 1 : 1 möglich ist, auf 27 % erhöht werden. Es können daher bei Anwendung des erfindungsgemäßen Verfahrens, bei Verwendung des erfindungsgemäßen Imprägniermittels, bei Papierbahnen mit niedrigem Flächengewicht Qualitäten erzielt werden, die bei üblichen Verfahren und üblichen Imprägniermitteln erst bei höheren Flächengewichten erreicht werden.When using the method according to the invention, the size press liquor can be increased from 8.5%, as is possible with starch, or from 14.5%, as is possible with a mixture of starch and lignin sulfonate to the extent of 1: 1. increase. When using the method according to the invention, when using the impregnating agent according to the invention, it is possible to achieve qualities in paper webs with a low basis weight, which in conventional methods and conventional impregnating agents can only be achieved with higher basis weights.
Die Geschwindigkeit der Papiermaschine kann gegenüber üblichen Geschwindigkeiten um ca. 5 % erhöht werden. Bei Anwendung des erfindungsgemäßen Verfahrens kann eine Steigerung der CMT-Festigkeitswerte um bis zu 108 % gegenüber dem unbehandelten Papier, und des Berstdruckes um 66,6 %, ebenfalls gegenüber dem unbehandelten Papier, erzielt werden. Dadurch ist es möglich, schlechtere Rohstoffe, d.h. praktisch 100 % gemischtes Altpapier (B12), als Faserstoffeintrag für die Herstellung von Wellenpapieren einzusetzen. Somit kann eine bedeutende Einsparung bei der Herstellung der Wellenpapiere erzielt werden.The speed of the paper machine can be increased by approx. 5% compared to normal speeds. When using the method according to the invention, the CMT strength values can be increased by up to 108% compared to the untreated paper, and the burst pressure by 66.6%, also compared to the untreated paper. This makes it possible to use poorer raw materials, ie practically 100% mixed waste paper (B12), as fiber input for the production of corrugated paper. This means that significant savings can be made in the production of the corrugated paper.
Eine Beeinträchtigung der Umweltbelastung durch den großen Anteil von Ligninsulfonaten ist bei Wiederauflösung der mit Ligninsulfonaten behandelten Papiere nicht zu befürchten. Versuche haben gezeigt, daß ein zwar verlangsamter CSB-Abbau (chemischer Sauerstoffbedarf) in der Kläranlage festgestellt wurde, daß insgesamt jedoch bei der biologischen Abwasserreinigung keine Schwierigkeiten zu erwarten sind. Die Ursache hiefür dürfte der Umstand sein, daß die Ligninsulfonate auf die Faser aufziehen und durch die dabei auftretende Vernetzung eine sehr hohe Faserretention erzielt wird.There is no reason to fear that the large proportion of lignin sulfonates will impair the environmental impact if the papers treated with lignin sulfonates are redissolved. Experiments have shown that although COD degradation (chemical oxygen demand) was slowed down in the sewage treatment plant, overall no difficulties are to be expected in biological wastewater treatment. The reason for this is probably the fact that the lignin sulfonates are drawn onto the fiber and that the resulting crosslinking results in very high fiber retention.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT1803/88 | 1988-07-12 | ||
AT180388A AT392809B (en) | 1988-07-12 | 1988-07-12 | IMPREGNATING AGENT FOR PAPER AND METHOD FOR IMPREGNATING PAPER |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0351397A2 true EP0351397A2 (en) | 1990-01-17 |
EP0351397A3 EP0351397A3 (en) | 1991-05-15 |
EP0351397B1 EP0351397B1 (en) | 1993-12-22 |
Family
ID=3521313
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890890186 Expired - Lifetime EP0351397B1 (en) | 1988-07-12 | 1989-07-12 | Use of a polyamide-polyamine-epichlor hydrine precondensate as an impregnation agent for paper |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0351397B1 (en) |
AT (1) | AT392809B (en) |
DE (1) | DE58906478D1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113690062A (en) * | 2021-07-28 | 2021-11-23 | 华南理工大学 | MXene/polypyrrole paper-based electrode material and preparation method and application thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8118976B2 (en) | 2007-05-23 | 2012-02-21 | Akzo Nobel N.V. | Process for the production of a cellulosic product |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2018088A1 (en) * | 1969-04-18 | 1971-02-18 | Unilever Nv | Process for treating cardboard |
FR2444750A1 (en) * | 1978-12-22 | 1980-07-18 | Hercules Inc | IMPROVED COMPOSITIONS CONTAINING A DIMENED CETENE FOR PRIMING PAPER. |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL231136A (en) * | 1957-09-05 | |||
JPS54159496A (en) * | 1978-06-07 | 1979-12-17 | Sumitomo Chem Co Ltd | Preparation of aqueous solution of cationic thermosetting resin |
-
1988
- 1988-07-12 AT AT180388A patent/AT392809B/en not_active IP Right Cessation
-
1989
- 1989-07-12 DE DE89890186T patent/DE58906478D1/en not_active Expired - Fee Related
- 1989-07-12 EP EP19890890186 patent/EP0351397B1/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2018088A1 (en) * | 1969-04-18 | 1971-02-18 | Unilever Nv | Process for treating cardboard |
FR2444750A1 (en) * | 1978-12-22 | 1980-07-18 | Hercules Inc | IMPROVED COMPOSITIONS CONTAINING A DIMENED CETENE FOR PRIMING PAPER. |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113690062A (en) * | 2021-07-28 | 2021-11-23 | 华南理工大学 | MXene/polypyrrole paper-based electrode material and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
EP0351397A3 (en) | 1991-05-15 |
DE58906478D1 (en) | 1994-02-03 |
EP0351397B1 (en) | 1993-12-22 |
ATA180388A (en) | 1990-11-15 |
AT392809B (en) | 1991-06-25 |
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