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EP0187666B1 - Internal sizing process in the manufacture of paper, cardboard, boards and other cellulosic materials - Google Patents

Internal sizing process in the manufacture of paper, cardboard, boards and other cellulosic materials Download PDF

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Publication number
EP0187666B1
EP0187666B1 EP86100189A EP86100189A EP0187666B1 EP 0187666 B1 EP0187666 B1 EP 0187666B1 EP 86100189 A EP86100189 A EP 86100189A EP 86100189 A EP86100189 A EP 86100189A EP 0187666 B1 EP0187666 B1 EP 0187666B1
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EP
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Prior art keywords
dicyandiamide
resin
cationic
sizing
paper
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EP86100189A
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German (de)
French (fr)
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EP0187666A1 (en
Inventor
Rudolf Dr. Eichinger
Horst Dr. Michaud
Josef Dr. Seeholzer
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Evonik Operations GmbH
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SKW Trostberg AG
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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
    • 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
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/50—Acyclic compounds

Definitions

  • the invention relates to a method for internal sizing in the production of paper, cardboard, cardboard and other cellulose-containing materials with and without fillers and / or coating pigments under neutral to weakly basic pH conditions without the use of aluminum salts.
  • Paper production requires a mediator or a fixing agent to bind the resin glue to the fiber surface, since both the resin glue and the cellulose fibers are electronegatively charged and repel each other.
  • Alum aluminum sulfate hydrate
  • Alum is used almost exclusively for this purpose in the production of the paper in an acidic medium, with the best sizing being achieved at a pH value of 4.5 to 5.5.
  • papers produced in this way are not resistant to aging as a result of progressive hydrolysis.
  • aluminum sulfate reacts with calcium carbonate, which is often used as a pigment and filler under neutral conditions, with the elimination of carbon dioxide, which leads to foaming and hole formation on the paper web. Failing calcium sulfate leads to deposits on the machine, so that trouble-free paper production is not possible. Since no substitute has yet been found for the aluminum sulfate, it is not possible to use the usual resin glue in paper production under neutral conditions, but had to fall back on synthetic glue, which made paper production considerably more expensive.
  • a modified pseudo-neutral paper making method is described in Japanese Patent Laid-Open No. 83-174696.
  • a dicyandiamide-formaldehyde condensation product is added to the aluminum sulfate as an additional agent.
  • this method still has the disadvantage that an expensive diketene resin has to be used.
  • European patent application 112 525 proposes an agent for the neutral sizing of cellulose-containing materials, which consists of water, an alcohol which is soluble in water to an unlimited extent, alkali metal or aluminum hydroxide and a saturated or unsaturated fatty acid with 12 to 24 carbon atoms.
  • the aim of the neutral paper production process is to largely reduce or eliminate the use of aluminum sulfate and to replace kaolin as filler or pigment with calcium carbonate.
  • the latter is less expensive than kaolin and its whiteness exceeds that of kaolin. Due to the more favorable flow behavior of calcium carbonate, higher degrees of filling can also be achieved in the paper. In addition, the corrosion on the machine equipment is reduced and the quality of the paper, in particular its resistance to aging, is significantly improved.
  • ketene resins are used together with cationic resins as wet strength agents, whereby a certain sizing effect is achieved.
  • Co-condensation products of dicyandiamide, urea and formaldehyde are used as cationic resins.
  • EP-A 82 373 discloses a process for sizing paper, in which a very special cationic resin is used.
  • the resin to be used according to this process is obtained in a three-step process from dicyandiamide formaldehyde, a polyaminopolyamide, an ammonium salt and from epihalohydrin, acrylamide or urea.
  • This condensation resin is used as a reaction accelerator (promoter) for diketene glues.
  • the present invention is based on the object of developing a paper production process which operates in neutral to weakly basic pH ranges and avoids the disadvantages of the previously known processes under these conditions.
  • This object is achieved by a process for internal sizing in the production of paper, cardboard, cardboard and other cellulose-containing materials with and without fillers and / or pigments by natural or synthetic sizing agents under neutral to weakly basic pH conditions without the use of aluminum salts, which characterized in that the sizing is carried out with the addition of a cationic dicyandiamide resin based on a condensation product of dicyandiamide, with formaldehyde and at least one inorganic or organic acid and / or at least one ammonium or amine salt thereof.
  • the cationic dicyandiamide resins are able to flocculate and fix natural sizing agents under neutral to weakly basic pH conditions. Even without the addition of aluminum sulfate, full sizing can therefore be achieved with the aid of such dicyandiamide resins.
  • Cationic dicyandiamide resins which have a high positive charge and which are therefore able to precipitate anionic, high molecular weight substances quickly and practically quantitatively have proven to be particularly suitable. These resins are expediently not made too acidic, so that after mixing with the stock suspension the pH does not drop significantly below 7.
  • the cationic dicyandiamide resins used according to the invention can be prepared, for example, by reacting 1 mol of dicyandiamide with 1.0 to 4.0 mol of formaldehyde in the presence of 0.1 to 2.0 mol of at least one inorganic or organic acid and / or at least one ammonium or amine salt thereof and optionally up to 0.5 mol of a di- or polyvalent amine.
  • Condensation products prepared in this way have pH values of about 3 to about 5, are miscible with water in any ratio and can be used well as an approximately 50% aqueous solution.
  • acids such as B. strong inorganic acids such as hydrochloric acid, sulfuric acid or nitric acid.
  • weakly acidic organic acids such as. B. formic acid, acetic acid or oxalic acid is used.
  • ammonium salt can be used in resin production such.
  • B. ammonium salts of strong inorganic acids such as ammonium chloride or ammonium sulfate or ammonium salts of organic acids such as ammonium formate or acetate can be used.
  • amine salts salts of organic amines with inorganic or organic acids such as.
  • B. ethylenediamine formate or triethylenetetramine hydrochloride can be used.
  • the salts mentioned can also be used in a mixture with inorganic or organic acids.
  • Divalent or polyvalent aliphatic amines can be used as the amine component to be added. Ethylene diamine, propylene diamine, diethylene triamine and triethylene tetramine are preferably used. Their derivatives substituted on the nitrogen by hydroxyl groups can also be used, such as, for. B. mono- or diethanolamine. If amines are added, their amount is preferably at least 0.05 mol per mol of dicyandiamide.
  • Formaldehyde can be used in any form, preferably in the form of its 30 to 40% by weight aqueous solutions.
  • Neutral to weakly basic pH values are understood to mean those between pH 6.5 and 8.5, preferably between 7.0 and 8.0.
  • the condensation products obtained by the process described are clear, colorless, water-miscible products.
  • cationic dicyandiamide resins produced by other processes can also be used within the scope of the invention.
  • the amount of cationic dicyandiamide resin to be used is based on the amount of material (cellulose) and is generally 0.1 to 10% by weight; 0.2 to 5% by weight of dicyandiamide resin is preferably used, advantageously in the form of an approximately 50% strength aqueous solution.
  • Suitable products are e.g. B. rosin, animal glue, casein, starch, waxes, fatty acids and tall resins.
  • synthetic glues products based on ketene dimers, polyvinyl alcohols or polyvinyl acetates are particularly suitable. Products used as ketene dimers are those which have been produced on the basis of alkyl-substituted, dimeric ketene with an oxetanone structure, starting from long-chain fatty acids, and which are sold under the brand name Aquapel.
  • modified resin glues such as z. B. by implementing z. B.
  • rosin can be obtained with dienophilic acids and are commercially available under the brand name Purtin 3 N / S.
  • extremely finely divided dispersions of specially modified, reinforced resins e.g. Furtin BVR 510) can be used with advantage.
  • the method according to the invention now surprisingly allows combinations of cationic dicyandiamide resin with the chemically very different glue components mentioned above, to flocculate them and fix them on the fiber.
  • full or partial sizing of the paper can be achieved with natural, synthetic or modified resin glues without the aid of further aids.
  • All fillers and pigments customary in paper production can also be used in the process according to the invention, such as, for. B. kaolin, aluminum silicates, calcium silicates, oxyhydrates of aluminum, talc, satin white, gypsum, barium sulfate, barium carbonate, magnesite, zinc oxide, titanium dioxide.
  • calcium carbonate is preferably used. This can consist of natural calcium carbonate in finely ground form or it can also be precipitated calcium carbonate. Calcium carbonate is preferred because its whiteness z. B. exceeds that of kaolin and its favorable flow behavior allows particularly high filling levels in the paper to be achieved. This also has a positive influence on the paper properties: opacity is increased, whiteness is improved, aging resistance is increased and mechanical properties are increased.
  • a cationic dicyandiamide-formaldehyde resin 84 parts by weight of dicyandiamide are placed in a stirred vessel equipped with a reflux condenser with 220 parts by weight of 30% strength aqueous formaldehyde and 43 parts by weight of ammonium chloride. At room temperature, 7.7 parts by weight of ethylenediamine (78%) are then added with stirring. The reaction starts immediately and the temperature of the reaction mixture rises to 90 to 95 ° C. The reaction is complete after about 10 minutes. Then water is added to adjust the concentration of 50% by weight of solid in the resin.
  • ammonium chloride instead of ammonium chloride, an inorganic or organic acid such as. B. hydrochloric acid or formic acid can be used.
  • Leaves are formed on a Rapid-Köthen sheet former using bleached pine pulp with a freeness of 24 ° SR, resin glue (free resin glue Furtin 3N) and 50% aqueous cationic dicyandiamide resin (made from dicyandiamide, formaldehyde, ammonium chloride and ethylenediamine) and thermally formed on cylinders for 3 minutes treated at 120 ° C for a long time. After the air conditioning, the sizing was determined by the water absorption using the Cobb test (60 sec.) In accordance with DIN 531 32. The use of the cationic dicyandiamide resin was compared to alum as a sizing agent, the pH adjusting itself.
  • resin glue free resin glue Furtin 3N
  • aqueous cationic dicyandiamide resin made from dicyandiamide, formaldehyde, ammonium chloride and ethylenediamine
  • Sheet formation using calcium carbonate as a filler Sheet formation using calcium carbonate as a filler.
  • test conditions were the same as in Example 1, but weakly anionic calcium carbonate was added as a filler.
  • the weight ratio of pulp to filler was 1 2.
  • the filler was processed for 5 minutes in an Ultra Turrax (dispersing device), then mixed with the pulp for 3 minutes and then the glue and the cationic dicyandiamide resin were added.
  • Example 2 The same cationic dicyandiamide resin and the same calcium carbonate quality were used as in Example 2.
  • a synthetic product based on diketene (Aquapel 2) was used for sizing. The quality of the sizing was determined using the Cobb test.
  • Example 4 The same dicyandiamide resin and the same resin size were used as in Example 4. Weakly anionic calcium carbonate was used as the filler. The sheets were produced in a manner analogous to that given in Example 1.
  • Example 6 Using the cationic dicyandiamide resin mentioned in Example 6, the same specially modified resin size and weakly anionic calcium carbonate as filler, sheets were produced in accordance with Example 1, the Cobb values of which are shown in the following table.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
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  • Wrappers (AREA)
  • Steroid Compounds (AREA)

Abstract

1. Process for the internal sizing in the production of paper, cardboard, paperboard and other cellulose-containing materials with and without filling materials and/or pigments by natural or synthetic sizing agents under neutral to weakly basic pH conditions without the use of aluminium salts, characterised in that one carries out the sizing with the addition of a cationic dicyandiamide resin based on a condensation product of dicyandiamide with formaldehyde and at least one inorganic or organic acid and/or at least one ammonium or amine salt thereof.

Description

Die Erfindung betrifft ein Verfahren zur internen Leimung bei der Herstellung von Papier, Karton, Pappen und anderen cellulosehaltigen Materialien mit und ohne Füllstoffen und/oder Streichpigmenten unter neutralen bis schwach basischen pH-Bedingungen ohne die Verwendung von Aluminiumsalzen.The invention relates to a method for internal sizing in the production of paper, cardboard, cardboard and other cellulose-containing materials with and without fillers and / or coating pigments under neutral to weakly basic pH conditions without the use of aluminum salts.

Die Papierherstellung erfordert zur Bindung des Harzleimes auf der Faseroberfläche einen Vermittler bzw. ein Fixiermittel, da sowohl der Harzleim als auch die Cellulosefasern elektronegativ geladen sind und sich gegenseitig abstoßen. Bei der Herstellung des Papieres im sauren Medium wird hierfür fast ausschließlich Alaun (Aluminiumsulfathydrat) verwendet, wobei die beste Leimung bei einem pH-Wert des Stoffes von 4,5 bis 5,5 erzielt wird. So hergestellte Papiere sind jedoch infolge fortschreitender Hydrolyse nicht alterungsbeständig.Paper production requires a mediator or a fixing agent to bind the resin glue to the fiber surface, since both the resin glue and the cellulose fibers are electronegatively charged and repel each other. Alum (aluminum sulfate hydrate) is used almost exclusively for this purpose in the production of the paper in an acidic medium, with the best sizing being achieved at a pH value of 4.5 to 5.5. However, papers produced in this way are not resistant to aging as a result of progressive hydrolysis.

Es wurde deshalb versucht, Papier unter neutralen Bedingungen intern zu leimen. Die Verwendung von Alaun ist hierbei jedoch nicht möglich, da das Aluminium-lon in diesem pH-Bereich schnell seine positive Ladung verliert und damit den negativ geladenen Leim nur noch unvollständig ausflocken kann.An attempt was therefore made to glue paper internally under neutral conditions. However, the use of alum is not possible because the aluminum ion quickly loses its positive charge in this pH range and can therefore only flocculate the negatively charged glue incompletely.

Darüberhinaus reagiert Aluminiumsulfat mit dem unter neutralen Bedingungen als Pigment und Füllstoff gerne verwendeten Calciumcarbonat unter Kohlendioxidabspaltung, was zu Schaumentwicklung und Löcherbildung auf der Papierbahn führt. Ausfallendes Calciumsulfat führt zu Ablagerungen an der Maschine, so daß eine störungsfreie Papierherstellung nicht möglich ist. Da für das Aluminiumsulfat bisher kein Ersatz gefunden wurde, kann man auch den üblichen Harzleim bei der Papierherstellung unter neutralen Bedingungen nicht verwenden sondern mußte auf synthetische Leime zurückgreifen, was die Papierherstellung wesentlich verteuerte.In addition, aluminum sulfate reacts with calcium carbonate, which is often used as a pigment and filler under neutral conditions, with the elimination of carbon dioxide, which leads to foaming and hole formation on the paper web. Failing calcium sulfate leads to deposits on the machine, so that trouble-free paper production is not possible. Since no substitute has yet been found for the aluminum sulfate, it is not possible to use the usual resin glue in paper production under neutral conditions, but had to fall back on synthetic glue, which made paper production considerably more expensive.

Einen Ausweg schien die « pseudo-neutral-Fahrweise unter Verwendung nur geringer Mengen Aluminiumsulfat zu bieten. Dieses wird dem Dünnstoff sehr spät zugesetzt, so daß die oben geschilderten unerwünschten Reaktionen zu keinen Schwierigkeiten führen. Um die verminderte Fällungswirkung des Alauns bei den hierbei vorliegenden pH-Werten von 6,5 bis 7,4 zu kompensieren, müssen aber noch andere kationische Mittel der Stoffsuspension zugegeben werden. Trotzdem besteht immer die Gefahr, daß das durch Reaktion von entbundener Kohlensäure mit Calciumcarbonat gebildete Calciumhydrogencarbonat im Laufe des Papierherstellungsverfahrens wieder zu Calciumcarbonat und Kohlendioxid zerfällt und Calciumcarbonatablagerungen entstehen, die zu Produktionsunterbrechungen führen.The pseudo-neutral driving style using only small amounts of aluminum sulfate seemed to offer a way out. This is added to the thin material very late, so that the undesired reactions described above do not lead to any difficulties. In order to compensate for the reduced precipitation effect of the alum at the present pH values of 6.5 to 7.4, other cationic agents have to be added to the pulp suspension. Nevertheless, there is always a risk that the calcium hydrogen carbonate formed by the reaction of released carbonic acid with calcium carbonate will decompose again into calcium carbonate and carbon dioxide in the course of the paper production process and calcium carbonate deposits will occur, which lead to production interruptions.

Eine modifizierte pseudoneutrale Papierherstellungsmethode wird in der japanischen Offenlegungsschrift 83-174696 beschrieben. Hierbei wird dem Aluminiumsulfat als zusätzliches Mittel noch ein Dicyandiamid-Formaldehyd-Kondensationsprodukt zugesetzt. Dieses Verfahren hat jedoch immer noch den Nachteil, daß ein teueres Diketenharz verwendet werden muß.A modified pseudo-neutral paper making method is described in Japanese Patent Laid-Open No. 83-174696. Here, a dicyandiamide-formaldehyde condensation product is added to the aluminum sulfate as an additional agent. However, this method still has the disadvantage that an expensive diketene resin has to be used.

In der europäischen Offenlegungsschrift 112 525 wird ein Mittel zur Neutralleimung von cellulosehaltigen Materialien vorgeschlagen, welches aus Wasser, einem in Wasser unbegrenzt löslichen Alkohol, Alkali- oder Aluminiumhydroxid sowie einer gesättigten oder ungesättigten Fettsäure mit 12 bis 24 C-Atomen besteht.European patent application 112 525 proposes an agent for the neutral sizing of cellulose-containing materials, which consists of water, an alcohol which is soluble in water to an unlimited extent, alkali metal or aluminum hydroxide and a saturated or unsaturated fatty acid with 12 to 24 carbon atoms.

Ziel der neutralen Fahrweise der Papierherstellung ist es, den Einsatz von Aluminiumsulfat weitgehend zu reduzieren oder ganz auszuschließen und Kaolin als Füllstoff oder Pigment durch Calciumcarbonat zu ersetzen. Letzteres ist kostengünstiger erhältlich als Kaolin, und sein Weißgrad übersteigt den des Kaolins. Durch das günstigere Fließverhalten des Calciumcarbonats können außerdem höhere Füllungsgrade im Papier realisiert werden. Darüberhinaus wird die Korrosion an den maschinellen Einrichtungen verringert und die Qualität des Papiers, insbesondere dessen Alterungsbeständigkeit deutlich verbessert.The aim of the neutral paper production process is to largely reduce or eliminate the use of aluminum sulfate and to replace kaolin as filler or pigment with calcium carbonate. The latter is less expensive than kaolin and its whiteness exceeds that of kaolin. Due to the more favorable flow behavior of calcium carbonate, higher degrees of filling can also be achieved in the paper. In addition, the corrosion on the machine equipment is reduced and the quality of the paper, in particular its resistance to aging, is significantly improved.

Aus der FR-A-1 218 904 ist ein Verfahren zur Massenleimung von Papier und analogen Materialien bekannt, bei dem man Ketenharze zusammen mit kationischen Harzen als Naßfestmittel verwendet, wodurch ein gewisser Leimungseffekt erzielt wird. Als kationische Harze werden darin Co-Kondensationsprodukte aus Dicyandiamid, Harnstoff und Formaldehyd eingesetzt.From FR-A-1 218 904 a process for the mass sizing of paper and analogous materials is known, in which ketene resins are used together with cationic resins as wet strength agents, whereby a certain sizing effect is achieved. Co-condensation products of dicyandiamide, urea and formaldehyde are used as cationic resins.

Desweiteren ist aus der DE-B-1 070 916 ein Verfahren zum Leimen von Papier bekannt, bei dem übliche Harz- und Wachsleime ohne Metallverbindungen zusammen mit kationischen Kondensationsprodukten aus Carbonamiden, Formaldehyd, Dicyandiamid und gewünstenfalls Hexamethylentetramin verwendet werden.Furthermore, a process for gluing paper is known from DE-B-1 070 916, in which conventional resin and wax glues without metal compounds are used together with cationic condensation products of carbonamides, formaldehyde, dicyandiamide and, if appropriate, hexamethylenetetramine.

Schließlich ist noch aus der EP-A 82 373 ein Verfahren zur Leimung von Papier bekannt, in dem ein ganz besonderes kationisches Harz eingesetzt wird. Das gemäß diesem Verfahren zu verwendende Harz wird in einem dreistufigen Verfahren aus Dicyandiamidformaldehyd einem Polyaminopolyamid, einem Ammoniumsalz und aus Epihalogenhydrin, Acrylamid oder Harnstoff gewonnen. Dieses Kondensationsharz wird als Reaktionsbeschleuniger (Promotor) für Diketenleime verwendet.Finally, EP-A 82 373 discloses a process for sizing paper, in which a very special cationic resin is used. The resin to be used according to this process is obtained in a three-step process from dicyandiamide formaldehyde, a polyaminopolyamide, an ammonium salt and from epihalohydrin, acrylamide or urea. This condensation resin is used as a reaction accelerator (promoter) for diketene glues.

In Ulmann's Encyclopädie der technischen Chemie, 4. Auflage, Band 10, Seite 147 ist die generelle Verwendung von Kondensationsharzen aus Dicyandiamid mit Formaldehyd zum Imprägnieren von Fasermaterialien wie Papier, Holz, Leder und Textilien angegeben. Die Eigenschaften der jeweils verwendeten Kondensationsharze bezüglich der Beständigkeit gegen Wasser und Alkalien, sowie der Härte und der Elastizität läßt sich durch teilweisen Ersatz des Dicyandiamids durch andere Stoffe wie Phenol, Melamin, Guanamine, Anilin oder Harnstoff verändern. Auch die Verwendung kationenaktiver Polykondensate des Dicyandiamids als Flockungsmittel zur Reinigung von Abwässern der Papierindustrie und aus Färbereien sowie zur Entfernung von Schmieröl und anderen Polymerdispersionen aus wäßrigen Systemen ist beschrieben.Ulmann's Encyclopedia of Technical Chemistry, 4th Edition, Volume 10, page 147 specifies the general use of condensation resins made from dicyandiamide with formaldehyde for impregnating fiber materials such as paper, wood, leather and textiles. The properties of the condensation resins used in each case with regard to their resistance to water and alkalis, as well as their hardness and elasticity, can be changed by partially replacing the dicyandiamide with other substances such as phenol, melamine, guanamine, aniline or urea. Also the use of cation-active polycondensates of dicyandiamide as flocculants for the purification of waste water from the paper industry and from dye shops and for removing lubricating oil and other polymer dispersions from aqueous systems is described.

Der vorliegenden Erfindung liegt nun die Aufgabe zugrunde, ein Papierherstellungsverfahren zu entwickeln, das bei neutralen bis schwach basischen pH-Bereichen arbeitet und unter diesen Bedingungen die Nachteile der bisher bekannten Verfahren vermeidet.The present invention is based on the object of developing a paper production process which operates in neutral to weakly basic pH ranges and avoids the disadvantages of the previously known processes under these conditions.

Gelöst wird diese Aufgabe durch ein Verfahren zur internen Leimung bei der Herstellung von Papier, Karton, Pappen und anderen cellulosehaltigen Materialien mit und ohne Füllstoffe und/oder Pigmente durch natürliche oder synthetische Leimungsmittel unter neutralen bis schwach basischen pH-Bedingungen ohne Verwendung von Aluminiumsalzen, welches dadurch gekennzeichnet ist, daß man die Leimung unter Zusatz eines kationischen Dicyandiamidharzes auf der Basis eines Kondensationsproduktes von Dicyandiamid, mit Formaldehyd und wenigstens einer anorganischen oder organischen Säure und/oder wenigstens einem Ammonium- oder Aminsalz davon durchführt.This object is achieved by a process for internal sizing in the production of paper, cardboard, cardboard and other cellulose-containing materials with and without fillers and / or pigments by natural or synthetic sizing agents under neutral to weakly basic pH conditions without the use of aluminum salts, which characterized in that the sizing is carried out with the addition of a cationic dicyandiamide resin based on a condensation product of dicyandiamide, with formaldehyde and at least one inorganic or organic acid and / or at least one ammonium or amine salt thereof.

Es wurde überraschenderweise gefunden, daß die kationischen Dicyandiamidharze in der Lage sind, unter neutralen bis schwach basischen pH-Bedingungen auch natürliche Leimungsmittel zu flocken und auf der Faser zu fixieren. Auch ohne Zugabe von Aluminiumsulfat kann daher mit Hilfe solcher Dicyandiamidharze eine Volleimung erzielt werden.It has surprisingly been found that the cationic dicyandiamide resins are able to flocculate and fix natural sizing agents under neutral to weakly basic pH conditions. Even without the addition of aluminum sulfate, full sizing can therefore be achieved with the aid of such dicyandiamide resins.

Auch bei synthetischen Leimen auf Diketenbasis kann überraschenderweise mittels kationischer Dicyandiamidharze eine Voll- oder Teilleimung erreicht werden, wobei keine weiteren Hilfsmittel oder Fixiermittel benötigt werden.Even with synthetic glues based on diketene, full or partial sizing can surprisingly be achieved using cationic dicyandiamide resins, with no further auxiliaries or fixing agents being required.

Als besonders geeignet haben sich kationische Dicyandiamidharze erwiesen, die eine hohe positive Ladung aufweisen und daher anionische höhermolekulare Stoffe schnell und praktisch quantitativ auszufällen in der Lage sind. Diese Harze werden zweckmäßigerweise nicht zu stark sauer eingestellt, damit nach dem Vermischen mit der Stoffsuspension der pH-Wert nicht wesentlich unter 7 absinkt.Cationic dicyandiamide resins which have a high positive charge and which are therefore able to precipitate anionic, high molecular weight substances quickly and practically quantitatively have proven to be particularly suitable. These resins are expediently not made too acidic, so that after mixing with the stock suspension the pH does not drop significantly below 7.

Die Herstellung der erfindungsgemäß verwendeten kationischen Dicyandiamidharze kann zum Beispiel durch Umsetzung von 1 Mol Dicyandiamid mit 1,0 bis 4,0 Mol Formaldehyd in Gegenwart von 0,1 bis 2,0 Mol wenigstens einer anorganischen oder organischen Säure und/oder wenigstens eines Ammonium- oder Aminsalzes davon und gegebenenfalls bis 0,5 Mol eines zwei- oder mehrwertigen Amins erfolgen. So hergestellte Kondensationsprodukte weisen pH-Werte von etwa 3 bis etwa 5 auf, sind in jedem Verhältnis mit Wasser mischbar und als etwa 50 %ige wäßrige Lösung gut anwendbar.The cationic dicyandiamide resins used according to the invention can be prepared, for example, by reacting 1 mol of dicyandiamide with 1.0 to 4.0 mol of formaldehyde in the presence of 0.1 to 2.0 mol of at least one inorganic or organic acid and / or at least one ammonium or amine salt thereof and optionally up to 0.5 mol of a di- or polyvalent amine. Condensation products prepared in this way have pH values of about 3 to about 5, are miscible with water in any ratio and can be used well as an approximately 50% aqueous solution.

Als Säuren können z. B. starke anorganische Säuren wie Salzsäure, Schwefelsäure oder Salpetersäure eingesetzt werden. Bevorzugt werden jedoch schwächer saure organische Säuren wie z. B. Ameisensäure, Essigsäure oder Oxalsäure verwendet.As acids such. B. strong inorganic acids such as hydrochloric acid, sulfuric acid or nitric acid. However, weakly acidic organic acids such as. B. formic acid, acetic acid or oxalic acid is used.

Als Ammoniumsalz können bei der Harzherstellung z. B. Ammoniumsalze starker anorganischer Säuren wie Ammoniumchlorid oder Ammoniumsulfat oder Ammoniumsalze organischer Säuren wie Ammoniumformiat oder -acetat verwendet werden. Als Aminsalze können Salze aus organischen Aminen mit anorganischen oder organischen Sauren wie z. B. Ethylendiamin-formiat oder Triethylentetramin-Hydrochlorid verwendet werden. Die genannten Salze können auch im Gemisch mit anorganischen oder organischen Säuren eingesetzt werden.As ammonium salt can be used in resin production such. B. ammonium salts of strong inorganic acids such as ammonium chloride or ammonium sulfate or ammonium salts of organic acids such as ammonium formate or acetate can be used. As amine salts, salts of organic amines with inorganic or organic acids such as. B. ethylenediamine formate or triethylenetetramine hydrochloride can be used. The salts mentioned can also be used in a mixture with inorganic or organic acids.

Als gegebenenfalls noch zuzusetzende Aminkomponente können zwei- oder mehrwertige aliphatische Amine verwendet werden. Bevorzugt werden Ethylendiamin, Propylendiamin, Diethylentriamin und Triethylentetramin verwendet. Auch ihre am Stickstoff durch Hydroxylgruppen substituierten Derivate sind einsetzbar wie z. B. Mono- oder Diethanolamin. Falls Amine zugesetzt werden, beträgt ihre Menge vorzugsweise wenigstens 0,05 Mol je Mol Dicyandiamid.Divalent or polyvalent aliphatic amines can be used as the amine component to be added. Ethylene diamine, propylene diamine, diethylene triamine and triethylene tetramine are preferably used. Their derivatives substituted on the nitrogen by hydroxyl groups can also be used, such as, for. B. mono- or diethanolamine. If amines are added, their amount is preferably at least 0.05 mol per mol of dicyandiamide.

Formaldehyd kann in beliebiger Form, vorzugsweise in Form seiner 30 bis 40 Gew.-%igen wäßrigen Lösungen verwendet werden.Formaldehyde can be used in any form, preferably in the form of its 30 to 40% by weight aqueous solutions.

Unter neutralen bis schwach basischen pH-Werten werden hier solche zwischen pH 6,5 und 8,5, vorzugsweise zwischen 7,0 und 8,0 verstanden.Neutral to weakly basic pH values are understood to mean those between pH 6.5 and 8.5, preferably between 7.0 and 8.0.

Die nach dem beschriebenen Verfahren erhaltenen Kondensationsprodukte sind klare, farblose, in jedem Verhältnis mit Wasser mischbare Produkte.The condensation products obtained by the process described are clear, colorless, water-miscible products.

Im Rahmen der Erfindung können jedoch auch nach anderen Verfahren hergestellte kationische Dicyandiamidharze verwendet werden.However, cationic dicyandiamide resins produced by other processes can also be used within the scope of the invention.

Die aufzuwendende Menge an kationischem Dicyandiamidharz wird auf die « Stoff (Cellulose)-Menge bezogen und beträgt im allgemeinen 0,1 bis 10 Gew.-% ; bevorzugt werden 0,2 bis 5 Gew.-% Dicyandiamidharz angewandt, zweckmäßig in Form einer etwa 50 %igen wäßrigen Lösung.The amount of cationic dicyandiamide resin to be used is based on the amount of material (cellulose) and is generally 0.1 to 10% by weight; 0.2 to 5% by weight of dicyandiamide resin is preferably used, advantageously in the form of an approximately 50% strength aqueous solution.

Bei dem erfindungsgemäßen Verfahren können alle handelsüblichen Leime auf Basis natürlicher oder synthetischer Ausgangsstoffe verwendet werden. Geeignete Produkte sind z. B. Kolophonium, Tierleim, Casein, Stärke, Wachse, Fettsäuren und Tallharze. Von synthetischen Leimen eignen sich besonders Produkte auf Basis von Ketendimeren, Polyvinylalkoholen oder Polyvinylacetaten. Als Ketendimere finden Produkte Anwendung, die auf Basis von alkylsubstituierten, dimeren Ketenen mit OxetanonStruktur, ausgehend von langkettigen Fettsäuren, hergestellt worden sind und unter dem Markennamen Aquapel vertrieben werden. In gleicher Weise eignen sich auch modifizierte Harzleime, wie sie z. B. durch Umsetzung von z. B. Kolophonium mit dienophilen Säuren erhalten werden und unter der Markenbezeichnung Purtin 3 N/S im Handel sind. Darüberhinaus sind auch äußerst fein verteilte Dispersionen speziell modifizierter, verstärkter Harze (z. B. Furtin BVR 510) vorteilhaft anwendbar.In the process according to the invention, all commercially available glues based on natural or synthetic starting materials can be used. Suitable products are e.g. B. rosin, animal glue, casein, starch, waxes, fatty acids and tall resins. Of synthetic glues, products based on ketene dimers, polyvinyl alcohols or polyvinyl acetates are particularly suitable. Products used as ketene dimers are those which have been produced on the basis of alkyl-substituted, dimeric ketene with an oxetanone structure, starting from long-chain fatty acids, and which are sold under the brand name Aquapel. In the same way, modified resin glues such as z. B. by implementing z. B. rosin can be obtained with dienophilic acids and are commercially available under the brand name Purtin 3 N / S. In addition, extremely finely divided dispersions of specially modified, reinforced resins (e.g. Furtin BVR 510) can be used with advantage.

Das erfindungsgemäße Verfahren erlaubt es nun überraschenderweise, durch Kombinationen von kationischem Dicyandiamidharz mit den vorstehend genannten, chemisch recht unterschiedlichen Leimkomponenten, diese zu flocken und auf der Faser zu fixieren. Ohne Zuhilfenahme weiterer Hilfsmittel kann auf diese Weise mit natürlichen, synthetischen oder modifizierten Harzleimen Voll- oder Teilleimung des Papieres erreicht werden.The method according to the invention now surprisingly allows combinations of cationic dicyandiamide resin with the chemically very different glue components mentioned above, to flocculate them and fix them on the fiber. In this way, full or partial sizing of the paper can be achieved with natural, synthetic or modified resin glues without the aid of further aids.

Sämtliche in der Papierherstellung üblichen Füllstoffe und Pigmente können auch beim erfindungsgemäßen Verfahren verwendet werden wie z. B. Kaolin, Aluminiumsilikate, Calciumsilikate, Oxihydrate von Aluminium, Talkum, Satinweiß, Gips, Bariumsulfat, Bariumcarbonat, Magnesit, Zinkoxid, Titandioxid. Bevorzugt wird jedoch Calciumcarbonat verwendet. Dieses kann in feingemahlener Form aus natürlichem Calciumcarbonat bestehen oder auch gefälltes Calciumcarbonat sein. Calciumcarbonat wird deshalb bevorzugt, da sein Weißgrad z. B. den des Kaolins übersteigt und sein günstiges Fließverhalten besonders hohe Füllungsgrade im Papier erreichen läßt. Damit werden auch die Papiereigenschaften positiv beeinflußt: Die Opazität wird erhöht, der Weißgrad verbessert, die Alterungsbeständigkeit erhöht und die mechanischen Eigenschaften gesteigert.All fillers and pigments customary in paper production can also be used in the process according to the invention, such as, for. B. kaolin, aluminum silicates, calcium silicates, oxyhydrates of aluminum, talc, satin white, gypsum, barium sulfate, barium carbonate, magnesite, zinc oxide, titanium dioxide. However, calcium carbonate is preferably used. This can consist of natural calcium carbonate in finely ground form or it can also be precipitated calcium carbonate. Calcium carbonate is preferred because its whiteness z. B. exceeds that of kaolin and its favorable flow behavior allows particularly high filling levels in the paper to be achieved. This also has a positive influence on the paper properties: opacity is increased, whiteness is improved, aging resistance is increased and mechanical properties are increased.

Die nachfolgenden Beispiele erläutern die Erfindung und zeigen insbesondere, welche unterschiedlichen Leimsorten durch kationische Dicyandiamidharze unter neutralen oder schwach basischen pH-Bedingungen auf Cellulosefasem aufgebracht werden können und welche guten Ergebnisse so erreicht werden.The following examples explain the invention and in particular show which different types of glue can be applied to cellulose fibers by cationic dicyandiamide resins under neutral or weakly basic pH conditions and which good results are achieved in this way.

BeispieleExamples

Herstellung eines kationischen Dicyandiamid-Formaldehyd-Harzes: 84 Gew.-Teile Dicyandiamid werden mit 220 Gew.-Teilen 30 %igen wäßrigen Formaldehyd und 43 Gew.-Teilen Ammoniumchlorid in ein mit Rückflußkühler ausgestattetes Rührgefäß vorgelegt. Bei Raumtemperatur werden sodann 7,7 Gew.-Teile Ethylendiamin (78 %ig) unter Rühren zugesetzt. Die Reaktion springt sofort an und die Temperatur des Reaktionsgemisches steigt auf 90 bis 95 °C. Nach etwa 10 Minuten ist die Reaktion beendet. Danach wird Wasser zugegeben, um eine Konzentration von 50 Gew.-% Feststoff im Harz einzustellen.Preparation of a cationic dicyandiamide-formaldehyde resin: 84 parts by weight of dicyandiamide are placed in a stirred vessel equipped with a reflux condenser with 220 parts by weight of 30% strength aqueous formaldehyde and 43 parts by weight of ammonium chloride. At room temperature, 7.7 parts by weight of ethylenediamine (78%) are then added with stirring. The reaction starts immediately and the temperature of the reaction mixture rises to 90 to 95 ° C. The reaction is complete after about 10 minutes. Then water is added to adjust the concentration of 50% by weight of solid in the resin.

Anstelle von Ethylendiamin kann z. B. auch die entsprechende Menge Diethylentriamin Triethylentetramin oder Diethanolamin verwendet werden.Instead of ethylenediamine z. B. also the appropriate amount of diethylenetriamine, triethylenetetramine or diethanolamine can be used.

Anstelle von Ammoniumchlorid kann eine anorganische oder organische Säure wie z. B. Salzsäure oder Ameisensäure verwendet werden.Instead of ammonium chloride, an inorganic or organic acid such as. B. hydrochloric acid or formic acid can be used.

Beispiel 1example 1

Auf einem Rapid-Köthen Blattbildner werden unter Verwendung von gebleichtem Kiefernzellstoff eines Mahlgrades 24° SR, Harzleim (Freiharzleim Furtin 3N) und 50 %igem wäßrigem kationischem Dicyandiamidharz (hergestellt aus Dicyandiamid, Formaldehyd, Ammonchlorid und Ethylendiamin) Blätter gebildet und auf Zylindern thermisch 3 Minuten lang bei 120 °C behandelt. Nach der Klimatisierung wurde die Leimung durch die Wasseraufnahme mittels des Cobb-Tests (60 sec.) nach DIN 531 32 bestimmt. Der Verwendung des kationischen Dicyandiamidharzes wurde Alaun als Leimungsmittel gegenübergestellt, wobei sich der pH-Wert von selbst einstellte.Leaves are formed on a Rapid-Köthen sheet former using bleached pine pulp with a freeness of 24 ° SR, resin glue (free resin glue Furtin 3N) and 50% aqueous cationic dicyandiamide resin (made from dicyandiamide, formaldehyde, ammonium chloride and ethylenediamine) and thermally formed on cylinders for 3 minutes treated at 120 ° C for a long time. After the air conditioning, the sizing was determined by the water absorption using the Cobb test (60 sec.) In accordance with DIN 531 32. The use of the cationic dicyandiamide resin was compared to alum as a sizing agent, the pH adjusting itself.

Gegenüberstellung der Wirksamkeit des erfindungsgemäßen Papierherstellungsverfahrens mit kationischem Dicyandiamidharz und Alaun :

Figure imgb0001
Comparison of the effectiveness of the paper production process according to the invention with cationic dicyandiamide resin and alum:
Figure imgb0001

Ergebnis : Bei pH-Werten oberhalb 7 kann bei Einsatz von kationischem Dicyandiamidharz eine Voll-Leimung erzielt werden, die sich bei Verwendung von Alaun in diesem pH-Bereich nicht erreichen läßt.Result: At pH values above 7, full sizing can be achieved when using cationic dicyandiamide resin, which cannot be achieved in this pH range when using alum.

Beispiel 2Example 2

Blattbildung unter Verwendung von Calciumcarbonat als Füllstoff.Sheet formation using calcium carbonate as a filler.

Die Versuchsbedingungen waren die gleichen wie in Beispiel 1, jedoch wurde schwach anionisches Calciumcarbonat als Füllstoff zugesetzt. Das Gewichtsverhältnis von Zellstoff zu Füllstoff betrug 1 2. Der Füllstoff wurde 5 Minuten im Ultra Turrax (Dispergiergerät) aufbereitet, anschließend 3 Minuten mit dem Zellstoff vermischt und danach der Leim und das kationische Dicyandiamidharz zugegeben.

Figure imgb0002
The test conditions were the same as in Example 1, but weakly anionic calcium carbonate was added as a filler. The weight ratio of pulp to filler was 1 2. The filler was processed for 5 minutes in an Ultra Turrax (dispersing device), then mixed with the pulp for 3 minutes and then the glue and the cationic dicyandiamide resin were added.
Figure imgb0002

Ergebnis : Die Verwendung von kationischem Dicyandiamidharz läßt bei Einsatz von Harzleim u. Calciumcarbonat als Füllstoff ohne Zusatz von Alaun im pH-Bereich von 7,5 eine Voll-Leimung erreichen.Result: The use of cationic dicyandiamide resin allows u. Calcium carbonate as a filler can achieve full sizing without adding alum in the pH range of 7.5.

Beispiel 3Example 3

Blattbildung unter Verwendung von Diketenleim und Calciumcarbonat als Füllstoff.Sheet formation using diketene glue and calcium carbonate as filler.

Es wurde das gleiche kationische Dicyandiamidharz und die gleiche Calciumcarbonatqualität verwendet wie im Beispiel 2. Zum Leimen wurde ein synthetisches Produkt'auf Diketenbasis (Aquapel 2) verwendet. Die Qualität der Leimung wurde mit dem Cobb-Test festgestellt.

Figure imgb0003
The same cationic dicyandiamide resin and the same calcium carbonate quality were used as in Example 2. A synthetic product based on diketene (Aquapel 2) was used for sizing. The quality of the sizing was determined using the Cobb test.
Figure imgb0003

Ergebnis : Bereits durch Zusatz von geringen Mengen an kationischem Dicyandiamidharz wird die Leimung stark verbessert ; der pH-Wert der Stoffsuspension wird durch Zusatz dieses Harzes nicht verändert.Result: The addition of small amounts of cationic dicyandiamide resin greatly improves the sizing; the pH of the stock suspension is not changed by adding this resin.

Beispiel 4Example 4

Blattbildung unter Verwendung eines vollverseiften Harzleims ohne Füllstoff.Sheet formation using a fully saponified resin glue without filler.

Als Dicyandiamidharz wurde in diesem Beispiel ein 50 Gew.-% Feststoff enthaltendes Kondensationsprodukt aus Dicyandiamid, Formaldehyd und Ameisensäure verwendet, wobei das Molverhältnis der Komponenten 1 : 1,5: 0,5 betrug. Als Leim wurde ein vollverseifter Harzleim (Furtin 3 N/S) verwendet. Von den, wie unter Beispiel 1 hergestellten Blättern, wurden die Cobb-Werte ermittelt.

Figure imgb0004
In this example, a 50% by weight solid condensation product of dicyandiamide, formaldehyde and formic acid was used as the dicyandiamide resin, the molar ratio of the components being 1: 1.5: 0.5. A fully saponified resin glue (Furtin 3 N / S) was used. The Cobb values were determined from the leaves produced as in Example 1.
Figure imgb0004

Ergebnis : Bei Verwendung eines vollverseiften Harzleims und Einsatz eines kationischen Dicyandiamidharzes läßt sich bei pH-Werten über 7 ein guter Leimungseffekt erzielen.Result: When using a fully saponified resin glue and a cationic dicyandiamide resin, a good sizing effect can be achieved at pH values above 7.

Beispiel 5Example 5

Blattbildung unter Verwendung eines vollverseiften Harzleims und Füllstoff.Sheet formation using a fully saponified resin glue and filler.

Es wurde das gleiche Dicyandiamidharz und der gleiche Harzleim verwendet wie im Beispiel 4. Als Füllstoff diente schwach anionisches Calciumcarbonat. Die Blätter wurden in analoger Weise, wie unter Beispiel 1 angegeben, hergestellt.

Figure imgb0005
The same dicyandiamide resin and the same resin size were used as in Example 4. Weakly anionic calcium carbonate was used as the filler. The sheets were produced in a manner analogous to that given in Example 1.
Figure imgb0005

Ergebnis : Auch bei Einsatz von anionischem Calciumcarbonat als Füllstoff und Verwendung von vollverseiftem Harzleim kann bei pH-Werten über 7 ein ausreichender Leimungseffekt erzielt werden.Result: Even when using anionic calcium carbonate as a filler and using fully saponified resin glue, a sufficient sizing effect can be achieved at pH values above 7.

Beispiel 6Example 6

Blattbildung ohne Füllstoff.Sheet formation without filler.

Unter Verwendung des gleichen, in Beispiel 4 genannten, kationischen Dicyandiamidharzes sowie eines fein dispergierten, speziell modifizierten Harzleims (Furtin BVR 510) wurden gemäß Beispiel 1 Blätter gebildet. Deren Eigenschaften werden in nachfolgender Tabelle dargestellt.

Figure imgb0006
Using the same cationic dicyandiamide resin mentioned in Example 4 and a finely dispersed, specially modified resin glue (Furtin BVR 510), sheets were formed in accordance with Example 1. Their properties are shown in the table below.
Figure imgb0006

Ergebnis : Die Kombination von kationischen Dicyandiamidharz mit einem speziell modifizierten Harzleim liefert auch bei pH-Werten . 7 hervorragende Cobb-Werte.Result: The combination of cationic dicyandiamide resin with a specially modified resin glue delivers even at pH values. 7 excellent Cobb values.

Beispiel 7Example 7

Blattbildung unter Verwendung eines modifizierten Harzleims und Füllstoff.Sheet formation using a modified resin glue and filler.

Unter Verwendung des in Beispiel 6 genannten kationischen Dicyandiamidharzes, des gleichen speziell modifizierten Harzleims und schwach anionischem Calciumcarbonat als Füllstoff wurden gemäß Beispiel 1 Blätter hergestellt, deren Cobb-Werte in der folgenden Tabelle dargestellt werden.

Figure imgb0007
Using the cationic dicyandiamide resin mentioned in Example 6, the same specially modified resin size and weakly anionic calcium carbonate as filler, sheets were produced in accordance with Example 1, the Cobb values of which are shown in the following table.
Figure imgb0007

Ergebnis : Durch Kombination eines kationischen Dicyandiamidharzes mit einem speziell modifizierten Harzleim und Füllstoff wird auch bei pH-Werten über 7 eine Voll-Leimung erzielt.Result: By combining a cationic dicyandiamide resin with a specially modified resin glue and filler, full sizing is achieved even at pH values above 7.

Claims (7)

1. Process for the internal sizing in the production of paper, cardboard, paperboard and other cellulose-containing materials with and without filling materials and/or pigments by natural or synthetic sizing agents under neutral to weakly basic pH conditions without the use of aluminium salts, characterised in that one carries out the sizing with the addition of a cationic dicyandiamide resin based on a condensation product of dicyandiamide with formaldehyde and at least one inorganic or organic acid and/or at least one ammonium or amine salt thereof.
2. Process according to claim 1, characterised in that, as cationic dicyandiamide resin, one uses a condensation product of 1 mole dicyandiamide with 1.0 to 4 mole formaldehyde and 0.1 to 2 mole of the inorganic or organic acid and/or of an ammonium or amine salt of the acid and 0 to 0.5 mole of a di- or polybasic amine in the form of its aqueous solution containing up to 60 wt.% of solids.
3. Process according to claim 1 or 2, characterised in that one uses 0.1 to 10 wt.% of the cationic dicyandiamide resin, referred to the amount of cellulose.
4. Process according to claim 3, characterised in that one uses 0.2 to 6 wt.% of the cationic dicyandiamide resin, referred to the amount of cellulose.
5. Process according to claim 2, characterised in that one uses ethylenediamine, diethylenetriamine or diethanolamine as amine.
6. Process according to claims 1 to 5, characterised in that one uses a condensation product of dicyandiamide with formaldehyde and mixtures of ammonium and amine salts, as well as of free acids, as cationic dicyandiamide resin.
7. Process according to claim 1, characterised in that one uses finely ground or precipitated calcium carbonate as filling material and/or pigment.
EP86100189A 1985-01-08 1986-01-08 Internal sizing process in the manufacture of paper, cardboard, boards and other cellulosic materials Expired EP0187666B1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8157961B2 (en) 2005-11-01 2012-04-17 International Paper Company Paper substrate having enhanced print density
US8465622B2 (en) 2007-12-26 2013-06-18 International Paper Company Paper substrate containing a wetting agent and having improved print mottle
US8460511B2 (en) 2008-10-01 2013-06-11 International Paper Company Paper substrate containing a wetting agent and having improved printability

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DK2986D0 (en) 1986-01-03
FI81861B (en) 1990-08-31
CA1274059A (en) 1990-09-18
DK2986A (en) 1986-07-09
DE3500408A1 (en) 1986-07-10
NO165810C (en) 1991-04-10
DE3666709D1 (en) 1989-12-07
EP0187666A1 (en) 1986-07-16
FI855199L (en) 1986-07-09
ATE47733T1 (en) 1989-11-15
NO165810B (en) 1991-01-02
FI81861C (en) 1990-12-10
NO855124L (en) 1986-07-09
FI855199A0 (en) 1985-12-31
US5026457A (en) 1991-06-25

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