EP0036993A1 - Process for ennobling paper and paper-board - Google Patents

Process for ennobling paper and paper-board Download PDF

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Publication number
EP0036993A1
EP0036993A1 EP81101918A EP81101918A EP0036993A1 EP 0036993 A1 EP0036993 A1 EP 0036993A1 EP 81101918 A EP81101918 A EP 81101918A EP 81101918 A EP81101918 A EP 81101918A EP 0036993 A1 EP0036993 A1 EP 0036993A1
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EP
European Patent Office
Prior art keywords
paper
weight
cardboard
copolymers
acrylic acid
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EP81101918A
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German (de)
French (fr)
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EP0036993B1 (en
Inventor
Rudolf Behn
Lutz Dr. Hoppe
Klaus Dr. Szablikowski
Helmut Dr. Huhn
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Dow Produktions und Vertriebs GmbH and Co oHG
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Wolff Walsrode AG
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Priority to AT81101918T priority Critical patent/ATE5089T1/en
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43Carboxyl groups or derivatives thereof

Definitions

  • the invention relates to methods for reinforcing paper and cardboard materials with aqueous solutions of copolymers of acrylonitrile, acrylamide and acrylic acid.
  • Sheets of corrugated cardboard, containers or boxes made of corrugated cardboard, boxes made of cardboard materials or other types of paper or cardboard materials do not have sufficient strength, in particular water resistance, which is required for many purposes.
  • thermoplastic resins such as polystyrenes in solvents or in solvent mixtures are used to reinforce paper or corrugated cardboard: Xylene and other solvents that have to be used in very specific proportions. The recovery of the solvents is difficult and expensive. Xylene is also highly flammable. Such systems are therefore not suitable for continuous working methods.
  • DAS 2 345 982 polymers based on styrene, acrylonitrile, butadiene and acrylate are dissolved in a halogenated hydrocarbon and paper or cardboard materials are treated with this solution for reinforcement.
  • a major disadvantage of this process is that the products must be dissolved in organic solvents, the physiological effects of which are not entirely harmless.
  • Another disadvantage of using the water-insoluble substances is that the paper material must be dried to a water content of below 5% before the treatment in order to allow the organic solutions to diffuse into the paper. This drying is forbidden for economic reasons.
  • the strength of paper materials can now be significantly improved if the surface of the materials is treated with aqueous solutions of copolymers of acrylonitrile, acrylamide and acrylic acid. Since no alkali metal or alkaline earth metal salts, in particular Ca or Mg salts, of the copolymers have to be used, it is also possible to avoid waste water problems.
  • the invention therefore relates to processes for the surface treatment of paper, cardboard and K artonmaterialien with aqueous solutions of copolymers of (meth) acrylic acid derivatives and optionally customary aggregates, characterized in that as co-polymers of used, the sum of 1) - 3) must add up to 100% by weight.
  • copolymer solution used according to the invention can be prepared by known hydrolysis reactions of the polyacrylonitrile in water at elevated temperatures.
  • the production of these water-soluble copolymers from water-insoluble polyacrylonitrile by hydrolysis is described in DTPS 1 207 086 and in DTPS 2031 972.
  • the aqueous solution according to the invention should be 0.5 to 40% by weight. preferably contain 3 - 30 wt .-% of the copolymer.
  • crosslinking agents e.g. formaldehyde and epichlorohydrin
  • suitable cationative compounds which do not cause any incompatibility with the acrylic acid groups of the resin solution, can also be introduced into the resin solution, in order to use e.g. denser types of paper to achieve an even better mounting on the anion-actively charged fiber surface and binding to it.
  • Quaternary ammonium compounds such as e.g. 3-chloro-2-hydroxypropyl-trimethyl-ammonium chloride, modified polyamidoamines or water-soluble polyacrylamides.
  • the surface treatment is preferably carried out by spraying solutions onto the surface of the still wet paper fleece on the paper machine screen, in modern and larger paper machines, predominantly via a surface size press in the dryer section.
  • the aqueous polymer solution is preferably applied to both sides of the paper web in amounts of 0.5-25 g / m 2 copolymer.
  • the paper web is dried in the dryer section of the machine in a customary and environmentally friendly manner to a residual moisture content of 4-8%.
  • foam emulsion which is obtained by incorporating air (if appropriate after adding foam stabilizers) into the aqueous resin solution, to application surfaces to the paper web.
  • Suitable aggregates for applying foam to paper, cardboard or Cardboard materials include the size press, spray nozzles, rollers with suitable doctor blades.
  • a great advantage of the foam applicator compared to the solution application is the slight increase in the moisture content of the paper web, which can increase the reaction rate by up to 30%.
  • the method according to the invention can be used both on corrugated paper materials and on other types of paper or cardboard materials of different basis weights.
  • the aqueous resin solution penetrates into the paper or cardboard material to be treated without the need for any penetrant, so that the material is sufficiently impregnated with the aqueous resin solution in a very short time and has good strength and water resistance.
  • the material treated according to the invention is also well suited for the production of boxes and containers.
  • reinforced core and / or cover layers can also be produced continuously for corrugated cardboard production and then corrugated.
  • a non-surface-treated corrugated material with a basis weight of 123 g / m 2 with a residual moisture content of 5% and a working width of 30 cm and a speed of 4m / min is passed through an application bath, in which contains a 7% by weight aqueous solution of a copolymer consisting of 3% by weight of acrylonitrile, 47% by weight of acrylic acid and 50% by weight of acrylamide.
  • the wound and surface-treated paper has a residual moisture of 5% and a basis weight of 131 g / m 2 , which corresponds to an application of 7.5 g / m 2 on both sides.
  • the foam which is obtained after stirring for 30 seconds in the kitchen mixer, is stable over 15 minutes and shows a volume increase of at least 20% compared to the 7% by weight copolymer solution.
  • This foam is applied to both sides of corrugated paper as indicated in Example 1.
  • the residual moisture is 5%
  • the basis weight is determined with 132 g / m 2 and the application with 8.4 g / m 2 .
  • Example 2 On the same test machine as described in Example 1, a diluted, broken down maize starch suspension, adjusted to 7% by weight, is used for the surface coating of corrugated paper analogous to Example 1.
  • the residual moisture after the drying process of the corrugated paper treated with corn starch is also 5%, the basis weight is determined at 133 g / m 2, which corresponds to an application of 9.4 g / m 2 on both sides.
  • the residual moisture is 5% and the basis weight is determined to be 132 g / m 2 .
  • the double-sided order is 8, 4 g / m 2.
  • a copolymer according to Example 1 of DT-OS 2 741 753 was converted into the corresponding salt with calcium hydroxide.
  • a 7% by weight copoly Merisat salt solution is applied to both sides of corrugated material (paper) as in Example 1.
  • the residual moisture is 5%, the basis weight is determined at 131 g / m 2 and the application at 7.5 g / m 2 .
  • Tables I and II show the physical values of the paper treated in this way.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)

Abstract

1. Process for improving the strength of paper, board or card materials by treating the surface of these materials with aqueous solutions of copolymers of (meth)acrylic acid derivatives and optionally customary additives, characterized in that the copolymers used are copolymers of 1. 0.1-10 % by weight of acrylonitrile, 2. at least 30 % by weight of acrylamide and 3. 30-60 % by weight of acrylic acid and/or methacrylic acid, which can optionally be present entirely or partially in the form of their ammonium salt.

Description

Die Erfindung betrifft Verfahren zur Verstärkung von Papier- und Pappmaterialien mit wäßrigen Lösungen von Copolymeren aus Acrylnitril, Acrylamid und Acrylsäure.The invention relates to methods for reinforcing paper and cardboard materials with aqueous solutions of copolymers of acrylonitrile, acrylamide and acrylic acid.

Bahnen aus Wellpappe, Behälter oder Schachteln aus Wellpappe, Schachteln aus Pappmaterialien oder anderen Arten von Papier oder Pappmaterialien haben keine ausreichende Festigkeit, insbesondere Wasserfestigkeit, die für viele Einsatzzwecke gefordert wird.Sheets of corrugated cardboard, containers or boxes made of corrugated cardboard, boxes made of cardboard materials or other types of paper or cardboard materials do not have sufficient strength, in particular water resistance, which is required for many purposes.

Bei der Herstellung von Verstärkungspappmaterialien ist es bereits bekannt, zur Verbesserung der Wasserfestigkeit das gewellte Pappmaterial in Bahnenform in eine Polycarbonatlösung einzutauchen, um das gewellte Pappmaterial zu imprägnieren oder beschichten. Dieses Verfahren hat jedoch den Nachteil, daß das Polycarbonat nun schwierig in Methylenchlorid oder Ethylenchlorid aufzulösen ist.In the production of reinforcing cardboard materials, it is already known to immerse the corrugated cardboard material in sheet form in a polycarbonate solution in order to improve the water resistance in order to impregnate or coat the corrugated cardboard material. However, this process has the disadvantage that the polycarbonate is now difficult to dissolve in methylene chloride or ethylene chloride.

Nach der US PS 3 479 213 werden zum Verstärken von Papier oder Wellpappe Lösungen von verschiedenen, insbesondere thermoplastischen Harzen wie Polystyrolen in Lösungsmitteln oder in Lösungsmittelgemischen verwendet :wie z.B. Xylol und weiteren Lösungsmitteln, die in ganz bestimmten Verhältnissen eingesetzt werden müssen. Die Rückgewinnung der Lösungsmittel ist schwieirig und aufwendig. Außerdem ist Xylol leicht brennbar. Für kontinuierliche Arbeitsweisen eignen sich daher solche Systeme nicht.According to US Pat. No. 3,479,213, solutions of various, in particular thermoplastic resins such as polystyrenes in solvents or in solvent mixtures are used to reinforce paper or corrugated cardboard: Xylene and other solvents that have to be used in very specific proportions. The recovery of the solvents is difficult and expensive. Xylene is also highly flammable. Such systems are therefore not suitable for continuous working methods.

In der DAS 2 345 982 werden Polymerisate auf Basis Styrol, Acrylnitril, Butadien und Acrylat in einem Halogenkohlenwasserstoff gelöst und Papier- oder Pappmaterialien zur Verstärkung mit dieser Lösung behandelt. Ein großer nachteil dieses Verfahren ist, daß die Produkte in organischen Lösungsmitteln gelöst werden müssen, deren physiologische Wirkungen nicht ganz unbedenklich sind.In DAS 2 345 982, polymers based on styrene, acrylonitrile, butadiene and acrylate are dissolved in a halogenated hydrocarbon and paper or cardboard materials are treated with this solution for reinforcement. A major disadvantage of this process is that the products must be dissolved in organic solvents, the physiological effects of which are not entirely harmless.

Ein weiterer Nachteil der Verwendung der wasserunlöslichen Substanzen ist, daß das Papiermaterial vor der Behandlung auf einen Wassergehalt von unter 5 % getrocknet werden muß, um ein Diffundieren der organischen Lösungen in das Papier zu erreichen. Diese Nachtrocknung verbietet sich schon aus wirtschaftlichen Gründen.Another disadvantage of using the water-insoluble substances is that the paper material must be dried to a water content of below 5% before the treatment in order to allow the organic solutions to diffuse into the paper. This drying is forbidden for economic reasons.

Weiter ist aus der DAS 1 182 047 bekannt, daß wasserlösliche Copolymerisate, bestehend aus 55 bis 94 Gew.-% Acrylsäureamid und/oder Methacrylsäureamid und 45 bis 6 Gew.-% Estern ungesättigter Carbonsäuren mit 1 - 4 Kohlenstoffatomen enthaltenen Alkoholen, zur Verbesserung der Fettundurchlässigkeit und zur Erhöhung der Beständigkeit gegen lösungsmittelhaltige Lacke und Paraffinschmelzen von Papieren eingesetzt werden können. Für viele Einsatzgebiete reicht die Festigkeit des so imprägnierten Papiermaterials aber nicht aus.It is also known from DAS 1 182 047 that water-soluble copolymers consisting of 55 to 94% by weight of acrylic acid amide and / or methacrylic acid amide and 45 to 6% by weight of esters of unsaturated carboxylic acids with 1-4 carbon atoms, to improve alcohols Greaseproof and to increase the resistance to solvent-based lacquers and paraffin melts of paper can be used. However, the strength of the paper material so impregnated is not sufficient for many areas of application.

Dies gilt auch für das Papier, das gemäß der DOS 2 741 753 mit Alkali- oder Erdalkalisalzen von Copolymerisaten aus (Meth)acrylsäure, Acrylnitril und/oder Acrylamid und gegebenenfalls (Meth)acrylsäureestern imprägniert wird.This also applies to paper that is impregnated with alkali or alkaline earth salts of copolymers of (meth) acrylic acid, acrylonitrile and / or acrylamide and optionally (meth) acrylic acid esters according to DOS 2 741 753.

überraschenderweise gelingt es nun, die Festigkeit von Papiermaterialien noch entscheidend zu verbessern, wenn man die Oberfläche der Materialien mit wäßrigen Lösungen von Copolymerisaten aus Acrylnitril, Acrylamid und Acrylsäure behandelt. Da keine Alkali- oder Erdalkalimetallsalze, insbesondere Ca- oder Mg Salze, der Copolymeren, eingesetzt werden müssen, gelingt es außerdem, Abwässerprobleme zu vermeiden.Surprisingly, the strength of paper materials can now be significantly improved if the surface of the materials is treated with aqueous solutions of copolymers of acrylonitrile, acrylamide and acrylic acid. Since no alkali metal or alkaline earth metal salts, in particular Ca or Mg salts, of the copolymers have to be used, it is also possible to avoid waste water problems.

Gegenstand der Erfindung sind daher Verfahren zur Oberflächenbehandlung von Papier-, Pappe- und Kartonmaterialien mit wäßrigen Lösungen von Copolymerisaten von (Meth)acrylsäurederivaten und ggf. üblichen Zuschlägen, dadurch gekennzeichnet, daß man als Co- polymerisate aus

Figure imgb0001
einsetzt, wobei die Summe aus 1) - 3) 100 Gew.-% ergeben muß.The invention therefore relates to processes for the surface treatment of paper, cardboard and K artonmaterialien with aqueous solutions of copolymers of (meth) acrylic acid derivatives and optionally customary aggregates, characterized in that as co-polymers of
Figure imgb0001
used, the sum of 1) - 3) must add up to 100% by weight.

Die Herstellung der erfindungsgemäß verwendeten Co-polymerisatlösung kann durch bekannte Hydrolyse-Reaktionen des Polyacrylnitrils in Wasser bei erhöhten Temperaturen erfolgen. Die Herstellung dieser wasserlöslichen Co-polymerisate aus wasserunlöslichen Polyacrylnitril durch Hydrolyse, wird in der DTPS 1 207 086 und in der DTPS 2031 972 beschrieben.The copolymer solution used according to the invention can be prepared by known hydrolysis reactions of the polyacrylonitrile in water at elevated temperatures. The production of these water-soluble copolymers from water-insoluble polyacrylonitrile by hydrolysis is described in DTPS 1 207 086 and in DTPS 2031 972.

Die erfindungsgemäße wäßrige Lösung soll 0.,5 - 40 Gew.-%. vorzugsweise 3 - 30 Gew.-% des Copolymeren enthalten.The aqueous solution according to the invention should be 0.5 to 40% by weight. preferably contain 3 - 30 wt .-% of the copolymer.

Außerdem werden vorzugsweise die verschiedenen, in der Papierindustrie üblichen Additive in die erfindungsgemäß zu verwendende Co-polymerlösung eingearbeitet.In addition, the various additives customary in the paper industry are preferably incorporated into the copolymer solution to be used according to the invention.

Zu nennen ist die Zugabe von Stärke- und Carboxymethylcellulose Produkten, die eine Verminderung der Staubbildung oder eine verbesserte Filmbildung auf der Oberfläche des Papiers oder des Pappmaterials bewirken können. Weiterhin können auch bei Bedarf Farbstoffe und Pigmente, sowie Füllstoffe, z.B. Kaolin, Kreide und Titandioxid, je nach individuellem Verwendungszweck in die Harzlösung eindispergiert werden.Worth mentioning is the addition of starch and carboxymethyl cellulose products, which can reduce dust formation or improve film formation on the surface of the paper or cardboard material. Furthermore, dyes and pigments, as well as fillers, e.g. Kaolin, chalk and titanium dioxide can be dispersed into the resin solution depending on the individual use.

Soll z.B. die Naßfestigkeit eines Papiers oder Pappmaterials erhöht werden, so können ebenfalls kationenaktive Naßfestmittel in die Harzlösung eingebracht werden. Auch kann durch Zugabe von geringen Mengen Vernetzungsmittel (z.B. Formaldehyd und Epichlorhydrin) eine erhöhte Wasserundurchlässigkeit nach dem Trocknen des Papiers und Pappenmaterials erreicht werden.Should e.g. If the wet strength of a paper or cardboard material is increased, cation-active wet strength agents can also be introduced into the resin solution. The addition of small amounts of crosslinking agents (e.g. formaldehyde and epichlorohydrin) can also increase the impermeability to water after drying the paper and cardboard material.

Schließlich können auch in die Harzlösung geeignete kationenative Verbindungen, die mit den Acrylsäuregruppen der Harzlösung keine Unverträglichkeit hervorrufen, eingebracht werden, um bei z.B. dichteren Papiersorten ein noch besseres Aufziehen auf die anionenaktiv geladene Faseroberfläche und Bindung 'an diese zu erreichen. Zu nennen sind quarternäre Ammoniumverbindungen wie z.B. 3-Chlor-2-Hydroxypropyl-Trimethyl-Ammoniumchlorid, modifizierte Polyamidoamine oder auch wasserlösliche Polyacrylamide.Finally, suitable cationative compounds, which do not cause any incompatibility with the acrylic acid groups of the resin solution, can also be introduced into the resin solution, in order to use e.g. denser types of paper to achieve an even better mounting on the anion-actively charged fiber surface and binding to it. Quaternary ammonium compounds such as e.g. 3-chloro-2-hydroxypropyl-trimethyl-ammonium chloride, modified polyamidoamines or water-soluble polyacrylamides.

Für Papierlagen und Wellbahnen, wie Materialien zur Herstellung von Wellpappe und anderen entsprechenden Papier- und Pappmaterialien, die nach dem erfindungsgemäßen Verfahren behandelt werden, ist eine Vortrocknung unter einem Restfeuchtigkeitsgehalt von 10 % nicht erforderlich.For paper layers and corrugated sheets, such as materials for the production of corrugated cardboard and other corresponding paper and cardboard materials, which are treated by the process according to the invention, predrying with a residual moisture content of 10% is not necessary.

In der Papierindustrie, z.B. bei der Herstellung von Wellstoffpapieren, erfolgt die Oberflächenbehandlung vorzugsweise durch Aufsprühung von Lösungen auf die Oberfläche des noch nassen Papiervlieses auf dem Papiermaschinensieb, bei modernen und größeren Papiermaschinen, überwiegend über eine Oberflächenleimpresse in der Trockenpartie.In the paper industry, e.g. in the production of corrugated paper, the surface treatment is preferably carried out by spraying solutions onto the surface of the still wet paper fleece on the paper machine screen, in modern and larger paper machines, predominantly via a surface size press in the dryer section.

Die wäßrige Polymerlösung wird vorzugsweise auf beiden Seiten der Papierbahn in Mengen von 0,5 - 25 g/m2 Copolymerisat aufgetragen.The aqueous polymer solution is preferably applied to both sides of the paper web in amounts of 0.5-25 g / m 2 copolymer.

Nach der Oberflächenveredelung der Papierbahn erfolgt eine übliche und umweltfreundliche Trocknung der Papierbahn in der Trockenpartie der Maschine bis auf eine Restfeuchtigkeit von 4 - 8 %.After the surface of the paper web has been finished, the paper web is dried in the dryer section of the machine in a customary and environmentally friendly manner to a residual moisture content of 4-8%.

Es ist auch möglich eine Schaumemulsion, die durch Einarbeiten von Luft (gegebenenfalls nach Zusatz von Schaumstabilisatoren) in die wäßrige Harzlösung erhalten wird, über Auftragsaggregate auf die Papierbahn oberflächlich aufzutragen. Geeignete Aggregate zum Auftragen von Schaum auf Papier-, Pappe oder Kartonmaterialien sind u.a. die Leimpresse, Sprühdüsen, Walzen mit geeigneten Rakeln. Ein großer Vorteil des Schaumaufträgers im Vergleich zum Lösungsauftrag ist die geringe Steigerung des Feuchtigkeitsgehaltes der Papierbahn, wodurch einer Steigerung der Reaktionsgeschwindigkeit bis zu 30 % erreicht werden kann.It is also possible to apply a foam emulsion, which is obtained by incorporating air (if appropriate after adding foam stabilizers) into the aqueous resin solution, to application surfaces to the paper web. Suitable aggregates for applying foam to paper, cardboard or Cardboard materials include the size press, spray nozzles, rollers with suitable doctor blades. A great advantage of the foam applicator compared to the solution application is the slight increase in the moisture content of the paper web, which can increase the reaction rate by up to 30%.

Das erfindungsgemäße Verfahren ist sowohl auf Wellpapiermaterialien als auch auf anderen Arten von Papier oder Pappmaterialien unterschiedlichster Flächengewichte anwendbar. Die wäßrige Harzlösung dringt in das zu behandelnde Papier oder Pappmaterial ein, ohne daß irgendein Durchdringungsmittel erforderlich wäre, so daß das Material innerhalb einer sehr kurzen Zeit ausreichend mit der wäßrigen Harzlösung imprägniert ist und eine gute Festigkeit- und Wasserbeständigkeit aufweist.The method according to the invention can be used both on corrugated paper materials and on other types of paper or cardboard materials of different basis weights. The aqueous resin solution penetrates into the paper or cardboard material to be treated without the need for any penetrant, so that the material is sufficiently impregnated with the aqueous resin solution in a very short time and has good strength and water resistance.

Das erfindungsgemäß behandelte Material eignet sich auch gut für die Herstellung von Schachteln und Behälter. Nach dem erfindungsgemäßen Verfahren können auch für die Wellpappenherstellung verstärkte Kern-und/oder Decklagen kontinuierlich hergestellt und anschließend gewellt werden.The material treated according to the invention is also well suited for the production of boxes and containers. With the method according to the invention, reinforced core and / or cover layers can also be produced continuously for corrugated cardboard production and then corrugated.

Beispiel 1example 1

Auf einer Versuchsmaschine der Firma Jagenberg, Typ: Laboranlage, wird ein nicht oberflächenbehandelter Wellenstoff mit einem Flächengewicht von 123 g/m2 mit einer Restfeuchte von 5 % und einer Arbeitsbreite von 30 cm und einer Geschwindigkeit von 4m/min durch ein Auftragsbad geführt, in dem ein 7 Gew.-%ige wäßrige Lösung eines Copolymerisats, bestehend aus 3 Gew.-% Acrylnitril, 47 Gew.-% Acrylsäure und 50 Gew.-% Acrylamid enthalten ist.On a test machine from Jagenberg, type: laboratory system, a non-surface-treated corrugated material with a basis weight of 123 g / m 2 with a residual moisture content of 5% and a working width of 30 cm and a speed of 4m / min is passed through an application bath, in which contains a 7% by weight aqueous solution of a copolymer consisting of 3% by weight of acrylonitrile, 47% by weight of acrylic acid and 50% by weight of acrylamide.

Nach Abquetschung des beidseitig behandelten Wellenstoffpapieres schließt sich eine Trocknung in einem Trockenkanal bei 150°C an. Das aufgewickelte und oberflächenbehandelte Papier hat eine Restfeuchtigkeit von 5 % und ein Flächengewicht von 131 g/m2, das einem Auftrag von 7,5 g/m2 beidseitig entspricht.After squeezing the corrugated paper treated on both sides, drying in a drying tunnel at 150 ° C follows. The wound and surface-treated paper has a residual moisture of 5% and a basis weight of 131 g / m 2 , which corresponds to an application of 7.5 g / m 2 on both sides.

Beispiel 2Example 2

Es wird eine 7 gew.-%ige, wäßrige Copolymerisat. Lösung wie in Beispiel 1 beschrieben, mit Hilfe eines Küchenmixers und durch Zusatz einer geringen Menge (1 %) eines üblichen Emulgators in die Schaumform überführt.It becomes a 7% by weight aqueous copolymer. Solution as described in Example 1, converted into the foam form with the aid of a kitchen mixer and by adding a small amount (1%) of a conventional emulsifier.

Der Schaum, der nach 30 sec. Rühren im Küchenmixer erhalten wird, ist über 15 Min. stabil und zeigt eine Volumenzunahme von mindestens 20 % im Vergleich zu der 7 Gew.-%igen Copolymerisat-Lösung.The foam, which is obtained after stirring for 30 seconds in the kitchen mixer, is stable over 15 minutes and shows a volume increase of at least 20% compared to the 7% by weight copolymer solution.

Dieser Schaum wird wie in Beispiel 1 angegeben auf Wellenstoffpapier beidseitig aufgetragen. Die Restfeuchtigkeit beträgt 5 %, das Flächengewicht wird mit 132 g/m2 und der Auftrag mit 8,4 g/m2 ermittelt.This foam is applied to both sides of corrugated paper as indicated in Example 1. The residual moisture is 5%, the basis weight is determined with 132 g / m 2 and the application with 8.4 g / m 2 .

Vergleichsbeispiel 1Comparative Example 1

Auf derselben wie im Beispiel 1 beschriebenen Versuchsmaschine wird eine verdünnte aufgeschlossene und auf 7 Gew.-% eingestellte Maisstärkesuspension für die Oberflächenbeschichtung von Wellenstoffpapier analog Beispiel 1 benutzt. Die Restfeuchtigkeit nach dem Trocknungsvorgang des so mit Maisstärke behandelten Wellenstoffpapiers beträgt ebenfalls 5 %, das Flächengewicht wird mit 133 g/m" ermittelt, das einem Auftrag von 9,4 g/m2 beidseitig entspricht.On the same test machine as described in Example 1, a diluted, broken down maize starch suspension, adjusted to 7% by weight, is used for the surface coating of corrugated paper analogous to Example 1. The residual moisture after the drying process of the corrugated paper treated with corn starch is also 5%, the basis weight is determined at 133 g / m 2, which corresponds to an application of 9.4 g / m 2 on both sides.

Zur Charakterisierung der Festigkeitseigenschaften werden folgende physikalische Daten nach angegebenen Standardmethoden ermittelt. Als 0-Probe wird der nicht behandelte Wellenstoff für die physikalischen Messungen herangezogen.

  • 1. Messung des CMT-Wertes nach DIN 53 143 als wesentliche Meßgröße zur Bestimmung des Flachstauchwiderstandes an labormäßig gewellten Papieren.
  • 2. Messung der Berstfestigkeit (Mullentest nach DIN 53141).
  • 3. Die Bestimmung der Wasseraufnahme nach Cobb nach DIN 53132.
To characterize the strength properties, the following physical data are determined using the specified standard methods. The untreated wave material is used as the 0 sample for the physical measurements.
  • 1. Measurement of the CMT value according to DIN 53 143 as an essential parameter for determining the flat crush resistance on corrugated papers in the laboratory.
  • 2. Measurement of the burst strength (gauze test according to DIN 53141).
  • 3. Determination of water absorption according to Cobb according to DIN 53132.

In Tabelle I sind die Untersuchungsergebnisse zusammengefaßt. In Tabelle II der Untersuchungen der Steifigkeit gemessen nach DIN 53121 enthalten.The test results are summarized in Table I. Contained in Table II of the tests of rigidity measured according to DIN 53121.

Vergleichsbeispiel 2 (gemäß DAS 1 182 047, Beispiel 1)Comparative Example 2 (according to DAS 1 182 047, Example 1)

Auf derselben wie im Beispiel 1 beschriebenen Versuchsmaschine wird eine 7 gew.-%ige wäßrige Lösung eines Copolymerisats, bestehend aus 80 Teilen Metacrylsäureamid und 20 Teilen Acrylsäureethylester mit einem K-Wert von 45, beidseitig wie im Beispiel 1 beschrieben, auf Wellenstoff aufgetragen. Die Restfeuchtigkeit beträgt 5 %, das Flächengewicht wird mit 132 g/m2 ermittelt. Der beidseitige Auftrag beträgt 8,4 g/m 2.A 7% strength by weight aqueous solution of a copolymer consisting of 80 parts of methacrylic acid amide and 20 parts of ethyl acrylate with a K value of 45, described on both sides as in Example 1, is applied to corrugated material on the same test machine as described in Example 1. The residual moisture is 5% and the basis weight is determined to be 132 g / m 2 . The double-sided order is 8, 4 g / m 2.

In den Tabelle I und II sind wieder die Untersuchungsergebnisse der physikalischen Messungen angegeben.The test results of the physical measurements are again given in Tables I and II.

Vergleichsbeispiel 3 (gemäß DOS 27 41 753)Comparative Example 3 (according to DOS 27 41 753)

Es wurde ein Copolymerisat gemäß Beispeil 1 der DT-OS 2 741 753 mit Calciumhydroxid in das entsprechende Salz überführt. Eine 7 Gew.-%ige Copolymerisat-Salz-Lösung wird wie im Beispiel 1 auf Wellenstoff (Papier) beidseitig, aufgetragen. Die Restfeuchtigkeit beträgt 5 %, das Flächengewicht wird mit 131 g/m2 und der Auftrag mit 7,5 g/m2 ermittelt.A copolymer according to Example 1 of DT-OS 2 741 753 was converted into the corresponding salt with calcium hydroxide. A 7% by weight copoly Merisat salt solution is applied to both sides of corrugated material (paper) as in Example 1. The residual moisture is 5%, the basis weight is determined at 131 g / m 2 and the application at 7.5 g / m 2 .

In den Tabellen I und II sind die physikalischen Werte des so behandelten Papiers eingetragen.

Figure imgb0002
Figure imgb0003
Tables I and II show the physical values of the paper treated in this way.
Figure imgb0002
Figure imgb0003

Claims (5)

1) Verfahren zur Verbesserung der Festigkeit von Papier-,-Pappe- oder Kartonmaterialien indem man die Oberfläche dieser Materialien mit wäßrigen Lösungen von Copolymerisaten von (Meth)-acrylsäurederivaten und ggf. üblichen Zuschlagstoffen behandelt, dadurch gekennzeichnet, daß man als Copolymerisate aus 1) 0,1 - 10 Gew.-% Acrylnitril 2) 30 - 70 Gew.-% Acrylamid und 3) 30 - 60 Gew.-% Acrylsäure und/oder Methacrylsäure, die gegebenenfalls ganz oder teilweise in Form ihres Ammoniumsalzes vorliegen können,
wobei die Summe aus 1) - 3) immer 100 Gew.-% ergeben muß, einsetzt.
1) Process for improving the strength of paper, cardboard or cardboard materials by treating the surface of these materials with aqueous solutions of copolymers of (meth) acrylic acid derivatives and, if appropriate, conventional additives, characterized in that copolymers of 1) 0.1-10% by weight acrylonitrile 2) 30-70% by weight of acrylamide and 3) 30-60% by weight of acrylic acid and / or methacrylic acid, which may optionally be wholly or partly in the form of their ammonium salt,
where the sum of 1) - 3) must always be 100% by weight.
2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß ein Copolymerisat aus 0,1 - 7 Gew.-% der Komponente 1, 35 - 65 Gew.-% der Komponente 2, und 30 - 60 Gew.-% der Komponente 3, verwendet wird.2) Method according to claim 1, characterized in that a copolymer of 0.1-7% by weight of component 1, 35-65% by weight of component 2, and 30-60% by weight of component 3, is used. 3) Verfahren nach Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die wäßrige Lösung 0,5 - 40 Gew.-% des Copolymerisats enthält.3) Process according to claims 1 and 2, characterized in that the aqueous solution contains 0.5 - 40 wt .-% of the copolymer. 4) Verfahren nach Ansprüchen 1 - 3, dadurch gekennzeichnet, daß das Copolymerisat in Mengen von 0,5 - 25 g/m2 aufgetragen wird.4) Process according to claims 1-3, characterized in that the copolymer in amounts from 0.5 to 25 g / m 2 is applied. 5) Verfahren nach Ansprüchen 1 - 4, dadurch gekennzeichnet, daß die wäßrige Polymersatlösung aufgesprüht oder in Form einer Schaumemulsion auf die zu behandelnde Oberfläche aufgebracht wird.5) Process according to claims 1-4, characterized in that the aqueous polymer solution is sprayed on or applied in the form of a foam emulsion to the surface to be treated.
EP81101918A 1980-03-28 1981-03-16 Process for ennobling paper and paper-board Expired EP0036993B1 (en)

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AT81101918T ATE5089T1 (en) 1980-03-28 1981-03-16 PROCESSES FOR FINISHING PAPER, CARDBOARD AND CARDBOARD.

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DE19803012002 DE3012002A1 (en) 1980-03-28 1980-03-28 METHOD FOR FINISHING PAPER, CARDBOARD AND CARDBOARD
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193111A2 (en) * 1985-02-27 1986-09-03 BASF Aktiengesellschaft Process for producing paper with a high dry strength
US5890530A (en) * 1995-06-21 1999-04-06 Electrovac, Fabrikation Elektrotechnischer Spezialartikel Gesellschaft M.B.H. Method of making MMC components
EP0953679A1 (en) * 1998-04-22 1999-11-03 Hymo Corporation Paper strengthening agent and paper strengthening method
US6159340A (en) * 1996-02-29 2000-12-12 Basf Aktiengesellschaft Hydrolyzed polymers of N-vinylcarboxamides as paper, paperboard and cardboard dry strength enhancers
US6740373B1 (en) * 1997-02-26 2004-05-25 Fort James Corporation Coated paperboards and paperboard containers having improved tactile and bulk insulation properties

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4423118A (en) * 1981-08-20 1983-12-27 The Dow Chemical Company Thickened paper coating composition
US6919111B2 (en) 1997-02-26 2005-07-19 Fort James Corporation Coated paperboards and paperboard containers having improved tactile and bulk insulation properties

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2164902A1 (en) * 1971-12-28 1973-08-02 Freudenberg Carl Fa Non-woven fabric prodn - using foamed latex binder

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999038A (en) * 1958-01-24 1961-09-05 Rohm & Haas Method of producing wet-strength papers
CA961212A (en) * 1970-09-29 1975-01-21 Kiyoharu Inoue Paper producing process
DE2741753B1 (en) * 1977-09-16 1979-03-22 Basf Ag Process for making paper with high dry strength and low wet strength

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2164902A1 (en) * 1971-12-28 1973-08-02 Freudenberg Carl Fa Non-woven fabric prodn - using foamed latex binder

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193111A2 (en) * 1985-02-27 1986-09-03 BASF Aktiengesellschaft Process for producing paper with a high dry strength
EP0193111A3 (en) * 1985-02-27 1987-05-20 Basf Aktiengesellschaft Process for producing paper with a high dry strength
US5890530A (en) * 1995-06-21 1999-04-06 Electrovac, Fabrikation Elektrotechnischer Spezialartikel Gesellschaft M.B.H. Method of making MMC components
US6159340A (en) * 1996-02-29 2000-12-12 Basf Aktiengesellschaft Hydrolyzed polymers of N-vinylcarboxamides as paper, paperboard and cardboard dry strength enhancers
US6740373B1 (en) * 1997-02-26 2004-05-25 Fort James Corporation Coated paperboards and paperboard containers having improved tactile and bulk insulation properties
EP0953679A1 (en) * 1998-04-22 1999-11-03 Hymo Corporation Paper strengthening agent and paper strengthening method

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DE3161211D1 (en) 1983-11-24
EP0036993B1 (en) 1983-10-19
ATE5089T1 (en) 1983-11-15
JPS56148995A (en) 1981-11-18
DE3012002A1 (en) 1981-10-08

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