EP0445161A1 - De-inking of old papers - Google Patents

De-inking of old papers

Info

Publication number
EP0445161A1
EP0445161A1 EP89912962A EP89912962A EP0445161A1 EP 0445161 A1 EP0445161 A1 EP 0445161A1 EP 89912962 A EP89912962 A EP 89912962A EP 89912962 A EP89912962 A EP 89912962A EP 0445161 A1 EP0445161 A1 EP 0445161A1
Authority
EP
European Patent Office
Prior art keywords
copolymers
water
polymers
average molecular
molecular weights
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP89912962A
Other languages
German (de)
French (fr)
Inventor
Konrad Engelskirchen
Herbert Fischer
Klaus Hornfeck
Doris Oberkobusch
Ludwig Schieferstein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0445161A1 publication Critical patent/EP0445161A1/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/02—Working-up waste paper
    • D21C5/025—De-inking
    • D21C5/027—Chemicals therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Definitions

  • the invention relates to a method for deinking waste paper and the use of at least partially water-soluble polymers containing amino and / or ammonium groups with number average molecular weights between 2,000 and 500,000 for deinking waste paper printed with water-thinnable printing inks.
  • waste paper For the production of, for example, newspaper printing and hygiene papers, waste paper is used in large quantities today. For these types of paper, brightness and color mean certain quality features. To achieve this, the printing inks must be removed from the printed waste paper. This is usually done using deinking processes, which essentially take place in two steps:
  • the second process step can be carried out by washing or flotation (Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, volume 17, pages 570-571 (1979)).
  • flotation in which the different wettability of printing inks and paper fibers is used, air is pressed or sucked through the fiber suspensions. Small air bubbles combine with the ink particles and form a foam on the surface of the water, which is removed with fabric hangers.
  • the deinking of waste paper is usually carried out at alkaline pH values in the presence of alkali hydroxides, alkali silicates, oxidative bleaches and surface-active substances at temperatures between 30 and 50 ° C.
  • Soaps and / or fatty alcohol polyglycol ethers are often used as surface-active substances which bring about the detachment and separation of the printing inks (Ullmanns Encyclopedia of technical chemistry, 4th edition, volume 17, pages 571-572 (1979) ). It is known from German published patent application DE 1517148 that in the presence of proteins with molecular weights of, for example, 10,000 or with polyvinylpyrrolidones, printing inks based on petroleum oils can be removed from waste paper.
  • German patent applications DE 33 22 330 and DE 33 47 906 describe the use of alkylamine polyethers for the removal of printing ink. Furthermore, from JP 84/137 587, referenced in Chem. Abstr. 102. 80638b (1985) Ethylene ⁇ imin-ethylene oxide propylene oxide copolymers and from JP 82/25489, referenced in Chem. Abstr. 97, 57393n (1982) ethylene oxide-propylene oxide-alkyl (alkenyl) amine adducts are known as deinging chemicals.
  • Water-thinnable printing inks have the decisive disadvantage that they can only be removed, if at all, completely inadequately with the usual surfactants contained in the deinking fleet (Wochenblatt für Textilfabr / ication .13., 537-538 (1988) ).
  • the result of this is that to date the accumulating waste paper that has been printed in water-thinnable printing inks is not being recycled and is therefore not available as a waste paper raw material for newsprint and hygiene paper.
  • the object of the invention was therefore to develop a deinking process with which it is possible to deink waste paper which contains waste paper components printed with water-dilutable printing inks.
  • the invention accordingly relates to a process for deinking waste paper, which is characterized in that waste paper printed with water-thinnable printing inks in the presence of at least partially water-soluble polymers containing amino and / or ammonium groups and / or copolymers with number average molecular weights between 2 000 and 500 000 are opened and then the ink particles are removed in a manner known per se by flotation or washing out of the fiber suspensions.
  • Another object of the invention is the use of at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2,000 and 500,000 for deinking waste paper printed with water-thinnable printing inks.
  • At least partially water-soluble means that the polymers and / or copolymers are more or less than 0.01% by weight soluble or water-soluble in water at the application pH.
  • At least partially water-soluble polymers and / or copolymers containing amino groups also includes polymers with pyridine groups, for example polymers based on 2-vinylpyridine and / or 4-vinylpyridine.
  • a polymer group which is particularly preferred for the process according to the invention are copolymers of polyethylene and / or ethyleneimine. If desired, these can be used together with other at least partially water-soluble polymers containing amino and / or ammonium groups and / or copolymers with number average molecular weights between 2000 and 500000.
  • Polymers and / or copolymers based on 2-vinylpyridine, 4-vinylpyridine and / or 1-vinylimidazole for example poly-4-vinylpyridine, copolymers of 1-vinylimidazole and N-vinylpyrrolidone with vinylimidazole contents between 10 and 90% by weight, if appropriate in combination with further at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2,000 and 500,000, are particularly suitable.
  • polymers and / or copolymers are prepared by polymerization processes known per se, for example in bulk in the presence of radical-forming substances (Ullman's Encyclopedia of Technical Chemistry, 4th edition, volume 23, pages 611-614, Verlag Chemie Weinheim 1983) ).
  • At least partially water-soluble primary, secondary, tertiary and / or quaternized cellulose-containing amino groups Hydroxyethyl celluloses, starches, chitosan and / or guar are examples of primary, secondary, tertiary and / or quaternized amino group-containing polysaccharides and / or heteropolysaccharides.
  • tertiary and / or quaternized amino groups into amino group-free polysaccharides and / or heteropolysaccharides is carried out in a manner known per se by reacting polysaccharides and / or heteropolysaccharides with tertiary amines which contain a glycidyl radical and / or with ammonium compounds (US 3,472 840).
  • tertiary amines which contain a glycidyl radical and / or with ammonium compounds (US 3,472 840).
  • Dimethylglycidylamine and 3-chloro-2-hydroxypropyltrimethylammonium chloride are examples of tertiary amines and ammonium compounds.
  • Water-dilutable printing inks can furthermore be removed particularly well in the presence of proteins, if appropriate in combination with further at least partially water-soluble polymers containing amino and / or ammonium groups and / or copolymers with number average molecular weights between 2000 and 500,000.
  • water-thinnable printing inks for example water-thinnable flexographic printing inks
  • printed waste paper for example newspapers, illustrated papers, computer papers, magazines, brochures, forms, telephone books and / or catalogs.
  • the deinked waste papers obtained are characterized by very high degrees of whiteness.
  • the waste papers to be deinked are dissolved in a cloth dissolver in an aqueous solution, which is typically 0.5 to 1.0% by weight 100% hydrogen peroxide, 0.5 to 2.5% by weight 100% NaOH up to 4.0% by weight of water glass, 35% by weight (37-40 ° B ⁇ ) and 0.01 to 1% by weight of active substance at least partially water-soluble amino and / or Polymers and / or copolymers containing ammonium groups - all% by weight - information relates to air-dry waste paper - contains, opened at temperatures between 20 and 60 ° C. In order to obtain good deinking results, 0.01 to 1 g of active substance, polymers and / or copolymers according to the invention are used per 100 g of air-dry waste paper.
  • the fiber suspensions are stirred into water, so that 0.6 to 1.6 wt .-% pulp suspensions are obtained.
  • the flotation is then preferably carried out in a manner known per se, for example in a Denver flotation cell.
  • the deinkability index (DEM) was calculated from the reflection factors R457nm (whiteness) of the printed (BS), deinked (DS) and unprinted (US) paper stocks using the following formula:
  • TZBLATT (0% means no ink removal, 100% means quantitative ink removal).

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Paper (AREA)

Abstract

Procédé de désencrage de vieux papiers en présence de polymères et/ou de copolymères au moins partiellement solubles dans l'eau et contenant des groupes amino et/ou ammonium.Method for deinking old paper in the presence of polymers and / or copolymers at least partially soluble in water and containing amino and / or ammonium groups.

Description

"Deinken von Altpapieren" "Deinking of waste paper"
Die Erfindung betrifft ein Verfahren zum Deinken von Altpapieren sowie die Verwendung von mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren mit Zahlenmitteln der Molekulargewichte zwischen 2 000 und 500 000 zum Deinken von mit wasserverdünnbaren Druckfarben bedruckten Altpapieren.The invention relates to a method for deinking waste paper and the use of at least partially water-soluble polymers containing amino and / or ammonium groups with number average molecular weights between 2,000 and 500,000 for deinking waste paper printed with water-thinnable printing inks.
Zur Herstellung von beispielsweise Zeitungsdruck- und Hygienepa¬ pieren werden heute in großen Mengen Altpapiere eingesetzt. Für diese Papiersorten bedeuten Helligkeit und Farbe bestimmte Quali¬ tätsmerkmale. Um diese zu erreichen, müssen die Druckfarben aus den bedruckten Altpapieren entfernt werden. Üblicherweise geschieht dies mittels Deinking-Verfahren, die im wesentlichen in 2 Teil¬ schritten ablaufen:For the production of, for example, newspaper printing and hygiene papers, waste paper is used in large quantities today. For these types of paper, brightness and color mean certain quality features. To achieve this, the printing inks must be removed from the printed waste paper. This is usually done using deinking processes, which essentially take place in two steps:
1. Aufschlagen der Altpapiere, d. h. Zerfasern in Wasser bei gleichzeitigem Einwirken der für die Ablösung der Druckfarben¬ teilchen benötigten Chemikalien und1. opening the waste paper, d. H. Defibrating in water with simultaneous action of the chemicals and. Required for the detachment of the printing ink particles
2. Ausscheidung der abgelösten Druckfarbenteilchen aus der Faser¬ stoffSuspension. Der 2. Verfahrensschritt kann durch Auswaschen oder Flotation er¬ folgen (Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Band 17, Seiten 570 - 571 (1979)). Bei der Flotation, bei der die unterschiedliche Benetzbarkeit von Druckfarben und Papierfasern ausgenutzt wird, wird Luft durch die Faserstoffsuspensionen ge¬ drückt oder gesaugt. Dabei verbinden sich kleine Luftbläschen mit den Druckfarbenteilchen und bilden an der Wasseroberfläche einen Schaum, der mit Stoffängern entfernt wird.2. Elimination of the detached ink particles from the fiber suspension. The second process step can be carried out by washing or flotation (Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, volume 17, pages 570-571 (1979)). In flotation, in which the different wettability of printing inks and paper fibers is used, air is pressed or sucked through the fiber suspensions. Small air bubbles combine with the ink particles and form a foam on the surface of the water, which is removed with fabric hangers.
Üblicherweise wird das Deinken von Altpapieren bei alkalischen pH-Werten in Gegenwart von Alkalihydroxiden, Alkalisilikaten, oxidativ wirkenden Bleichmitteln und oberflächenaktiven Substanzen bei Temperaturen zwischen 30 und 50 °C durchgeführt. Als ober¬ flächenaktive Substanzen, die das Ablösen und Trennen der Druck¬ farben bewirken, werden häufig Seifen und/oder Fettalkoholpoly- glykolether eingesetzt (Ullmanns Encyclopädie der technischen Che¬ mie, 4. Auflage, Band 17, Seiten 571-572 (1979)). Aus der deutschen Offenlegungsschrift DE 1517148 ist bekannt, daß sich in Gegenwart ' von Proteinen mit Molekulargewichten von beispielsweise 10000 oder mit Polyvinylpyrrolidonen Druckfarben auf der Basis von Petroleum¬ ölen aus Altpapieren entfernen lassen. In den deutschen Offenle- gungsschriften DE 33 22 330 und DE 33 47 906 wird die Verwendung ' von Alkylaminpolyethem zur Entfernung von Druckerschwärze be¬ schrieben. Des weiteren sind aus JP 84/137 587, referiert in Chem. Abstr. 102. 80638b (1985) Ethyleπimin-Ethylenoxidpropylenoxid-Co- polymere und aus JP 82/25489, referiert in Chem. Abstr. 97, 57393n (1982) Ethylenoxid-Propylenoxid-Alkyl(alkenyl)amin-Addukte als De- inkingchemikalien bekannt.The deinking of waste paper is usually carried out at alkaline pH values in the presence of alkali hydroxides, alkali silicates, oxidative bleaches and surface-active substances at temperatures between 30 and 50 ° C. Soaps and / or fatty alcohol polyglycol ethers are often used as surface-active substances which bring about the detachment and separation of the printing inks (Ullmanns Encyclopedia of technical chemistry, 4th edition, volume 17, pages 571-572 (1979) ). It is known from German published patent application DE 1517148 that in the presence of proteins with molecular weights of, for example, 10,000 or with polyvinylpyrrolidones, printing inks based on petroleum oils can be removed from waste paper. The German patent applications DE 33 22 330 and DE 33 47 906 describe the use of alkylamine polyethers for the removal of printing ink. Furthermore, from JP 84/137 587, referenced in Chem. Abstr. 102. 80638b (1985) Ethyleneπimin-ethylene oxide propylene oxide copolymers and from JP 82/25489, referenced in Chem. Abstr. 97, 57393n (1982) ethylene oxide-propylene oxide-alkyl (alkenyl) amine adducts are known as deinging chemicals.
Die klassischen Druckfarbensysteme, beispielsweise auf Basis Nitrocellulose, • Maleinatharze und/oder Schellack, die Ester und/oder etone, beispielsweise Ethylacetat und/oder Methylethylketon, oder Alkohole als Lösungsmittel enthalten, werden in den letzten Jahren aus Umweltschutzgründen in zunehmendem Maße durch wasserverdünnbare Druckfarben ersetzt. Ein weiterer Grund für die zunehmende Verwendung wasserverdünnbarer Druckfarben liegt in der Unbrennbarkeit von Wasser, wodurch in den Druckereien die bei Verwendung lösungsmittelhaltiger Druckfarben notwendige Installa¬ tion aufwendiger Schutzeinrichtungen überflüssig wird. Die meisten wasserverdünnbaren Druckfarben enthalten als Bindemittel anionische Polymere, beispielsweise carboxylgruppenhaltige Polymere, durch deren Neutralisation mit Basen die Druckfarben wasserverdünnbar werden.The classic printing ink systems, for example based on nitrocellulose, maleate resins and / or shellac, the esters and / or etones, for example ethyl acetate and / or For reasons of environmental protection, methyl ethyl ketone or alcohols as solvents have been increasingly replaced by water-dilutable printing inks in recent years. Another reason for the increasing use of water-thinnable printing inks is the incombustibility of water, as a result of which the installation of expensive protective devices necessary when using solvent-containing printing inks is no longer necessary. Most water-thinnable printing inks contain anionic polymers as binders, for example polymers containing carboxyl groups, which neutralize with bases make the printing inks water-thinnable.
Wasserverdünnbare Druckfarben haben jedoch den entscheidenden Nachteil, daß sie mit den üblichen in der Deinking-Flotte enthal¬ tenen Tensiden - wenn überhaupt - nur völlig unzureichend ent¬ fernt werden können (Wochenblatt für Papierfabr/ikation .13., 537-538 (1988)). Das hat zur Folge, daß bis heute die in immer größeren Mengen anfallenden Altpapiere, die mit wasserverdünnbaren Druck¬ farben bedruckt wurden, nicht wiederverwertet werden und somit auch nicht als Altpapierrohstoff für Zeitungsdruck- und Hygienepapiere zur Verfügung stehen.Water-thinnable printing inks, however, have the decisive disadvantage that they can only be removed, if at all, completely inadequately with the usual surfactants contained in the deinking fleet (Wochenblatt für Papierfabr / ication .13., 537-538 (1988) ). The result of this is that to date the accumulating waste paper that has been printed in water-thinnable printing inks is not being recycled and is therefore not available as a waste paper raw material for newsprint and hygiene paper.
Die Aufgabe der Erfindung bestand somit in der Entwicklung eines Deinking-Verfahrens, mit dem es möglich ist, Altpapiere, die mit wasserverdünnbaren Druckfarben bedruckte Altpapierbestandteile enthalten, zu deinken.The object of the invention was therefore to develop a deinking process with which it is possible to deink waste paper which contains waste paper components printed with water-dilutable printing inks.
Überraschenderweise wurde gefunden, daß wasserverdünnbare Druck¬ farben in Wasch-Deinking- oder Flotation-Deinking-Verfahren in Ge¬ genwart von mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren entfernt werden können. Gegenstand der Erfindung ist dementsprechend ein Verfahren zum Deinken von Altpapieren, welches dadurch gekennzeichnet ist, daß mit wasserverdünnbaren Druckfarben bedruckte Altpapiere in Gegen¬ wart von mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlen¬ mitteln der Molekulargewichte zwischen 2 000 und 500 000 aufge¬ schlagen werden und anschließend die Druckfarbenteilchen in an sich bekannter Weise durch Flotation oder Auswaschen aus den Faser- stoffsuspensionen entfernt werden.Surprisingly, it has been found that water-thinnable printing inks can be removed in the wash deinking or flotation deinking process in the presence of at least partially water-soluble polymers and / or copolymers containing amino and / or ammonium groups. The invention accordingly relates to a process for deinking waste paper, which is characterized in that waste paper printed with water-thinnable printing inks in the presence of at least partially water-soluble polymers containing amino and / or ammonium groups and / or copolymers with number average molecular weights between 2 000 and 500 000 are opened and then the ink particles are removed in a manner known per se by flotation or washing out of the fiber suspensions.
Weiterer Erfindungsgegenstand ist die Verwendung von mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekularge¬ wichte zwischen 2 000 und 500 000 zum Deinken von mit wasserverdünnbaren Druckfarben bedruckten Altpapieren.Another object of the invention is the use of at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2,000 and 500,000 for deinking waste paper printed with water-thinnable printing inks.
Vorzugsweise kommen mindestens teilweise wasserlösliche amino- und/oder ammoniumgruppenhaltige Polymere und/oder Copolymere mit / Zahlenmitteln der Molekulargewichte zwischen 5 000 und 200 000, besonders bevorzugt solche mit Zahlenmitteln der Molekulargewichte zwischen 10000 und 100000 zum Einsatz.Preferably at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with / number average molecular weights between 5,000 and 200,000, particularly preferably those with number average molecular weights between 10,000 and 100,000 are used.
"Mindestens teilweise wasserlöslich" bedeutet, daß die Polymeren und/oder Copolymeren beim Anwendungs-pH-Wert zu mehr als 0,01 Gew.-% in Wasser klar oder trübe löslich sind."At least partially water-soluble" means that the polymers and / or copolymers are more or less than 0.01% by weight soluble or water-soluble in water at the application pH.
Der Begriff "mindestens teilweise wasserlösliche aminogruppenhal- tige Polymere und/oder Copolymere" umfaßt auch Polymere mit Pyri- dingruppen, beispielsweise Polymere auf Basis von 2-Vinylpyridin und/oder 4-Vinylpyridin. Eine für das erfindungsgemäße Verfahren besonders bevorzugte Poly¬ merengruppe sind Polyethyleni ine und/oder ethyleniminhaltige Copolymere. Diese können gewünschtenfalls zusammen mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgrup¬ penhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und 500000 eingesetzt werden.The term “at least partially water-soluble polymers and / or copolymers containing amino groups” also includes polymers with pyridine groups, for example polymers based on 2-vinylpyridine and / or 4-vinylpyridine. A polymer group which is particularly preferred for the process according to the invention are copolymers of polyethylene and / or ethyleneimine. If desired, these can be used together with other at least partially water-soluble polymers containing amino and / or ammonium groups and / or copolymers with number average molecular weights between 2000 and 500000.
Zum Deinken von Altpapieren sind ferner Polymere und/oder Copolymere auf der Basis von 2-Vinylpyridin, 4-Vinylpyridin und/oder 1-Vinylimidazol, beispielsweise Poly-4-vinylpyridin, Copolymere aus 1-Vinylimidazol und N-Vinylpyrrolidon mit Vinylimidazolgehalten zwischen 10 und 90 Gew.-%, gegebenenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2 000 und 500 000 besonders geeignet. Die Herstellung dieser Polymeren und/oder Copolymeren wird nach an sich bekannten Polymerisations¬ verfahren beispielsweise in Substanz in Gegenwart radikalbildender > Substanzen durchgeführt (Ullmans Encyclopädie der technischen Che¬ mie, 4. Auflage, Band 23, Seiten 611 - 614, Verlag Chemie Weinheim 1983).Polymers and / or copolymers based on 2-vinylpyridine, 4-vinylpyridine and / or 1-vinylimidazole, for example poly-4-vinylpyridine, copolymers of 1-vinylimidazole and N-vinylpyrrolidone with vinylimidazole contents between 10 and 90% by weight, if appropriate in combination with further at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2,000 and 500,000, are particularly suitable. These polymers and / or copolymers are prepared by polymerization processes known per se, for example in bulk in the presence of radical-forming substances (Ullman's Encyclopedia of Technical Chemistry, 4th edition, volume 23, pages 611-614, Verlag Chemie Weinheim 1983) ).
Primäre, sekundäre, tertiäre und/oder quaternierte aminogruppenhaltige Polysaccharide und/oder Heteropolysaccharide und/oder deren Derivate, die gegebenenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlen¬ mitteln der Molekulargewichte zwischen 2000 und 500000 eingesetzt werden können, sind eine weitere besonders bevorzugte Polymerengruppe für das erfindungsgemäße Deinking-Verfahren. Min¬ destens teilweise wasserlösliche primäre, sekundäre, tertiäre und/oder quaternierte aminogruppenhaltige Cellulosen, Hydroxyethylcellulosen, Stärken, Chitosan und/oder Guar sind Bei¬ spiele für primäre, sekundäre, tertiäre und/oder quaternierte aminogruppenhaltige Polysaccharide und/oder Heteropolysaccharide. Die Einführung tertiärer und/oder quaternierter Aminogruppen in aminogruppenfreie Polysaccharide und/oder Heteropolysaccharide er¬ folgt in an sich bekannter Weise, indem Polysaccharide und/oder Heteropolysaccharide mit tertiären Aminen, die einen Glycidylrest enthalten, und/oder mit Ammoniumverbindungen umgesetzt werden (US 3 472 840). Dimethylglycidylamin und 3-Chlor-2-hydroxypropyl- trimethylammoniumchlorid sind Beispiele für tertiäre Amine und Am- moniumverbindungen.Primary, secondary, tertiary and / or quaternized amino group-containing polysaccharides and / or heteropolysaccharides and / or their derivatives, optionally in combination with further at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2000 and 500,000 can be used are another particularly preferred group of polymers for the deinking process according to the invention. At least partially water-soluble primary, secondary, tertiary and / or quaternized cellulose-containing amino groups, Hydroxyethyl celluloses, starches, chitosan and / or guar are examples of primary, secondary, tertiary and / or quaternized amino group-containing polysaccharides and / or heteropolysaccharides. The introduction of tertiary and / or quaternized amino groups into amino group-free polysaccharides and / or heteropolysaccharides is carried out in a manner known per se by reacting polysaccharides and / or heteropolysaccharides with tertiary amines which contain a glycidyl radical and / or with ammonium compounds (US 3,472 840). Dimethylglycidylamine and 3-chloro-2-hydroxypropyltrimethylammonium chloride are examples of tertiary amines and ammonium compounds.
Wasserverdünnbare Druckfarben lassen sich weiterhin besonders gut in Gegenwart von Proteinen, gegebenenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copo'lymeren mit Zahlen¬ mittel der Molekulargewichte zwischen 2000 und 500000 aus Altpa¬ pieren entfernen.Water-dilutable printing inks can furthermore be removed particularly well in the presence of proteins, if appropriate in combination with further at least partially water-soluble polymers containing amino and / or ammonium groups and / or copolymers with number average molecular weights between 2000 and 500,000.
In Gegenwart der o. g. Polymeren und/oder Copolymeren lassen sich wasserverdünnbare Druckfarben, beispielsweise wasserverdünnbare Flexodruckfarben aus bedruckten Altpapieren, beispielsweise Zei- ' tungen, Illustrierten, Computerpapieren, Zeitschriften, Broschüren, Formularen, Telefonbüchern und/oder Katalogen entfernen. Die er¬ haltenen deinkten Altpapiere zeichnen sich durch sehr hohe Wei߬ grade aus.In the presence of the above Polymers and / or copolymers can be removed from water-thinnable printing inks, for example water-thinnable flexographic printing inks, from printed waste paper, for example newspapers, illustrated papers, computer papers, magazines, brochures, forms, telephone books and / or catalogs. The deinked waste papers obtained are characterized by very high degrees of whiteness.
Die zu deinkenden Altpapiere werden in einem Stofflöser in einer wässrigen Lösung, die typischerweise 0,5 bis 1,0 Gew.-% 100%iges Wasserstoffperoxid, 0,5 bis 2,5 Gew.-% 100%iges NaOH, 2,0 bis 4,0 Gew.-% Wasserglas, 35 Gew.-%ig (37 - 40 °B§) und 0,01 bis 1 Gew-% Aktivsubstanz mindestens teilweise wasserlösliche amino- und/oder ammoniumgruppenhaltige Polymere und/oder Copolymere - alle Gew.-%-Angaben beziehen sich auf lufttrockenes Altpapier - ent¬ hält, bei Temperaturen zwischen 20 und 60 °C aufgeschlagen. Um gute Deinking-Ergebnisse zu bekommen, werden pro 100 g lufttrockenem Altpapier 0.01 bis 1 g Aktivsubstanz erfindungsgemäße Polymere und/oder Copolymere eingesetzt. Nach einer Verweilzeit zwischen 60 und 120 Minuten bei Temperaturen zwischen 20 und 60 °C werden die Faserstoffsuspensionen in Wasser eingerührt, so daß 0,6 bis 1,6 Gew.-%ige StoffSuspensionen erhalten werden. Anschließend wird vorzugsweise in an sich bekannter Weise, beispielsweise in einer Denver-Flotationszelle flotiert.The waste papers to be deinked are dissolved in a cloth dissolver in an aqueous solution, which is typically 0.5 to 1.0% by weight 100% hydrogen peroxide, 0.5 to 2.5% by weight 100% NaOH up to 4.0% by weight of water glass, 35% by weight (37-40 ° B§) and 0.01 to 1% by weight of active substance at least partially water-soluble amino and / or Polymers and / or copolymers containing ammonium groups - all% by weight - information relates to air-dry waste paper - contains, opened at temperatures between 20 and 60 ° C. In order to obtain good deinking results, 0.01 to 1 g of active substance, polymers and / or copolymers according to the invention are used per 100 g of air-dry waste paper. After a dwell time between 60 and 120 minutes at temperatures between 20 and 60 ° C, the fiber suspensions are stirred into water, so that 0.6 to 1.6 wt .-% pulp suspensions are obtained. The flotation is then preferably carried out in a manner known per se, for example in a Denver flotation cell.
ERSATZBLATT BeispieleREPLACEMENT LEAF Examples
AnwendunosbeispieleApplication examples
98 g lutro ( = 90 g atro bei 8 % Feuchte) bedrucktes Altpapier98 g lutro (= 90 g atro at 8% moisture) printed waste paper
(lutro = lufttrocken, atro = absolut trocken) aus 100 % Zeitungen, bedruckt mit wasserverdünnbaren Flexodruckfarben, wurde bei 3,5(lutro = air dry, atro = absolutely dry) from 100% newspapers, printed with water-dilutable flexographic printing inks, was at 3.5
Gew.-% Stoffdichte im Laborpulper mit wäßrigen Lösungen, bestehend aus% By weight consistency in the laboratory pulper with aqueous solutions consisting of
2 Gew.-% Natronwasserglas, 37 - 40 °B§ 1 Gew.-% Natriumhydroxid (100 %ig) 0,7 Gew.-% Wasserstoffperoxid (100 Gew.-%ig) 0,4 Gew.-% Tensid oder 0,2 Gew.-% erfindungsgemäßes Polymer oder Copolymer2% by weight soda water glass, 37 - 40 ° B§ 1% by weight sodium hydroxide (100%) 0.7% by weight hydrogen peroxide (100% by weight) 0.4% by weight surfactant or 0 , 2 wt .-% polymer or copolymer according to the invention
bei 45 °C mittels Dispergierseheibe (3000 Umdrehungen pro Minute) aufgeschlagen und nach 1 3/4 Stunde bei 45 °C auf 1 Gew.-% ver¬ dünnt, indem die Faserstoffsuspensionen in Wasser eingerührt wur- den. Anschließend wurden die FaserstoffSuspensionen bei 45 °C in einer Denver-Flotationszelle bei 1 900 Umdrehungen pro Minute in¬ nerhalb von 15 Minuten flotiert.whipped at 45 ° C using a dispersing disc (3000 revolutions per minute) and diluted to 1% by weight after 1 3/4 hours at 45 ° C by stirring the fiber suspensions into water. The fibrous suspensions were then floated at 45 ° C. in a Denver flotation cell at 1,900 revolutions per minute within 15 minutes.
Die Deinking-Ergebnisse des in Gegenwart unterschiedlicher Poly¬ merer und Copolymerer sowie in Gegenwart von Tensiden erhaltenen deinkten Altpapiers sind in Tabelle 1 zusammengefaßt. Die Deinkbarkeitsmaßzahl (DEM) wurde aus den Reflexionsfaktoren R457nm (Weißgrad) der bedruckten (BS), deinkten (DS) und unbedruckten (US) Papierstoffe noch folgender Formel errechnet:The deinking results of the deinked waste paper obtained in the presence of different polymers and copolymers and in the presence of surfactants are summarized in Table 1. The deinkability index (DEM) was calculated from the reflection factors R457nm (whiteness) of the printed (BS), deinked (DS) and unprinted (US) paper stocks using the following formula:
Weißgrad (DS) - Weißgrad (BS) DEM (%) = : x 100Whiteness (DS) - Whiteness (BS) DEM (%) =: x 100
Weißgrad (US) - Weißgrad (BS)Whiteness (US) - Whiteness (BS)
TZBLATT (0 % bedeutet keine Druckfarbenentfernung, 100 % bedeutet quanti- tat i ve Druckfarbenentfernung ) .TZBLATT (0% means no ink removal, 100% means quantitative ink removal).
« /«/
ERSATZBLATT REPLACEMENT LEAF
-) neutralisiertes Polyethylenimin - 50 Gew.-%ige wäßrige-) neutralized polyethyleneimine - 50 wt .-% aqueous
Lösung, mittleres Molekulargewicht (MG) = 100 000, Brookfield-Viskosität (25 °C, 20 Umdrehungen pro Minute): 300 Pas; Hersteller: Cyanamid (USA)Solution, average molecular weight (MW) = 100,000, Brookfield viscosity (25 ° C, 20 revolutions per minute): 300 Pas; Manufacturer: Cyanamid (USA)
2) quaternierte Hydroxyethylcellulose - Quaternierungsmittel: 3-Chlor-2-hydroxypropyltrimethylammoniumchlorid, Quaternierungsgrad: 0,4/Anhydroglucoseeinheit; Aktivsub¬ stanzgehalt: 95 %; Hersteller: Union Carbide2) quaternized hydroxyethyl cellulose quaternizing agent: 3-chloro-2-hydroxypropyltrimethylammonium chloride, degree of quaternization: 0.4 / anhydroglucose unit; Active substance content: 95%; Manufacturer: Union Carbide
3) 01inorR 4010, Henkel KGaA 3 ) 01inor R 4010, Henkel KGaA
ERSATZBLATT ERS A TZBLATT

Claims

Patentansprüche Claims
1. Verfahren zum Deinken von Altpapieren, dadurch gekennzeichnet, daß mit wasserverdünnbaren Druckfarben bedruckte Altpapiere in Gegenwart von mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der mittleren Molekulargewichte zwischen1. A process for deinking waste paper, characterized in that waste paper printed with water-thinnable printing inks in the presence of at least partially water-soluble polymers containing amino and / or ammonium groups and / or copolymers with number average molecular weights between
2 000 und 500 000 aufgeschlagen werden und anschließend die Druckfarbenteilchen in an sich bekannter Weise durch Flotation oder Auswaschen aus den FaserstoffSuspensionen entfernt werden.2,000 and 500,000 are opened and then the ink particles are removed in a manner known per se by flotation or washing out of the fiber suspensions.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß mit wasserverdünnbaren Druckfarben bedruckte Altpapiere in Gegen¬ wart von mindestens teilweise wasserlöslichen amino- und/oder arnmoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 5000 und 200000, vorzugsweise zwischen 10000 und 100000, aufgeschlagen werden.2. The method according to claim 1, characterized in that waste paper printed with water-thinnable printing inks in the presence of at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 5000 and 200000, preferably between 10000 and 100000, be opened.
3. Verfahren nach einem oder beiden der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß mit wasserverdünnbaren Druckfarben be¬ druckte Altpapiere in Gegenwart von Polyethyleni inen und/oder ethyleni inhaltigen Copolymeren, gewünschtenfalls in Kombina- ' tion mit weiteren mindestens teilweise wasserlöslichen amirto- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und3. The method according to one or both of claims 1 to 2, characterized in that be¬ printed with water-dilutable printing inks in the presence of Polyethyleni inen and / or ethyleni-containing copolymers, if desired in combination with ' at least partially water-soluble amirto and / or polymers and / or copolymers containing ammonium groups with number average molecular weights between 2000 and
500000 aufgeschlagen werden.500,000 to be served.
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 2, da¬ durch gekennzeichnet, daß mit wasserverdünnbaren Druckfarben bedruckte Altpapiere in Gegenwart von Polymeren und/oder Copolymeren auf Basis von 2-Vinylpyridin, 4-Vinylpyridin und/oder 1-Vinylimidazol, gewünschtenfalls in Kombination mit4. The method according to one or more of claims 1 to 2, characterized in that waste paper printed with water-thinnable printing inks in the presence of polymers and / or copolymers based on 2-vinylpyridine, 4-vinylpyridine and / or 1-vinylimidazole, if desired in combination with
ERSATZBLATT weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und 500 000 aufgeschlagen werden.REPLACEMENT LEAF other at least partially water-soluble amino- and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2000 and 500,000.
5. Verfahren nach einem oder beiden der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß mit wasserverdünnbaren Druckfarben be¬ druckte Altpapiere in Gegenwart von primäre, sekundäre, ter¬ tiäre und/oder quaternierte A inogruppen enthaltenen Polysac- chariden und/oder Heteropolysacchariden, gewünschtenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen5. The method according to one or both of claims 1 to 2, characterized in that waste paper printed with water-dilutable printing inks in the presence of primary, secondary, tertiary and / or quaternized amino groups containing polysaccharides and / or heteropolysaccharides, if desired in combination with further at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between
2000 und 500000 aufgeschlagen werden.2000 and 500000 are served.
6. Verfahren nach einem oder beiden der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß mit wasserverdünnbaren Druckfarben be¬ druckte Altpapiere in Gegenwart von Proteinen, gewünschtenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Poly¬ meren und/oder Copolymeren mit Zahlenmitteln der Molekularge¬ wichte zwischen 2000 und 500000 aufgeschlagen werden.6. The method according to one or both of claims 1 to 2, characterized in that waste paper printed with water-dilutable printing inks in the presence of proteins, if desired in combination with further at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers be opened with number average molecular weights between 2000 and 500000.
7. Verwendung von mindestens teilweise wasserlöslichen a ino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und 500 000 zum Deinken von mit wasserverdünnbaren Druckfarben be¬ druckten Altpapieren.7. Use of at least partially water-soluble polymers containing a ino and / or ammonium group and / or copolymers with number average molecular weights between 2000 and 500,000 for deinking waste paper printed with water-thinnable printing inks.
8. Verwendung nach Anspruch 7, dadurch gekennzeichnet, daß minde¬ stens teilweise wasserlösliche amino- und/oder ammoniumgruppenhaltige Polymere und/oder Copolymere mit Zahlenmitteln der Molekulargewichte zwischen 5000 und 200000, vorzugsweise zwischen 10000 und 100000, verwendet werden.8. Use according to claim 7, characterized in that at least partially water-soluble amino and / or ammonium group-containing polymers and / or copolymers with Number average molecular weights between 5000 and 200000, preferably between 10000 and 100000, can be used.
9. Verwendung nach einem oder beiden der Ansprüche 7 bis 8, da¬ durch gekennzeichnet, daß Polyethylenimine und/oder ethyleniminhaltige Copolymere, gewünschtenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und9. Use according to one or both of claims 7 to 8, characterized in that polyethyleneimines and / or ethyleneimine-containing copolymers, if desired in combination with further at least partially water-soluble amino- and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2000 and
500000 verwendet werden.500000 can be used.
10. Verwendung nach einem oder mehreren der Ansprüche 7 bis 8, da¬ durch gekennzeichnet, daß Polymere und/oder Copolymere auf Ba¬ sis von 2-Vinylpyridin, 4-Vinylpyridin und/oder 1- Vinylimidazol, gewünschtenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen / amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und 500 000 verwendet werden.10. Use according to one or more of claims 7 to 8, characterized in that polymers and / or copolymers based on 2-vinylpyridine, 4-vinylpyridine and / or 1-vinylimidazole, if desired in combination with further at least partially water-soluble / amino and / or ammonium group-containing polymers and / or copolymers with number average molecular weights between 2000 and 500,000 can be used.
11. Verwendung nach einem oder beiden der Ansprüche 7 bis 8, da¬ durch gekennzeichnet, daß primäre, sekundäre, tertiäre und/oder ' quaternierte aminogruppenhaltige Polysaccharide und/oder Heteropolysaccharide, gewünschtenfalls in Kombination mit weiteren mindestens teilweise wasserlöslichen amino- und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und 500 000 verwendet werden.11. Use according to one or both of claims 7 to 8, characterized in that primary, secondary, tertiary and / or 'quaternized amino group-containing polysaccharides and / or heteropolysaccharides, if desired in combination with further at least partially water-soluble amino and / or ammonium group-containing Polymers and / or copolymers with number average molecular weights between 2000 and 500,000 can be used.
12. Verwendung nach einem oder beiden der Ansprüche 7 bis 8, da¬ durch gekennzeichnet, daß Proteine, gewünschtenfalls in Kombi¬ nation mit weiteren mindestens teilweise wasserlöslichen amino-12. Use according to one or both of claims 7 to 8, characterized in that proteins, if desired in combination with other at least partially water-soluble amino
ER und/oder ammoniumgruppenhaltigen Polymeren und/oder Copolymeren mit Zahlenmitteln der Molekulargewichte zwischen 2000 und 500000 verwendet werden. HE and / or polymers and / or copolymers containing ammonium groups with number-average molecular weights between 2000 and 500000.
EP89912962A 1988-11-23 1989-11-14 De-inking of old papers Pending EP0445161A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19883839478 DE3839478A1 (en) 1988-11-23 1988-11-23 THINKING OF WASTE PAPER
DE3839478 1988-11-23

Publications (1)

Publication Number Publication Date
EP0445161A1 true EP0445161A1 (en) 1991-09-11

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DE (2) DE3839478A1 (en)
TR (1) TR24029A (en)
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DE19631150B4 (en) * 1996-08-01 2007-04-19 Süd-Chemie AG Process for the removal of printing inks (deinking) of cellulosic print substrates
DE19703360A1 (en) * 1997-01-30 1998-08-06 Henkel Kgaa Use of alkyl polyglycosides to deink waste paper
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TR24029A (en) 1991-02-04
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WO1990005806A3 (en) 1990-07-12
EP0372267A3 (en) 1990-08-01
DE3839478A1 (en) 1990-06-07
YU46704B (en) 1994-04-05
EP0372267B1 (en) 1994-01-12
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WO1990005806A2 (en) 1990-05-31
CA2003407A1 (en) 1990-05-23

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