EP0200002B1 - Paper-sizing agents and their use - Google Patents

Paper-sizing agents and their use Download PDF

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Publication number
EP0200002B1
EP0200002B1 EP86104329A EP86104329A EP0200002B1 EP 0200002 B1 EP0200002 B1 EP 0200002B1 EP 86104329 A EP86104329 A EP 86104329A EP 86104329 A EP86104329 A EP 86104329A EP 0200002 B1 EP0200002 B1 EP 0200002B1
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Prior art keywords
agents
dispersions
colophony
paper
polyaluminum
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German (de)
French (fr)
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EP0200002A1 (en
EP0200002B2 (en
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Awie Dr. Dipl.-Chem. Phau
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Chemische Fabrik Bruehl Oppermann GmbH
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Chemische Fabrik Bruehl Oppermann GmbH
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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
    • 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
    • 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
    • D21H17/62—Rosin; Derivatives thereof
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums

Definitions

  • the present invention relates to paper sizing agents based on rosin dispersions and their use for the production of sized papers, cardboards and cardboard as well as a process for the production of sized papers.
  • a process for sizing paper is known from EP-A 0 099 547, in which aluminum polyhydroxychloride is used for the aqueous suspension of the fibers with the rosin dispersion and calcium carbonate can be used as filler. This process is carried out in the pH range of at least 7.
  • EP-A 0 133 902 discloses a process for sizing paper, in which a synthetic sizing agent is added to the cellulose fibers, and a filler which is sensitive in the acidic range, aluminum polyhydroxychlorides being used as retention agents. In this process too, the aluminum polyhydroxychloride is only added after the fiber material has been homogeneously mixed with the sizing agent and the filler calcium carbonate.
  • rosin and polyaluminium hydroxychlorides are also known from CA-A 759 363, it being expressly recommended that the rosin and then the precipitant be added first. It is not advisable to add these substances in reverse order or even together to form a precipitate.
  • the object of the invention is to develop new paper sizing agents based on rosin dispersions which, on the one hand, are based on the customary and inexpensive raw material, rosin, and, on the other hand, can be used in various pH ranges of the material mass which occur in practice, so that can be worked without alum or other additional retention aids or fixatives.
  • the new paper sizing agents should also be able to be used with inferior material qualities such as waste paper and wood-containing materials and still lead reliably and easily to perfectly sized products.
  • the invention has also set itself the task of simplifying the process for the production of sized papers using rosin dispersions and polyaluminium hydroxychlorides as precipitants, and thereby being able to carry out the process more reliably and reproducibly.
  • the first object is surprisingly achieved by paper sizing agents, which are characterized in that they additionally contain polyaluminium hydroxychlorides and optionally retention and / or fixing agents and / or wet strength agents, the components being premixed while avoiding agglomeration.
  • the paper sizing agents preferably contain the polyaluminium hydroxychlorides in a commercially available aqueous solution with a content of 8 to 20% by weight of aluminum oxide.
  • the total mixture preferably contains 5 to 50% by weight of such polyaluminium hydroxychloride solutions.
  • the further object of the invention namely to improve a process for the production of sized papers using rosin dispersions and polyaluminium hydroxychlorides as precipitants, is achieved in that the rosin dispersions are mixed with the polyaluminum hydroxychlorides before use, avoiding agglomeration.
  • the rosin dispersions used are either conventionally unreinforced rosin resin dispersions or the conventionally reinforced resin glue dispersions which are prepared from rosin or hydrocarbon resin modified with maleic anhydride or fumaric acid, usually with the addition of protective colloids or surface-active substances.
  • the proportion of this resin size dispersion in the paper size according to the invention is 10 to 60% by weight, preferably 30 to 50% by weight.
  • These rosin dispersions are commercially available and usually have a solids content of 10 to 50% by weight.
  • the new paper sizing agents preferably already contain retention and / or fixing agents and / or wet strength agents.
  • These additives generally consist of aqueous solutions or dispersions, for example of polyamine-epichlorohydrin resins, polyamide-epichlorohydrin resins, polyacrylamides, polyethyleneimines, condensation products of formaldehyde with urea or dicyandiamide or melamine or mixtures of these solutions and dispersions.
  • the proportion of these additives is 1 to 20% by weight, preferably 4 to 15% by weight. These are also mostly commercial products.
  • the polyaluminium hydroxychlorides are also commercial products that have so far been used in particular for the precipitation and flocculation of dissolved constituents of waste water. According to the abovementioned patents, it is also possible to use them as a precipitant instead of alum or as a retention agent in the case of artificial sizing agents. However, considerable difficulties and disruptions have been shown in practical testing. Surprisingly, however, it has now been found that these polyaluminium chlorides can be added to conventional rosin dispersions without the resin flocculating or precipitating out or completely useless mixtures being formed. Surprisingly, such mixtures are able to glue paper, cardboard and cardboard correctly and differentially in a wide pH range. The pH insensitivity is so great that even the addition of alum does not interfere, although according to the invention the use of alum can be dispensed with.
  • the paper sizing agents according to the invention are able to properly glue inferior starting materials such as waste paper and wood-containing fibers.
  • kaolin has primarily been used as a filler.
  • chalk i.e. Calcium carbonate used as a filler.
  • This filler is sensitive to alum and acid, so that it leads to undesired reactions, sticking, precipitation and other malfunctions.
  • waste paper it is increasingly to be expected today that considerable amounts of chalk are present in the product, which leads to the above-mentioned disturbances in the case of acid fixation.
  • the paper sizes according to the invention can be used without problems at least in the pH range between 3.5 and 9.0. They are preferably used in the neutral area, since experience has shown that this area produces the optimal mechanical properties of the sized paper.
  • the paper sizes according to the invention have the further advantage that they can be produced ready for use.
  • the new paper sizing agents are stable for a sufficiently long time and, if desired, can be diluted with water in any ratio.
  • the new paper sizing agents are less corrosive, they lead to reduced deposits on the screen, in the felts and the other machine parts and do not form any foam in the fabric system.
  • the paper sizing agents according to the invention are preferably metered continuously into the material stream shortly before the headbox of the paper or board machine. With this method of working it is possible to eliminate mechanical influences and to achieve a maximum sizing effect. This continuous dosage makes it possible to quickly influence the sizing effect if necessary.
  • the sizing can thus be set very differently from half-sizing to full-sizing.
  • the production of the product according to the invention is relatively simple. It can be done, for example, by introducing the individual components into a stirred tank.
  • the order of adding the components is not critical.
  • the rosin dispersion (resin glue dispersion) is preferably introduced and then the solution of the polyaluminium hydroxychloride is added tet.
  • the third and further components namely retention aid, fixative and wet strength agent, are added to the mixture simultaneously or in succession with further stirring.
  • the paper sizes according to the invention are liquid and are in dispersion form.
  • the products according to the invention for sizing paper, cardboard and cardboard are used in the mass of material.
  • the point of addition can be between pulper or Dutch until just before the headbox.
  • the amount used is usually between 0.5 and 2% solid resin based on dry fiber.
  • the degree of sizing that can be achieved is then between 15 and 35 Cobbeo.
  • a paper sizing agent is produced with the addition of 50 g of a dispersion of formaldehyde and aliphatic amides (Levogen PNK / Bayer) or fixing agent (FP / BASF).
  • the dispersion is stable for at least 6 weeks.
  • a paper sizing agent is produced with the addition of 50 g of polyethyleneimines (Polymin types / BASF).
  • the dispersion is stable for at least 6 weeks.
  • Sample sheets were produced to test the effectiveness of the products described in Examples 1 to 4.
  • a cellulose was used which consisted of 50% bleached sulfite pulp and 50% bleached sulfate pulp. This material was beaten with city water, ground to 40 ° SR and brought to 2% consistency. With the addition of 20% chalk as filler and a corresponding amount of sizing agent according to Examples 1 to 4, the sample sheets were produced using a Rapid-Köthen device. The Cobb method (60 seconds) was used to check the degree of sizing. The results are summarized in the table below.

Abstract

1. Paper sizing agents based on colophony dispersions, characterized in that they additionally contain polyaluminum hydroxychlorides and optionally retention agents and/or fixing agents and/or wetstrength agents, the components having been premixed such as to avoid agglomeration.

Description

Gegenstand der vorliegenden Erfindung sind Papierleimungsmittel auf Basis von Kolophonium-Dispersionen sowie ihre Verwendung zur Herstellung von geleimten Papieren, Pappen und Karton sowie ein Verfahren zur Herstellung von geleimten Papieren.The present invention relates to paper sizing agents based on rosin dispersions and their use for the production of sized papers, cardboards and cardboard as well as a process for the production of sized papers.

Die Leimung von Papier, Pappe und Karton erfolgt insbesondere, um diese wasser- und tintenfest zu machen. Prinzipiell ist es auch möglich, fertige Papiere nachträglich zu leimen, vorzugsweise findet jedoch die Leimung bereits während der Produktion in der Masse statt. In der Praxis werden insbesondere drei verschiedene Leimungsverfahren in der Masse eingesetzt:

  • 1. Saure Harzleimung: Bei diesem Verfahren wird erst der Harzleim und dann ein saurer Stoff wie Alaun zugesetzt. Der Harzleim kann sowohl in Seifenform als auch in Dispersionsform vorliegen. Eine effektvolle und problemlose Anwendung dieses Verfahrens ist nur im sauren pH-Bereich des Stoffes möglich. Saure Harzleimung ist in Gegenwart des zunehmend verwendeten billigen Füllstoffs Kreide wegen deren Zersetzung ungeeignet. Die Anwendung des Verfahrens wird weiterhin dadurch in zunehmendem Maße beschränkt, daß die Auflagen bezüglich des Sulfatgehaltes im Abwasser aus Umweltschutzgründen verschärft wurden.
  • 2. Pseudoneutrale Leimung: Bei diesem Verfahren wird der gleiche Harzleim wie bei der sauren Harzleimung verwendet, jedoch wird zur Fixierung statt Alaun Natriumaluminat verwendet. Wegen der alkalischen Eigenschaft und der Wirksamkeit des Natriumaluminats im sauren pH-Bereich ist es notwendig, die zunächst mit Harzleim und dann mit Natriumaluminat behandelte Stoffmasse mit Hilfe von Säuren auf einem pH-Wert dicht unterhalb des Neutralpunktes zu bringen, um überhaupt eine Leimung zu erzielen. Wesentliche Nachteile dieses Verfahrens sind die höheren Kosten für Natriumaluminat und die Notwendigkeit, den pH-Wert im Stoff genau einzuhalten.
  • 3. Neutrale Leimung: Bei dieser Methode wird mit einer reaktiven Substanz (z.B. Ketendimeren) oder einer kationischen Kunststoff-Dispersion als Papierleimungsmittel gearbeitet. Die Verwendung dieser Leimungsmittel bereitet oft Schwierigkeiten, wenn z.B. Alaun, Holzstoff oder andere Störstoffe in der Stoffmasse zugegen sind. Dies erfordert zumindest einen hohen Mengeneinsatz des Leimungsmittels und bedingt somit sehr hohe Kosten des Verfahrens.
The gluing of paper, cardboard and cardboard is done in particular to make them water and ink resistant. In principle, it is also possible to subsequently glue finished papers, but preferably the glue takes place in bulk during production. In practice, three different sizing processes are used in bulk:
  • 1. Acid resin sizing: In this process, the resin glue is added first and then an acidic substance such as alum. The resin glue can be in both soap form and dispersion form. This method can only be used effectively and without problems in the acidic pH range of the substance. Acid resin sizing is unsuitable in the presence of the increasingly used cheap filler chalk because of its decomposition. The application of the method is further limited by the fact that the requirements regarding the sulfate content in the wastewater have been tightened for environmental reasons.
  • 2. Pseudoneutral sizing: This process uses the same resin glue as for acid resin sizing, but instead of alum, sodium aluminate is used for fixation. Because of the alkaline properties and effectiveness of sodium aluminate in the acidic pH range, it is necessary to bring the mass of material first treated with resin glue and then with sodium aluminate to a pH just below the neutral point with the help of acids in order to achieve sizing at all . The main disadvantages of this process are the higher costs for sodium aluminate and the need to precisely maintain the pH in the substance.
  • 3. Neutral sizing: This method uses a reactive substance (e.g. ketene dimers) or a cationic plastic dispersion as a paper sizing agent. The use of these sizing agents is often difficult if, for example, alum, wood pulp or other contaminants are present in the material mass. This requires at least a large amount of use of the sizing agent and therefore very high costs of the process.

Aus der CH-A 623 371 ist bekannt, zur Ausfällung von Kolophonium-Dispersionen anstelle von Alaun praktisch sulfatfreie Aluminiumpolyhydroxychloride zu verwenden. Auch bei diesem Verfahren wird das Aluminiumpolyhydroxychlorid als Fällungsmittel erst zugegeben, nachdem der Faserstoff bereits mit der Kolophonium-Dispersion als Leimungsmittel homogen vermischt worden ist.From CH-A 623 371 it is known to use practically sulfate-free aluminum polyhydroxychlorides for the precipitation of rosin dispersions instead of alum. In this process, too, the aluminum polyhydroxychloride is added as a precipitant only after the fibrous material has been homogeneously mixed with the rosin dispersion as a sizing agent.

Aus der EP-B 0 063 812 ist bekannt, zur Fällung ein Aluminiumpolyhydroxychlorid zu verwenden, welches ein Chlor/OH-Verhältnis von 3n-m/m von 5:1 aufweist.From EP-B 0 063 812 it is known to use an aluminum polyhydroxychloride for the precipitation, which has a chlorine / OH ratio of 3n-m / m of 5: 1.

Aus der EP-A 0 099 547 ist ein Verfahren zur Leimung von Papier bekannt, bei welchem zu der wäßrigen Suspension der Fasern mit der Kolophonium-Dispersion Aluminiumpolyhydroxychloride verwendet werden und als Füllstoff Calciumcarbonat eingesetzt werden kann. Dieses Verfahren wird im pH-Bereich von mindestens 7 durchgeführt.A process for sizing paper is known from EP-A 0 099 547, in which aluminum polyhydroxychloride is used for the aqueous suspension of the fibers with the rosin dispersion and calcium carbonate can be used as filler. This process is carried out in the pH range of at least 7.

Aus der EP-A 0 133 902 ist ein Verfahren zur Leimung von Papier bekannt, bei dem den Cellulosefasern ein synthetisches Leimungsmittel zugegeben wird, sowie ein Füllstoff, der im sauren Bereich empfindlich ist, wobei als Retentionsmittel Aluminiumpolyhydroxychloride eingesetzt werden. Auch bei diesem Verfahren wird das Aluminiumpolyhydroxychlorid erst zugesetzt, nachdem das Fasermaterial mit dem Leimungsmittel und dem Füllstoff Calciumcarbonat homogen vermischt worden war.EP-A 0 133 902 discloses a process for sizing paper, in which a synthetic sizing agent is added to the cellulose fibers, and a filler which is sensitive in the acidic range, aluminum polyhydroxychlorides being used as retention agents. In this process too, the aluminum polyhydroxychloride is only added after the fiber material has been homogeneously mixed with the sizing agent and the filler calcium carbonate.

Aus der CA-A 759 363 ist ebenfalls die Verwendung von Kolophonium und Polyaluminiumhydroxychloriden bekannt, wobei ausdrücklich empfohlen wird, erst das Kolophonium und dann das Fällungsmittel zuzusetzen. Es wird davon abgeraten, diese Substanzen in umgekehrter Reihenfolge oder gar zusammen unter Bildung eines Niederschlags zuzugeben.The use of rosin and polyaluminium hydroxychlorides is also known from CA-A 759 363, it being expressly recommended that the rosin and then the precipitant be added first. It is not advisable to add these substances in reverse order or even together to form a precipitate.

Die Erfindung hat sich die Aufgabe gestellt, neue Papierleimungsmittel auf Basis von Kolophonium-Dispersionen zu entwickeln, die einerseits von dem üblichen, und preiswerten Rohstoff Kolophonium ausgehen und zum anderen in verschiedenen in der Praxis vorkommenden pH-Bereichen der Stoffmasse zur Anwendung kommen können, so daß ohne Alaun oder sonstige zusätzliche Retentionsmittel oder Fixiermittel gearbeitet werden kann. Insbesondere sollen die neuen Papierleimungsmittel auch bei minderwertigen Materialqualitäten wie Altpapier und holzhaltigen Materialien eingesetzt werden können und dennoch zuverlässig und einfach zu einwandfrei geleimten Produkten führen.The object of the invention is to develop new paper sizing agents based on rosin dispersions which, on the one hand, are based on the customary and inexpensive raw material, rosin, and, on the other hand, can be used in various pH ranges of the material mass which occur in practice, so that can be worked without alum or other additional retention aids or fixatives. In particular, the new paper sizing agents should also be able to be used with inferior material qualities such as waste paper and wood-containing materials and still lead reliably and easily to perfectly sized products.

Die Erfindung hat sich weiterhin die Aufgabe gestellt, das Verfahren zur Herstellung von geleimten Papieren unter Verwendung von Kolophonium-Dispersionen und Polyaluminiumhydroxychloriden als Fällungsmittel zu vereinfachen und dadurch das Verfahren auch sicherer und reproduzierbarer durchführen zu können.The invention has also set itself the task of simplifying the process for the production of sized papers using rosin dispersions and polyaluminium hydroxychlorides as precipitants, and thereby being able to carry out the process more reliably and reproducibly.

Die erste Aufgabe wird überraschenderweise durch Papierleimungsmittel gelöst, die dadurch gekennzeichnet sind, daß sie zusätzlich Polyaluminiumhydroxychloride und ggf. Retentions- und/oder Fixierungsmittel und/oder Naßfestmittel enthalten, wobei die Komponenten vorgemischt wurden unter Vermeidung von Agglomeration.The first object is surprisingly achieved by paper sizing agents, which are characterized in that they additionally contain polyaluminium hydroxychlorides and optionally retention and / or fixing agents and / or wet strength agents, the components being premixed while avoiding agglomeration.

Vorzugsweise enthalten die Papierleimungsmittel die Polyaluminiumhydroxychloride in handelsüblicher wäßriger Lösung mit einem Gehalt von 8 bis 20 Gew.-% Aluminiumoxid. Das Gesamtgemisch enthält vorzugsweise 5 bis 50 Gew.-% derartiger Polyaluminiumhydroxychlorid-Lösungen.The paper sizing agents preferably contain the polyaluminium hydroxychlorides in a commercially available aqueous solution with a content of 8 to 20% by weight of aluminum oxide. The total mixture preferably contains 5 to 50% by weight of such polyaluminium hydroxychloride solutions.

Dieses Ergebnis war völlig überraschend, da der Fachmann zunächst davon ausgehen mußte, daß beim Zusammengeben der Kolophonium-Dispersion mit den Polyaluminiumhydroxychloriden als Fällungsmittel eine vorzeitige Ausfällung erfolgt, die zu völlig unbrauchbaren Ergebnissen führt. Keinesfalls konnte erwartet werden, daß derartige Mischungen aus Leimungsmitteln und Fällungsmitteln, die gegebenenfalls auch die Retentions- und/oder Fixierungsmittel und/oder Naßfestmittel enthalten, überhaupt noch homogen auf und in das Fasermaterial eingebracht werden können und damit zur Leimung des Papieres führen.This result was completely surprising since the person skilled in the art had to assume that when the rosin dispersion was combined with the polyaluminium hydroxychlorides as precipitates premature precipitation occurs, which leads to completely unusable results. Under no circumstances could it be expected that such mixtures of sizing agents and precipitants, which may also contain the retention and / or fixing agents and / or wet strength agents, could be introduced homogeneously onto and into the fiber material and thus lead to the sizing of the paper.

Es hat sich weiterhin gezeigt, daß bei Verwendung der erfindungsgemäßen Gemische aus Papierleimungsmittel und Fällungsmittel wesentlich bessere und zuverlässigere Ergebnisse bei der Leimung erzielt werden können und sich das Verfahren zur Herstellung von geleimten Papieren dabei leichter und zuverlässiger durchführen läßt.It has also been shown that when using the mixtures of paper sizing agent and precipitating agent according to the invention, significantly better and more reliable results can be achieved in the sizing process and that the process for producing sized papers can be carried out more easily and reliably.

Die weitere Aufgabe der Erfindung, nämlich ein Verfahren zur Herstellung von geleimten Papieren unter Verwendung von Kolophonium-Dispersionen und Polyaluminiumhydroxychloriden als Fällungsmittel zu verbessern, wird dadurch gelöst, daß die Kolophonium-Dispersionen bereits vor dem Einsatz mit den Polyaluminiumhydroxychloriden unter Vermeidung von Agglomeration vermischt werden.The further object of the invention, namely to improve a process for the production of sized papers using rosin dispersions and polyaluminium hydroxychlorides as precipitants, is achieved in that the rosin dispersions are mixed with the polyaluminum hydroxychlorides before use, avoiding agglomeration.

Überraschenderweise ist es möglich und sogar bevorzugt, diesen Gemischen auch bereits die Retentions- und/oder Fixierungsmittel und/oder Naßfestmittel zuzugeben.Surprisingly, it is possible and even preferred to add the retention and / or fixing agents and / or wet strength agents to these mixtures.

Als Kolophonium-Dispersionen werden entweder herkömmlich unverstärkte Dispersionen aus Kolophoniumharz oder die herkömmlich verstärkten Harzleim-Dispersionen verwendet, die aus maleinsäureanhydrid- oder fumarsäuremodifiziertem Kolophonium oder Kohlenwasserstoffharz meist unter Zusatz von Schutzkolloiden oder oberflächenaktiven Substanzen hergestellt werden. Der Mengenanteil dieser Harzleimdispersion in dem erfindungsgemäßen Papierleimungsmittel beträgt 10 bis 60 Gew: %, vorzugsweise 30 bis 50 Gew.-%. Diese Kolophonium-Dispersionen sind im Handel erhältlich und besitzen üblicherweise einen Feststoffgehalt von 10 bis 50 Gew.-%.The rosin dispersions used are either conventionally unreinforced rosin resin dispersions or the conventionally reinforced resin glue dispersions which are prepared from rosin or hydrocarbon resin modified with maleic anhydride or fumaric acid, usually with the addition of protective colloids or surface-active substances. The proportion of this resin size dispersion in the paper size according to the invention is 10 to 60% by weight, preferably 30 to 50% by weight. These rosin dispersions are commercially available and usually have a solids content of 10 to 50% by weight.

Vorzugsweise enthalten die neuen Papierleimungsmittel bereits Retentions- und/oder Fixierungsmittel und/oder Naßfestmittel. Diese Zusätze bestehen im allgemeinen aus wäßrigen Lösungen oder Dispersionen beispielsweise von Polyamin-Epichlorhydrin-Harzen, Polyamid-Epichlorhydrin-Harzen, Polyacrylamiden, Polyethyleniminen, Kondensationsprodukten aus Formaldehyd mit Harnstoff oder Dicyandiamid oder Melamin oder Gemischen dieser Lösungen und Dispersionen. Der Mengenanteil dieser Zusätze beträgt 1 bis 20 Gew.- %, vorzugsweise 4 bis 15 Gew.-%. Auch hierbei handelt es sich meist um Handelsprodukte.The new paper sizing agents preferably already contain retention and / or fixing agents and / or wet strength agents. These additives generally consist of aqueous solutions or dispersions, for example of polyamine-epichlorohydrin resins, polyamide-epichlorohydrin resins, polyacrylamides, polyethyleneimines, condensation products of formaldehyde with urea or dicyandiamide or melamine or mixtures of these solutions and dispersions. The proportion of these additives is 1 to 20% by weight, preferably 4 to 15% by weight. These are also mostly commercial products.

Die Polyaluminiumhydroxychloride sind ebenfalls Handelsprodukte, die bisher insbesondere zur Fällung und Ausflockung gelöster Bestandteile von Abwässern eingesetzt wurden. Gemäß den oben genannten Patentschriften ist es möglich, sie auch anstelle von Alaun als Fällungsmittel oder bei künstlichen Leimungsmitteln als Retentionsmittel einzusetzen. Bei der praktischen Erprobung haben sich jedoch erhebliche Schwierigkeiten und Störungen gezeigt. Überraschenderweise wurde aber jetzt festgestellt, daß diese Polyaluminiumchloride üblichen Kolophonium-Dispersionen zugesetzt werden können, ohne daß es zur Ausflockung oder Ausfällung des Harzes kommt, oder hierbei völlig unbrauchbare Gemische entstehen. Überraschenderweise sind derartige Gemische in der Lage, in einem breiten pH-Bereich Papier, Pappe und Karton einwandfrei und differenziert zu leimen. Die pH-Unempfindlichkeit ist so groß, daß sogar der Zusatz von Alaun nicht stört, obwohl erfindungsgemäß gerade auf den Einsatz von Alaun verzichtet werden kann.The polyaluminium hydroxychlorides are also commercial products that have so far been used in particular for the precipitation and flocculation of dissolved constituents of waste water. According to the abovementioned patents, it is also possible to use them as a precipitant instead of alum or as a retention agent in the case of artificial sizing agents. However, considerable difficulties and disruptions have been shown in practical testing. Surprisingly, however, it has now been found that these polyaluminium chlorides can be added to conventional rosin dispersions without the resin flocculating or precipitating out or completely useless mixtures being formed. Surprisingly, such mixtures are able to glue paper, cardboard and cardboard correctly and differentially in a wide pH range. The pH insensitivity is so great that even the addition of alum does not interfere, although according to the invention the use of alum can be dispensed with.

Die erfindungsgemäßen Papierleimungsmittel sind im Gegensatz zu den synthetischen Leimungsmitteln in der Lage, minderwertige Ausgangsmaterialien wie Altpapier und holzhaltige Fasern einwandfrei zu verleimen.In contrast to synthetic sizing agents, the paper sizing agents according to the invention are able to properly glue inferior starting materials such as waste paper and wood-containing fibers.

Als Füllstoff wurde nämlich bisher in erster Linie Kaolin verwendet. In zunehmendem Maße wird aber auch Kreide, d.h. Calciumcarbonat als Füllstoff verwendet. Dieser Füllstoff ist gegen Alaun und Säure empfindlich, so daß es zu unerwünschten Umsetzungen, Verklebungen, Ausfällungen und sonstigen Betriebsstörungen kommt. Insbesondere bei Verwendung von Altpapier muß heute in zunehmendem Maße damit gerechnet werden, daß erhebliche Mengen von Kreide im Produkt vorhanden sind, welche bei der sauren Fixierung zu den genannten Störungen führt. Die erfindungsgemäßen Papierleimungsmittel können zumindest im pH-Bereich zwischen 3,5 und 9,0 einwandfrei eingesetzt werden. Vorzugsweise werden sie im neutralen Bereich eingesetzt, da in diesem Bereich erfahrungsgemäß die optimalen mechanischen Eigenschaften des geleimten Papieres entstehen. Die erfindungsgemäßen Papierleimungsmittel weisen den weiteren Vorteil auf, daß sie anwendungsfertig herstellbar sind. Sie sind ausreichend lange stabil und können gewünschtenfalls in jedem beliebigen Verhältnis mit Wasser verdünnt werden. Gegenüber herkömmlichen Papierleimungsmitteln unter Verwendung von Alaun wirken die neuen Papierleimungsmittel weniger korrosiv, sie führen zu verringerten Ablagerungen am Sieb, in den Filzen und den übrigen Maschinenteilen und bilden keinen Schaum im Stoffsystem.So far, kaolin has primarily been used as a filler. However, chalk, i.e. Calcium carbonate used as a filler. This filler is sensitive to alum and acid, so that it leads to undesired reactions, sticking, precipitation and other malfunctions. Particularly when using waste paper, it is increasingly to be expected today that considerable amounts of chalk are present in the product, which leads to the above-mentioned disturbances in the case of acid fixation. The paper sizes according to the invention can be used without problems at least in the pH range between 3.5 and 9.0. They are preferably used in the neutral area, since experience has shown that this area produces the optimal mechanical properties of the sized paper. The paper sizes according to the invention have the further advantage that they can be produced ready for use. They are stable for a sufficiently long time and, if desired, can be diluted with water in any ratio. Compared to conventional paper sizing agents using alum, the new paper sizing agents are less corrosive, they lead to reduced deposits on the screen, in the felts and the other machine parts and do not form any foam in the fabric system.

Die erfindungsgemäßen Papierleimungsmittel werden vorzugsweise kontinuierlich kurz vor dem Stoffauflauf der Papier- oder Kartonmaschine in den Stoffstrom eindosiert. Bei dieser Arbeitsweise gelingt es, mechanische Einflüsse auszuschalten und ein Maximum an Leimungswirkung zu erreichen. Diese kontinuierliche Dosierung erlaubt es, rasch auf den Leimungseffekt Einfluß nehmen zu können, wenn dies erforderlich ist. Die Leimung kann somit sehr differenziert eingestellt werden von der Halb-Leimung bis zur Voll-Leimung.The paper sizing agents according to the invention are preferably metered continuously into the material stream shortly before the headbox of the paper or board machine. With this method of working it is possible to eliminate mechanical influences and to achieve a maximum sizing effect. This continuous dosage makes it possible to quickly influence the sizing effect if necessary. The sizing can thus be set very differently from half-sizing to full-sizing.

Die Herstellung des erfindungsgemäßen Produktes ist relativ einfach. Sie kann beispielsweise erfolgen, in dem man die einzelnen Komponenten in einen Rührbehälter einleitet. Die Reihenfolge der Zugabe der Komponenten ist nicht kritisch. Vorzugsweise wird jedoch die Kolophonium-Dispersion (Harzleim-Dispersion) vorgelegt und dann die Lösung des Polyaluminiumhydroxychlorids zugeleitet. Dabei ist jedoch darauf zu achten, daß die Dosiergeschwindigkeit und die Rührgeschwindigkeit so eingestellt werden, daß eine Agglomeration vermieden wird. Die dritten und weiteren Komponenten, nämlich Retentionsmittel, Fixiermittel und Naßfestmittel werden gleichzeitig oder nacheinander der Mischung unter weiterem Rühren zugegeben. Die erfindungsgemäßen Papierleimungsmittel sind flüssig und liegen in Dispersionsform vor.The production of the product according to the invention is relatively simple. It can be done, for example, by introducing the individual components into a stirred tank. The order of adding the components is not critical. However, the rosin dispersion (resin glue dispersion) is preferably introduced and then the solution of the polyaluminium hydroxychloride is added tet. However, care must be taken that the metering speed and the stirring speed are set so that agglomeration is avoided. The third and further components, namely retention aid, fixative and wet strength agent, are added to the mixture simultaneously or in succession with further stirring. The paper sizes according to the invention are liquid and are in dispersion form.

Die Anwendung der erfindungsgemäßen Produkte zur Leimung von Papier, Pappe und Karton erfolgt in der Stoffmasse. Die Zugabestelle kann zwischen Pulper oder Holländer bis kurz vor dem Stoffauflauf liegen. Die Einsatzmenge wird meist zwischen 0,5 und 2% Festharz bezogen auf trockenen Faserstoff gewählt. Der damit erzielbare Leimungsgrad liegt dann zwischen 15 und 35 Cobbeo.The products according to the invention for sizing paper, cardboard and cardboard are used in the mass of material. The point of addition can be between pulper or Dutch until just before the headbox. The amount used is usually between 0.5 and 2% solid resin based on dry fiber. The degree of sizing that can be achieved is then between 15 and 35 Cobbeo.

In den nachfolgenden Beispielen sind einige typische Rezepturen sowie ihre Anwendung näher beschrieben.The following examples describe some typical recipes and their application.

Beispiel 1example 1

In einem Rührbehälter, versehen mit einem Rührer und Zuleitungen wird 200 g Harzleimdispersion (Kolophonium-Dispersion) mit einem Feststoffgehalt von 15 Gew.-% vorgelegt. Unter ständigem Rühren werden 200 g Poiyaiuminiumhydroxychiorid mit einem A1203-Gehalt von 10 Gew.-% zudosiert. Die Dosierungsgeschwindigkeit und Rührgeschwindigkeit werden so eingestellt, daß eine Agglomeration der beiden Komponenten vermieden wird. Nach der Beendigung der Zudosierung des Polyaluminiumhydroxychlorids wird noch eine halbe Stunde weiter gerührt, bis eine homogene Mischung entstanden ist. Das so hergestellte flüssige Produkt hat einen Feststoffgehalt von 22,5 Gew.-%. Das Mischverfahren kann auch umgekehrt werden, wobei das Polyaluminiumhydroxychlorid vorgelegt und die Harzdispersion zugemischt wird. Die Dispersion ist ca. 3 Wochen stabil.200 g of resin glue dispersion (rosin dispersion) with a solids content of 15% by weight are placed in a stirred container provided with a stirrer and feed lines. 200 g of Poiyaiuminiumhydroxychiorid with an A1 2 0 3 content of 10 wt .-% are metered in with constant stirring. The metering speed and stirring speed are adjusted so that agglomeration of the two components is avoided. After the addition of the polyaluminium hydroxychloride has ended, stirring is continued for another half an hour until a homogeneous mixture has formed. The liquid product thus produced has a solids content of 22.5% by weight. The mixing process can also be reversed, with the polyaluminium hydroxychloride being introduced and the resin dispersion being mixed in. The dispersion is stable for about 3 weeks.

Beispiel 2Example 2

In der gleichen Apparatur wie im Beispiel 1 werden 200 g Harzleim-Dispersionen mit einem Feststoffgehalt von 15 Gew.-% vorgelegt. Unter ständigem Rühren werden 150 g Polyaluminiumhydroxychlorid mit einem A1203-Gehalt von 10 Gew.-% zugemischt. Anschließend gibt man 50 g Polyamidoamin-Epichlorhydrinharz als 20%-ige Dispersion zu (Luresin/BASF). Nach weiterem Rühren von 30 Min. erhält man ein flüssiges Produkt mit einem Feststoffgehalt von 21,25 Gew.-%. Die Reihenfolge der Zusammengabe der drei Komponenten kann beliebig variiert werden. Die Dispersion ist mindestens 6 Wochen stabil.200 g of resin glue dispersions with a solids content of 15% by weight are placed in the same apparatus as in Example 1. 150 g of polyaluminium hydroxychloride with an A1 2 0 3 content of 10% by weight are mixed in with constant stirring. Then 50 g of polyamidoamine-epichlorohydrin resin are added as a 20% dispersion (Luresin / BASF). After stirring for a further 30 minutes, a liquid product with a solids content of 21.25% by weight is obtained. The order in which the three components are combined can be varied as required. The dispersion is stable for at least 6 weeks.

Beispiel 3Example 3

In gleicher Weise wie im Beispiel 2 beschrieben wird ein Papierleimungsmittel hergestellt unter Zusatz von 50 g einer Dispersion aus Formaldehyd und aliphatischen Amiden (Levogen PNK/Bayer) oder Fixiermittel (FP/BASF). Die Dispersion ist mindestens 6 Wochen stabil.In the same way as described in Example 2, a paper sizing agent is produced with the addition of 50 g of a dispersion of formaldehyde and aliphatic amides (Levogen PNK / Bayer) or fixing agent (FP / BASF). The dispersion is stable for at least 6 weeks.

Beispiel 4Example 4

In gleicher Weise wie im Beispiel 2 beschrieben wird ein Papierleimungsmittel hergestellt unter Zusatz von 50 g Polyethyleniminen (Polymin-Typen/BASF). Die Dispersion ist mindestens 6 Wochen stabil.In the same way as described in Example 2, a paper sizing agent is produced with the addition of 50 g of polyethyleneimines (Polymin types / BASF). The dispersion is stable for at least 6 weeks.

Beispiel 5Example 5

Zur Prüfung der Wirksamkeit der in den Beispielen 1 bis 4 beschriebenen Produkte wurden Probenblätter hergestellt. Dazu wurde ein Zellstoff verwendet, der aus 50% gebleichtem Sulfitzellstoff und 50% gebleichtem Sulfatzellstoff bestand. Dieser Stoff wurde mit Stadtwasser aufgeschlagen, auf 40°SR gemahlen und auf 2% Stoffdichte gebracht. Unter Zugabe von 20% Kreide als Füllstoff und entsprechender Menge an Leimungsmittel gemäß den Beispielen 1 bis 4 wurden die Probenblätter mittels Rapid-Köthen-Gerät hergestellt. Zur Prüfung des Leimungsgrades wurde die Cobb-Methode (60 Sek.) angewendet. Die Ergebnisse sind in der nachfolgenden Tabelle zusammengestellt.

Figure imgb0001
Sample sheets were produced to test the effectiveness of the products described in Examples 1 to 4. For this purpose, a cellulose was used which consisted of 50% bleached sulfite pulp and 50% bleached sulfate pulp. This material was beaten with city water, ground to 40 ° SR and brought to 2% consistency. With the addition of 20% chalk as filler and a corresponding amount of sizing agent according to Examples 1 to 4, the sample sheets were produced using a Rapid-Köthen device. The Cobb method (60 seconds) was used to check the degree of sizing. The results are summarized in the table below.
Figure imgb0001

Zum Vergleich wurde ein Probeblatt mit 1% atro Harzdispersion und 2% Alaun hergestellt. Dies wies einen Cobb-Wert von 35 auf.For comparison, a sample sheet with 1% atro resin dispersion and 2% alum was prepared. This had a Cobb value of 35.

Claims (8)

1. Paper sizing agents based on colophony dispersions, characterized in that they additionally contain polyaluminum hydroxychlorides and optionally retention agents and/or fixing agents and/or wet-strength agents, the components having been premixed such as to avoid agglomeration.
2. Paper sizing agents according to claim 1, characterized in that the polyaluminum hydroxychlorides are employed in the form of aqueous solutions having a content of from 8 to 20% by weight of aluminum oxide.
3. Paper sizing agents according to claim 1 or 2, characterized in that the polyaluminum hydroxychloride solution content is from 5 to 50% by weight, based on the total mixture.
4. Paper sizing agents according to any one of claims 1 to 3, characterized in that they contain, as retention agents, fixing agents and wet-strength agents, from 1 to 20% by weight of aqueous solutions or dispersions of polyamine-epichlorohydrin resins, polyamide-epichlorohydrin resins, polyacryl amides, polyethylene imines, condensation products of formaldehydes with urea or dicyandiamide or melamine or mixtures of said solutions and dispersions.
5. Paper sizing agents according to any one of claims 1 to 4, characterized in that there are used, as the colophony dispersion, conventional un- strengthened dispersions of colophony or conventionally strengthened resin size dispersions which are prepared from colophony modified with maleic anhydride or fumaric acid or from hydrocarbon resin, optionally with the addition of protective colloids or surface-active substances.
6. Use of paper sizing agents according to any one of claims 1 to 5 for the preparation of sized paper with out an addition of alum or other additional precipitating agents.
7. A process for the preparation of sized paper by using colophony dispersions and polyaluminum hydroxychlorides as precipitating agents characterized in that the colophony dispersions are already mixed with the polyaluminum hydroxychlorides prior to use such as to avoid agglomeration.
8. The process according to claim 7, characterized in that also the retention agents and/or fixing agents and/or wet-strength agents are already added to the mixture of colophony dispersion and polyaluminum hydroxychlorides.
EP86104329A 1985-04-13 1986-03-28 Paper-sizing agents and their use Expired - Lifetime EP0200002B2 (en)

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AT86104329T ATE40429T1 (en) 1985-04-13 1986-03-28 PAPER SIZES AND THEIR USE.

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DE3513249 1985-04-13
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AT406492B (en) * 1998-01-26 2000-05-25 Krems Chemie Ag AQUEOUS PAPER SIZING DISPERSIONS AND METHOD FOR THE PRODUCTION THEREOF

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FR2612961B1 (en) * 1987-03-23 1989-10-13 Atochem PROCESS FOR THE MANUFACTURE OF PAPER BY ADDITION TO THE FIBROUS SUSPENSION OF A MINERAL FILLER, A GLUING AGENT, CATIONIC STARCH AND ALUMINUM POLYCHLORIDE
DE3742764A1 (en) * 1987-12-17 1989-06-29 Sueddeutsche Kalkstickstoff FLOCKING AND / OR FIXING AGENTS FOR PAPER SIZING
GB8806432D0 (en) * 1988-03-18 1988-04-20 Albright & Wilson Paper sizing methods & compositions
ES2011990A6 (en) * 1989-02-02 1990-02-16 Costas Poch Juan Jose Method for obtaining a reactive cationized glue for mass sizing or press sizing of paper, and emulsion thus obtained
DE4306557C2 (en) * 1993-03-03 2000-08-10 Chem Fab Bruehl Oppermann Gmbh Use of a composition for surface sizing
DE19522832A1 (en) * 1995-06-23 1997-01-02 Chem Fab Bruehl Oppermann Gmbh Means for gluing paper, cardboard and cardboard and their use
SE513080C2 (en) 1998-04-14 2000-07-03 Kemira Kemi Ab Bonding composition and method of bonding

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DE897648C (en) * 1951-10-17 1953-11-23 Zschimmer & Schwarz Vormals Ch Process for the production of sizing agents for paper products and fiber boards
GB2050453B (en) * 1979-05-23 1983-02-09 Tenneco Chem Chemical compositions useful in the manufacture of paper sizing agents
ATE24559T1 (en) * 1983-05-02 1987-01-15 Schultz & Nauth Collodin Kleb NEUTRAL SIZE FOR CELLULOSIC SHEET STRUCTURES, PROCESS FOR ITS PRODUCTION AND ITS USE.
GB2159183A (en) * 1984-03-20 1985-11-27 Roe Lee Paper Chemicals Limite Paper sizing composition
SE8405260L (en) * 1984-10-22 1986-04-23 Eka Ab HYDROPHOBING AGENTS FOR ORGANIC FIBERS, Separate CELLULOS FIBERS, SET TO MAKE THIS AGENT AND THE USE OF THE MELD HYDROPHOBING AGENT

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AT406492B (en) * 1998-01-26 2000-05-25 Krems Chemie Ag AQUEOUS PAPER SIZING DISPERSIONS AND METHOD FOR THE PRODUCTION THEREOF

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