EP0161443A1 - Manufacture of dry or wet crepe papers - Google Patents

Manufacture of dry or wet crepe papers Download PDF

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Publication number
EP0161443A1
EP0161443A1 EP85103781A EP85103781A EP0161443A1 EP 0161443 A1 EP0161443 A1 EP 0161443A1 EP 85103781 A EP85103781 A EP 85103781A EP 85103781 A EP85103781 A EP 85103781A EP 0161443 A1 EP0161443 A1 EP 0161443A1
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Prior art keywords
propoxylated
ethoxylated
carbon atoms
use according
carboxylic acid
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EP85103781A
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German (de)
French (fr)
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EP0161443B1 (en
Inventor
Hasan Dr. Dipl.-Ing. Ulubay
Horst Schürmann
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Akzo Patente Te Wuppertal Bondsrepubliek Dui GmbH
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Akzo 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds

Definitions

  • the invention relates to the production of papers, in particular wet or dry creped papers with increased suction speed compared to aqueous media.
  • Increased water absorption speed is particularly required for the papers that are used in the field of hygiene, such. B. toilet paper, paper towels, kitchen rolls, etc.
  • Fibers with a low degree of grinding and large fiber diameters generally lead to more voluminous and therefore more absorbent papers.
  • pulps come from softwoods such. B. pine or Douglas fir, followed by spruce.
  • Hardwoods generally result in low absorbency with the exception of beech.
  • Tissue types such as handkerchiefs and kitchen rolls, are given more or less wet strength.
  • cationic wet strength agents such as B. polyamide-epichlorohydrin condensation products used.
  • the creping of the paper is carried out, for example, in such a way that the paper web is guided to a drying cylinder with a large diameter and dried there and at the end of the path on the cylinder is detached from the cylinder surface by means of a so-called creping doctor.
  • the degree of creping is determined by the speed difference between the drying cylinder and the subsequent reeling.
  • creping aids adheresives
  • Increased use of waste paper with a high degree of grinding and a high proportion of filler and fine material as a raw material for tissue generally leads to a deterioration in the drainage in the wire section, to increased adhesion to the drying cylinder and to a strong abrasion of the crepe scrapers.
  • the chemicals used to increase the wet strength additionally deteriorate the drainage and absorbency of the papers and increase the adhesive effect on the drying cylinder.
  • absorbent cellulose products are used which are produced by dry defibrillation of cellulose pulp or cellulose fiber pulp with the formation of flakes.
  • the cellulose pulp should have a low mechanical strength in order to enable the fibers to be separated from one another without destroying them and to reduce the energy required for the breakdown.
  • the flakes obtained after dry-cutting should have a good liquid absorption capacity and a short absorption time.
  • cationic surfactants such as quaternary ammonium compounds to reduce the bonds between the cellulosic fibers. These compounds result in a noticeable impairment of the water absorption time.
  • quaternary ammonium compounds are that they usually have a chloride ion as the anion Causing corrosion damage to the device and often reducing the brightness of the flakes.
  • non-ionic substances which are ethoxylated or propoxylated aliphatic alcohols or alkylphenols are used and the Swedish patent 402 607, referenced in Chemical Abstracts Vol. 89, 181 429, teaches a process in which alkoxylated aliphatic alcohols in combination with quaternary ammonium compounds can be used as retention agents.
  • Non-ionic compounds are used in the production of absorbent cellulose pulp, these compounds being made from partial fatty acid esters of polyhydric alcohols having 2 to 8 carbon atoms or their anhydrides, i.e. Anhydro derivatives such as B. inner ethers or of polyethylene or polypropylene glycols with molecular weights up to 500.
  • the object of the present invention was to improve the known processes for the production of absorbent papers, in particular dry or wet creped papers, in such a way that the adhesion to the drying cylinder is reduced and the formation of deposits on the drying cylinder is prevented.
  • Carboxylic acid esters and / or polyethers in which the alkyl group of the ethoxylated and / or propoxylated alkylphenol has 8 to 16 carbon atoms, for example an ethoxylated and / or propoxylated nonylphenol, are preferably used.
  • Particularly suitable alcohols are ethylhexanol, dodecanol, lauryl alcohol, stearyl alcohol and the so-called Guerbet alcohols.
  • Suitable ethoxylated and / or propoxylated amines include, for example, polyoxyethylene cocosamines, polyoxyethylene valley amines, polyoxyethylene oleylamines and polyoxyethylene octadecylamines, which have different degrees of ethoxylation the trade name EthomeenÜ are commercially available.
  • Ethoxylated amides are commercially available under the trade name Ethomid "and consist, for example, of polyoxyethylene oleoamides or polyoxyethylene valley amides. These are also suitable starting products for the carboxylic acid esters and / or polyethers to be used according to the invention.
  • carboxylic acids are fatty and resin acids.
  • Preferred carboxylic acids are those containing 12 to 20 carbon atoms, for example oleic acid, palmitic acid or abietic acid.
  • Long-chain epoxides which are suitable for the invention are in particular 1,2-epoxides with 8 to 30 carbon atoms.
  • Polyethers in which the long-chain 1,2-epoxide contains 12 to 18 carbon atoms are preferably used.
  • the degree of ethoxylation and / or propoxylation of the ethoxylated and / or propoxylated primary or secondary alcohols, alkylphenols, amines and / or amides converted into carboxylic acid esters or polyethers is preferably 5 to 15.
  • the carboxylic acid esters are prepared by reacting the ethoxylated and / or propoxylated alcohols, alkylphenols, amines and / or amides with corresponding carboxylic acids at temperatures between about 160-225 ° C. and under normal pressure, using 0.1 to 0.5 as the catalyst % By weight p. Toluenesulfonic acid, based on the total batch, can be added. After the majority of the water of reaction has been distilled off, the rest of the water of reaction is drawn off under a vacuum of 80 to 100 mbar. The acid number of the finished products is approx. 5 - 8.
  • the polyethers are prepared by reacting the ethoxylated and / or propoxylated alcohols, alkylphenols, amines and / or amides with the corresponding long-chain 1,2-epoxides with 0.1 to 0.5% by weight KOH, based on the total batch , as a catalyst at temperatures between 100 - 180 ° C.
  • the carboxylic acid esters and / or polyethers used according to the invention also have excellent self-emulsification properties that make predilution superfluous. It is therefore a preferred embodiment of the present invention that the carboxylic acid esters and / or polyethers are added in liquid form in an active ingredient concentration of more than 80% by weight.
  • polyethers which are solid, it is preferred that the addition is made in an aqueous dispersion or solution for better metering of the polyether.
  • the carboxylic acid esters and / or polyethers are added to the paper in an amount of 0.05 to 0.5% by weight, based on dry cellulose.
  • the carboxylic acid esters and / or polyethers are added in the Dutch, pulper and / or during sheet formation.
  • a Kämmerer laboratory test machine was used for the examples below, the chemicals being metered continuously into the mixture of substances in the amounts indicated.
  • As a wet strength agent 4% of a commercially available wet agent based on a polyamide amine epichlorohydrin condensate (Etadurin N76 12.5% strength) was added to all examples.
  • Commercial products for increasing the suction speed which are mixtures of high molecular weight cationic condensates and a non-ionic dispersant, served as comparison products 1 and 2.
  • Comparative product 3 was an alkylphenol polyglycol ether.
  • a carboxylic ester C ester of nonylphenol ethoxylate with 9 ED and stearic acid was used as a means of increasing the suction strength.
  • Raw material 50% pine sulfate pulp 25% birch sulfate pulp 25% beech sulfate pulp
  • Product F Polyether from nonylphenol ethoxylate with 9 EO and C 18 epoxy
  • Raw material 70% spruce sulfate pulp 30% beech sulfate pulp

Abstract

Herstellung von insbesondere nass- oder trockengekreppten Papieren mit erhöhter Sauggeschwindigkeit gegenüber wäßrigen Medien durch Verwendung von Umsetzungsprodukten erhältlich durch Ester-, bzw. Ätherbildung aus einerseits ethoxilierten und/oder propoxilierten primären und/oder sekundären Alkoholen mit 12 bis 40 C-Atomen, ethoxilierten und/oder propoxilierten Alkyl-Phenolen, ethoxilierten und/oder propoxilierten Aminen und/oder ethoxilierten und/oder propoxilierten Amiden mit einem Eth- bzw. Propoxilierungsgrad von 3 bis 50 und andererseits Carbonsäuren mit 8 bis 30 C-Atomen, insbesondere Fett- oder Harzsäuren, oder langkettigen 1,2-Epoxiden mit 8 bis 30 C-Atomen.Production of, in particular, wet or dry creped papers with increased suction speed compared to aqueous media by using reaction products obtainable by ester or ether formation from, on the one hand, ethoxylated and / or propoxylated primary and / or secondary alcohols with 12 to 40 C atoms, ethoxylated and / or propoxylated alkyl phenols, ethoxylated and / or propoxylated amines and / or ethoxylated and / or propoxylated amides with a degree of eth or propoxylation of 3 to 50 and on the other hand carboxylic acids with 8 to 30 C atoms, in particular fatty or resin acids, or long-chain 1,2-epoxides with 8 to 30 carbon atoms.

Description

Die Erfindung betrifft die Herstellung von Papieren insbesondere naß- oder trockengekreppten Papieren mit erhöhter Sauggeschwindigkeit gegenüber wäßrigen Medien.The invention relates to the production of papers, in particular wet or dry creped papers with increased suction speed compared to aqueous media.

Erhöhte Wasserabsorbtionsgeschwindigkeit wird insbesondere bei den Papieren gefordert, die im Bereich der Hygiene eingesetzt werden, so z. B. Toilettenpapier, Papierhandtücher,Küchenrollen u.s.w..Increased water absorption speed is particularly required for the papers that are used in the field of hygiene, such. B. toilet paper, paper towels, kitchen rolls, etc.

Um die Anforderungen an Weichheit und Saugfähigkeit zu gewährleisten, werden noch heute zum größten Teil hochwertige Zellstoffe eingesetzt, wobei Saugfähigkeit eines Zellstoffes von der Faserlänge, dem Faserdurchmesser und dem Mahlgrad bestimmt wird.To ensure the requirements for softness and absorbency, high-quality cellulose is still used to a large extent, whereby the absorbency of a cellulose is determined by the fiber length, the fiber diameter and the degree of grinding.

Fasern mit niedrigem Mahlgrad sowie großen Faserdurchmessern führen im allgemeinen zu voluminöseren und damit saugfähigeren Papieren. Als Zellstoffe kommen hierzu solche aus Nadelhölzern z. B. Kiefer oder Douglasfichte, gefolgt von Fichte, infrage. Laubhölzer führen im allgemeinen zu einer niedrigen Saugfähigkeit mit Ausnahme von Buche.Fibers with a low degree of grinding and large fiber diameters generally lead to more voluminous and therefore more absorbent papers. As pulps come from softwoods such. B. pine or Douglas fir, followed by spruce. Hardwoods generally result in low absorbency with the exception of beech.

Aus Gründen der Rohstoffverknappung und Rohstoffverteuerung ist man jedoch heute stärker bemüht,auch Altpapier und geringerwertige Zellstoffe einzusetzen.However, due to the shortage of raw materials and the increase in raw material prices, efforts are now being made to use waste paper and low-quality pulp.

Diese Rohstoffe führen jedoch durch ihren hohen Mahlgrad zu einer Verdichtung der Papierbahn und damit zu einer geringeren Saugfähigkeit.However, due to their high degree of grinding, these raw materials lead to a compression of the paper web and thus to a lower absorbency.

Darüber hinaus wird auch die Entwässerung auf der Papiermaschine durch den hohen Mahlgrad verschlechtert, was zusätzlich zu einer Reduzierung der Papiermaschinengeschwindigkeit führt.In addition, the dewatering on the paper machine is also impaired by the high degree of grinding, which additionally leads to a reduction in the paper machine speed.

Tissue-Sorten, wie beispielsweise Taschentücher und Küchenrol- len,werden dabei mehr oder weniger stark naßfest ausgerüstet.Tissue types, such as handkerchiefs and kitchen rolls, are given more or less wet strength.

Zu diesem Zweck werden kationische Naßfestmittel wie z. B. Polyamidamin-Epichlorhydrin-Kondensationsprodukte eingesetzt.For this purpose, cationic wet strength agents such. B. polyamide-epichlorohydrin condensation products used.

Die Kreppung des Papiers wird beispielsweise so vorgenommen, daß die Papierbahn an einen Trockenzylinder mit großem Durchmesser geführt und dort getrocknet und am Ende des Weges auf dem Zylinder mittels eines sogenannten Kreppschabers von der Zylinder-Oberfläche abgelöst wird. Das Ausmaß der Kreppung wird von der Geschwindigkeitsdifferenz zwischen Trockenzylinder und der nachfolgenden Aufrollung bestimmt.The creping of the paper is carried out, for example, in such a way that the paper web is guided to a drying cylinder with a large diameter and dried there and at the end of the path on the cylinder is detached from the cylinder surface by means of a so-called creping doctor. The degree of creping is determined by the speed difference between the drying cylinder and the subsequent reeling.

Beim Einsatz von hochwertigen Faserstoffen war es zum Teil notwendig,die erforderliche Adhäsion zwischen Papierbahn und Trockenzylinder durch sogenannte Krepphilfsmittel (Haftmittel) zu verbessern. Verstärkter Einsatz von Altpapier mit hohem Mahlgrad sowie hohem Füll- und Feinstoffanteil als Rohstoff für Tissue führt im allgemeinen zu einer Verschlechterung der Entwässerung in der Siebpartie, zu einer erhöhten Haftung am Trockenzylinder und zu einem starken Abrieb der Kreppschaber. Die zur Erhöhung der Naßfestigkeit eingesetzten Chemikalien verschlechtern zusätzlich die Entwässerung und die Saugfähigkeit der Papiere und erhöhen die Klebwirkung am Trockenzylinder.When using high-quality fibrous materials, it was sometimes necessary to improve the required adhesion between the paper web and drying cylinder using so-called creping aids (adhesives). Increased use of waste paper with a high degree of grinding and a high proportion of filler and fine material as a raw material for tissue generally leads to a deterioration in the drainage in the wire section, to increased adhesion to the drying cylinder and to a strong abrasion of the crepe scrapers. The chemicals used to increase the wet strength additionally deteriorate the drainage and absorbency of the papers and increase the adhesive effect on the drying cylinder.

Bei sanitären Produkten wie Windeln oder sanitären Tüchern bzw. Binden werden absorbierende Zelluloseprodukte verwendet,die durch Trocken-Defibrierung von Zellulosepulpe bzw. Zellulosefaserbrei unter Bildung von Flocken hergestellt werden. Hierbei soll die Zellulosepulpe eine niedrige mechanische Festigkeit besitzen, um die Trennung der Fasern voneinander ohne ihre Zerstörung zu ermöglichen und um die für die Zerteilung erforderliche Energie herabzusetzen. Die Flocken, die nach der Trocken-Zerteilung erhalten werden, sollten eine gute Flüssigkeitsabsorptionskapazität und eine kurze Absorptionszeit besitzen.In the case of sanitary products such as diapers or sanitary wipes or sanitary napkins, absorbent cellulose products are used which are produced by dry defibrillation of cellulose pulp or cellulose fiber pulp with the formation of flakes. The cellulose pulp should have a low mechanical strength in order to enable the fibers to be separated from one another without destroying them and to reduce the energy required for the breakdown. The flakes obtained after dry-cutting should have a good liquid absorption capacity and a short absorption time.

Es ist bekannt, kationische oberflächenaktive Mittel wie quaternäre Ammoniumverbindungen für die Reduktion der Bindungen zwischen den Zellulosefasern zu verwenden. Diese Verbindungen ergeben eine merkliche Beeinträchtigung der Wasserabsorptionszeit. Weitere Nachteile der quaternären Ammoniumverbindungen sind, da sie gewöhnlich ein Chloridion als Anion besitzen, die Herbeiführung von Korrosionsschäden an der Vorrichtung und häufig die Reduktion der Helligkeit der Flocken.It is known to use cationic surfactants such as quaternary ammonium compounds to reduce the bonds between the cellulosic fibers. These compounds result in a noticeable impairment of the water absorption time. Other disadvantages of the quaternary ammonium compounds are that they usually have a chloride ion as the anion Causing corrosion damage to the device and often reducing the brightness of the flakes.

Es ist auch bekannt, nicht-ionische Substanzen zu Zellulosepulpe zuzugeben, um die Bindekräfte zu reduzieren. Gemäß der DE-OS 19 55 454 werden nicht-ionische Substanzen, die äthoxylierte oder propoxylierte aliphatische Alkohole oder Alkylphenole sind, verwendet und das schwedische Patent 402 607,referiert in Chemical Abstracts Vol. 89, 181 429, lehrt ein Verfahren, bei dem alkoxylierte aliphatische Alkohole in Kombination mit quaternären Ammoniumverbindungen als Retentionsmittel verwendet werden.It is also known to add non-ionic substances to cellulose pulp in order to reduce the binding forces. According to DE-OS 19 55 454, non-ionic substances which are ethoxylated or propoxylated aliphatic alcohols or alkylphenols are used and the Swedish patent 402 607, referenced in Chemical Abstracts Vol. 89, 181 429, teaches a process in which alkoxylated aliphatic alcohols in combination with quaternary ammonium compounds can be used as retention agents.

Aus der DE-OS 29 29 512 ist ein weiteres Verfahren bekannt, bei dem nicht-ionische Verbindungen bei der Herstellung von absorbierender Zellulosepulpe verwendet werden, wobei diese Verbindungen aus partiellen Fettsäureestern von mehrwertigen Alkoholen mit 2 bis 8 Kohlenstoffatomen oder deren Anhydriden d.h. Anhydroderivaten wie z. B. inneren Äthern oder von Polyäthylen- oder Polypropylenglykolen mit Molekulargewichten bis zu 500 bestehen.Another method is known from DE-OS 29 29 512, in which non-ionic compounds are used in the production of absorbent cellulose pulp, these compounds being made from partial fatty acid esters of polyhydric alcohols having 2 to 8 carbon atoms or their anhydrides, i.e. Anhydro derivatives such as B. inner ethers or of polyethylene or polypropylene glycols with molecular weights up to 500.

Aufgabe der vorliegenden Erfindung war es,die bekannten Verfahren zur Herstellung von saugfähigen Papieren, insbesondere trocken- oder naßgekreppten Papieren dahingehend zu verbessern, daß die Haftung am Trockenzylinder reduziert und die Belagbildung auf dem Trockenzylinder verhindert wird.The object of the present invention was to improve the known processes for the production of absorbent papers, in particular dry or wet creped papers, in such a way that the adhesion to the drying cylinder is reduced and the formation of deposits on the drying cylinder is prevented.

Gelöst wird diese Aufgabe dadurch, daß Carbonsäureester aus Carbonsäuren mit 8 bis 30 C-Atomen und ethoxilierten und/oder propoxilierten primären und/oder sekundären Alkoholen mit 12 bis 40 C-Atomen, ethoxilierten und/oder propoxilierten Alkyl- Phenolen, ethoxilierten und/oder propoxilierten Aminen und/oder ethoxilierten und/oder propoxilierten Amiden mit einem Eth- bzw Propoxilierungsgrad von 3 bis 50 verwendet.This object is achieved in that carboxylic esters from carboxylic acids with 8 to 30 carbon atoms and ethoxylated and / or propoxylated primary and / or secondary alcohols with 12 up to 40 carbon atoms, ethoxylated and / or propoxylated alkyl phenols, ethoxylated and / or propoxylated amines and / or ethoxylated and / or propoxylated amides with a degree of eth or propoxylation of 3 to 50.

Sie wird ebenfalls gelöst, dadurch daß Polyäther, erhalten aus der Umsetzung von eth- und/oder propoxilierten primären und/ oder sekundären Alkoholen mit 12 bis 40 C-Atomen, ethoxilierten und/oder propoxilierten Alkyl-Phenolen, ethoxilierten und/oder propoxilierten Aminen und/oder ethoxilierten und/oder propoxilierten Amiden mit einem Eth- bzw. Propoxilierungsgrad von 3 bis 50 und langkettigen Epoxiden mit 8 bis 30 C-Atomen verwendet werden.It is also solved in that polyethers obtained from the reaction of eth- and / or propoxylated primary and / or secondary alcohols with 12 to 40 carbon atoms, ethoxylated and / or propoxylated alkyl phenols, ethoxylated and / or propoxylated amines and / or ethoxylated and / or propoxylated amides with a degree of eth- or propoxylation of 3 to 50 and long-chain epoxides with 8 to 30 C atoms can be used.

Vorzugsweise werden solche Carbonsäureester und/oder Polyäther verwendet, bei denen die Alkylgruppe des eth- und/oder propoxilierten Alkylphenols 8 bis 16 C-Atome, beispielsweise ein eth- und/oder propoxiliertes Nonylphenol. Als Alkohole sind insbesondere Ethylhexanol, Dodecanol, Laurylalkohol, Stearylalkohol sowie die sogenannten Guerbet-Alkohole geeignet.Carboxylic acid esters and / or polyethers in which the alkyl group of the ethoxylated and / or propoxylated alkylphenol has 8 to 16 carbon atoms, for example an ethoxylated and / or propoxylated nonylphenol, are preferably used. Particularly suitable alcohols are ethylhexanol, dodecanol, lauryl alcohol, stearyl alcohol and the so-called Guerbet alcohols.

Diese Guerbet-Alkohole lassen sich durch die Strukturformel

Figure imgb0001
beschreiben, wobei R einer Alkylgruppe der allgemeinen Formel Cn H2n+1 und R1 einer Alkylgruppe der allgemeinen Formel Cn-2 H2n-3 entspricht. Vorzugsweise ist dabei n = 8 - 19.These Guerbet alcohols can be identified by the structural formula
Figure imgb0001
 describe, wherein R is an alkyl group of the general formula C n H 2n + 1 and R 1 is an alkyl group of the general formula C n-2 H 2n-3 . Preferably n = 8-19 .

Als geeignete eth- und/oder propoxilierte Amine kommen dabei beispielsweise Polyoxyethylen-cocosamine, Polyoxyethylentalgamine, Polyoxyethylenoleylamine und Polyoxyethylenoctadecylamine infrage, die mit unterschiedlichen Ethoxilierungsgraden unter der Handelsbezeichnung EthomeenÜ im Handel erhältlich sind. Ethoxilierte Amide sind unter der Handelsbezeichnung Ethomid" im Handel erhältlich und bestehen z. B. aus Polyoxyethylenoleoamiden, bzw. Polyoxyethylentalgamiden. Auch diese sind geeignete Ausgangsprodukte für die gemäß der Erfindung einzusetzenden Carbonsäureester und/oder Polyäther.Suitable ethoxylated and / or propoxylated amines include, for example, polyoxyethylene cocosamines, polyoxyethylene valley amines, polyoxyethylene oleylamines and polyoxyethylene octadecylamines, which have different degrees of ethoxylation the trade name EthomeenÜ are commercially available. Ethoxylated amides are commercially available under the trade name Ethomid "and consist, for example, of polyoxyethylene oleoamides or polyoxyethylene valley amides. These are also suitable starting products for the carboxylic acid esters and / or polyethers to be used according to the invention.

Als Carbonsäuren kommen insbesondere Fett- und Harzsäuren infrage. Bevorzugt sind solche Carbonsäuren die 12 bis 20 C-Atome enthalten, beispielsweise Oleinsäure, Palmitinsäure oder Abietinsäure.Particularly suitable carboxylic acids are fatty and resin acids. Preferred carboxylic acids are those containing 12 to 20 carbon atoms, for example oleic acid, palmitic acid or abietic acid.

Langkettige Epoxide die sich für die Erfindung eignen sind insbesondere 1,2-Epoxide mit 8 bis 30 C-Atomen. Hier sind im einzelnen zu nennen: 1,2-Epoxyoctan, 1,2-Epoxynonan, 1,2-Epoxydecan, 1,2-Epoxyundecan, 1,2-Epoxydodecan, 1,2-Epoxytridecan, 1,2-Epoxytetradecan, 1,2-Epoxypentadecan, 1,2-Epoxyhexadecan, 1,2-Epoxyheptadecan, 1,2-Epoxyoctadecan, 1,2-Epoxynonadecan, 1,2-Epoxyeicosan, 1,2-Epoxyuneicosan, 1,2-Epoxydocosan, 1,2-Epoxytricosan, 1,2-Epoxytetracosan, 1,2-Epoxypentacosan, 1,2-Epoxyhexacosan, 1,2-Epoxyheptacosan, 1,2-Epoxyoctacosan, 1,2-Epoxynonacosan, 1,2-Epoxytriacontan.Long-chain epoxides which are suitable for the invention are in particular 1,2-epoxides with 8 to 30 carbon atoms. The following are to be mentioned in detail: 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1 , 2-Epoxypentadecan, 1,2-Epoxyhexadecan, 1,2-Epoxyheptadecan, 1,2-Epoxyoctadecan, 1,2-Epoxynonadecan, 1,2-Epoxyeicosan, 1,2-Epoxyuneicosan, 1,2-Epoxydocosan, 1,2 -Epoxytricosan, 1,2-epoxytetracosane, 1,2-epoxypentacosan, 1,2-epoxyhexacosane, 1,2-epoxyheptacosane, 1,2-epoxyoctacosane, 1,2-epoxynonacosane, 1,2-epoxytriacontane.

Bevorzugt werden solche Polyäther verwendet, bei denen das langkettige 1,2-Epoxid 12 bis 18 C-Atome enthält.Polyethers in which the long-chain 1,2-epoxide contains 12 to 18 carbon atoms are preferably used.

Der Eth- und/oder Propoxilierungsgrad der zu Carbonsäureestern oder Polyäthern umgesetzten eth- und/oder propoxilierten primären oder sekundären Alkoholen, Alkylphenolen, Aminen und/ oder Amiden beträgt vorzugsweise 5 bis 15.The degree of ethoxylation and / or propoxylation of the ethoxylated and / or propoxylated primary or secondary alcohols, alkylphenols, amines and / or amides converted into carboxylic acid esters or polyethers is preferably 5 to 15.

Die Herstellung der Carbonsäureester erfolgt durch Reaktion der eth- und/oder propoxilierten Alkohole, Alkylphenole, Amine und/oder Amide mit entsprechenden Carbonsäuren bei Temperaturen zwischen ca. 160 - 225 °C und unter Normaldruck, wobei als Katalysator 0,1 bis 0,5 Gew.-% p. Toluolsulfonsäure, bezogen auf den Gesamtansatz, zugesetzt werden. Nach dem Abdestillieren der Hauptmenge des Reaktionswassers, wird der Rest des Reaktionswassers bei einem Vakuum von 80 bis 100 mbar abgezogen. Die Säurezahl der Fertigprodukte liegt bei ca. 5 - 8.The carboxylic acid esters are prepared by reacting the ethoxylated and / or propoxylated alcohols, alkylphenols, amines and / or amides with corresponding carboxylic acids at temperatures between about 160-225 ° C. and under normal pressure, using 0.1 to 0.5 as the catalyst % By weight p. Toluenesulfonic acid, based on the total batch, can be added. After the majority of the water of reaction has been distilled off, the rest of the water of reaction is drawn off under a vacuum of 80 to 100 mbar. The acid number of the finished products is approx. 5 - 8.

Die Herstellung der Polyäther erfolgt durch Reaktion der eth-und/oder propoxilierten Alkohole, Alkylphenole, Amine und/ oder Amide mit den entsprechenden langkettigen 1,2-Epoxiden mit 0,1 bis 0,5 Gew.-% KOH, bezogen auf den Gesamtansatz, als Katalysator bei Temperaturen zwischen 100 - 180 °C.The polyethers are prepared by reacting the ethoxylated and / or propoxylated alcohols, alkylphenols, amines and / or amides with the corresponding long-chain 1,2-epoxides with 0.1 to 0.5% by weight KOH, based on the total batch , as a catalyst at temperatures between 100 - 180 ° C.

Durch die erfindungsgemäße Verwendung von Carbonsäureestern und/oder Polyäthern entsprechend den Patentansprüchen werden nachfolgende Ergebnisverbesserungen erzielt.

  • - Beschleunigung der Entwässerung
  • - Entschäumende Wirkung auf das Siebwasser
  • - Reduzierung der Haftung am Trockenzylinder
  • - Verhinderung der Belagbildung auf dem Trockenzylinder
  • - Erhöhung der Standzeiten für Kreppschaber
  • - Erhöhung der Sauggeschwindigkeit der hergestellten Papiere bei der Wiederbefeuchtung auf mehr als das Doppelte
By using carboxylic acid esters and / or polyethers according to the invention, the following improvements in results are achieved.
  • - Accelerate drainage
  • - Defoaming effect on the white water
  • - Reduction of adhesion to the drying cylinder
  • - Prevention of the formation of deposits on the drying cylinder
  • - Increased service life for crepe scrapers
  • - Increase the suction speed of the paper produced during rewetting to more than double

Die erfindungsgemäß verwendeten Carbonsäureester und/oder Polyäther weisen auch hervorragende Selbstemulgierungseigenschaften auf, die eine Vorverdünnung überflüssig machen. Deshalb ist eine bevorzugte Ausführungsform der vorliegenden Erfindung, daß die Zugabe der Carbonsäureester und/oder Polyäther in einer Wirkstoffkonzentration von mehr als 80 Gew.-% flüssig erfolgt.The carboxylic acid esters and / or polyethers used according to the invention also have excellent self-emulsification properties that make predilution superfluous. It is therefore a preferred embodiment of the present invention that the carboxylic acid esters and / or polyethers are added in liquid form in an active ingredient concentration of more than 80% by weight.

Bei solchen Polyäthern, die fest sind, ist es bevorzugt, daß die Zugabe zur besseren Dosierung des Polyäthers in einer wäßrigen Dispersion oder Lösung erfolgt.In the case of such polyethers which are solid, it is preferred that the addition is made in an aqueous dispersion or solution for better metering of the polyether.

Erfindungsgemäß werden die Carbonsäureester und/oder Polyäther in einer Menge von 0,05 bis 0,5 Gew.-%, bezogen auf atro Zellstoff dem Papier zugegeben.According to the invention, the carboxylic acid esters and / or polyethers are added to the paper in an amount of 0.05 to 0.5% by weight, based on dry cellulose.

In Ausgestaltung der Erfindung erfolgt die Zugabe der Carbonsäureester und/oder Polyäther im Holländer, Pulper und/oder bei der Blattbildung.In one embodiment of the invention, the carboxylic acid esters and / or polyethers are added in the Dutch, pulper and / or during sheet formation.

Sie kann aber auch vor den Mahlorganen, in der Mischbütte oder kurz vor dem Stoffauflauf erfolgen.But it can also be done in front of the grinding elements, in the mixing chest or just before the headbox.

Bei den nachfolgend zur weiteren Erläuterung der Erfindung beschriebenen Beispielen wurden folgende Meßgrößen ermittelt:

  • Flächengewicht der Papiere, Wasserabsorptionszeit, Reißlänge (trocken), Reißlänge (naß).
The following measured variables were determined in the examples described below for further explanation of the invention:
  • Basis weight of the papers, water absorption time, tear length (dry), tear length (wet).

Zur Bestimmung dieser Meßgrößen wurden folgende Meßverfahren angewandt:

Figure imgb0002
The following measuring methods were used to determine these measured variables:
Figure imgb0002

Für die nachfolgenden Beispiele wurde eine Kämmerer Labor-Versuchsmaschine eingesetzt, wobei die Chemikalien kontinuierlich der Stoffmischung in den angegebenen Mengen zudosiert wurden. Als Naßfestmittel wurde bei allen Beispielen 4 % eines handelsüblichen Naßmittels auf der Basis eines Polyamidaminepichlorhydrinkondensates (Etadurin N76 12,5 %ig) zugegeben. Als Vergleichsprodukte 1 und 2 dienten handelsübliche Produkte zur Erhöhung der Sauggeschwindigkeit, die Gemische aus hochmolekularen kationischen Kondensaten und einem nichtionogenen Dispergiermittel darstellen. Vergleichsprodukt 3 war ein Alkylphenolpolyglykoläther.A Kämmerer laboratory test machine was used for the examples below, the chemicals being metered continuously into the mixture of substances in the amounts indicated. As a wet strength agent, 4% of a commercially available wet agent based on a polyamide amine epichlorohydrin condensate (Etadurin N76 12.5% strength) was added to all examples. Commercial products for increasing the suction speed, which are mixtures of high molecular weight cationic condensates and a non-ionic dispersant, served as comparison products 1 and 2. Comparative product 3 was an alkylphenol polyglycol ether.

Beispiel 1:Example 1:

Als Rohstoff wurde ein Altpapiergemisch aus

  • 50 % Tageszeitungen
  • 50 % Wellpappe

mit einem Mahlgrad von 53 °SR bei einer Temperatur von 30 °C zu einem Papier mit 50 g/m2 Flächengewicht verarbeitet. Der pH beim Stoffauflauf betrug 7,5. Hierbei wurden erfindungsgemäß Carbonsäureester verwendet und zwar A = Ester aus Nonylphenolethoxylat mit 8 EO und Abietinsäure, B = Ester aus Oleylethoxylat mit 8 EO und Abietinsäure.A waste paper mixture was used as the raw material
  • 50% daily newspapers
  • 50% corrugated cardboard

processed with a freeness of 53 ° SR at a temperature of 30 ° C to a paper with 50 g / m 2 basis weight. The headbox pH was 7.5. Here, carboxylic acid esters were used according to the invention, namely A = ester from nonylphenol ethoxylate with 8 E O and abietic acid, B = ester from oleyl ethoxylate with 8 EO and abietic acid.

Die hierbei ermittelten Daten und Vergleichsdaten ohne Zugabe von Mitteln zur Erhöhung der Sauggeschwindigkeit bzw. der handelsüblichen Mittel 1 und 2 sind nachfolgend in der Tabelle I dargestellt.

Figure imgb0003
The data and comparative data determined in this case without the addition of agents for increasing the suction speed or the commercially available agents 1 and 2 are shown in Table I below.
Figure imgb0003

Beispiel 2:Example 2:

Hier wurde als Rohstoff ein Gemisch aus Kiefernsulfatzellstoff und Altpapier eingesetzt und zwar:

  • 50 % Kiefernsulfatzellstoff
  • 25 % Tageszeitungen
  • 25 % Illustrierte
  • Mahlgrad 54 °C
  • Temperatur 30 °C
  • Der pH beim Stoffauflauf betrug 8,2.
A mixture of pine sulphate pulp and waste paper was used as raw material here:
  • 50% pine sulfate pulp
  • 25% daily newspapers
  • 25% magazines
  • Freeness 54 ° C
  • Temperature 30 ° C
  • The headbox pH was 8.2.

Als Mittel zur Erhöhung der Saugfestigkeit diente erfindungsgemäß ein Carbonsäureester C = Ester aus Nonylphenolethoxylat mit 9 ED und Stearinsäure.According to the invention, a carboxylic ester C = ester of nonylphenol ethoxylate with 9 ED and stearic acid was used as a means of increasing the suction strength.

Die Ergebnisse und Vergleichsergebnisse sind in der Tabelle II zusammengestellt. Das Flächengewicht der Papiere betrug 34 g/m2.

Figure imgb0004
The results and comparative results are summarized in Table II. The basis weight of the papers was 34 g / m2.
Figure imgb0004

Beispiel 3:Example 3:

Als Rohstoff wurde ein Zellstoffgemisch aus

  • 50 % Kiefernsulfatzellstoff
  • 25 % Birkensulfatzellstoff
  • 25 % Buchenzellstoff
  • Mahlgrad = 24 °SR
  • Stofftemperatur 20 °C
  • Der pH beim Stoffauflauf betrug 7,5.
A pulp mixture was used as the raw material
  • 50% pine sulfate pulp
  • 25% birch sulfate pulp
  • 25% beech pulp
  • Freeness = 24 ° SR
  • Fabric temperature 20 ° C
  • The headbox pH was 7.5.

Als weiteres Hilfsmittel waren 0,1 Gew.-% Carboxymethylcellulose zugesetzt worden. Das Flächengewicht der Papiere betrug 72 g/m2. Als Carbonsäureester wurde hier erfindungsgemäß das gleiche Produkt verwendet, wie im Beispiel 2. Die Ergebnisse zeigt die Tabelle III.0.1% by weight of carboxymethyl cellulose had been added as a further aid. The weight per unit area of the papers was 72 g / m 2 . According to the invention, the same product as in Example 2 was used here as the carboxylic acid ester. The results are shown in Table III.

Figure imgb0005
Figure imgb0005

Beispiel 4:Example 4:

Rohstoff: 50 % Kiefernsulfatzellstoff 25 % Birkensulfatzellstoff 25 % BuchensulfatzellstoffRaw material: 50% pine sulfate pulp 25% birch sulfate pulp 25% beech sulfate pulp

Mahlgrad: 24 °SR Stofftemperatur: 20 °C Weiteres Hilfsmittel: 0,1 % Carboxymethylcellulose pH am Stoffauflauf: 7,5 Flächengewicht der Papiere: ca. 50 g/m2 Freeness: 24 ° SR fabric temperature: 20 ° C other auxiliary: 0.1% carboxymethyl cellulose pH at the headbox: 7.5 basis weight of the papers: approx. 50 g / m 2

Zur Erhöhung der Sauggeschwindigkeit wurden die Produkte C, D, E und F zugegeben, wobei C identisch ist mit den Produkten C aus Beispiel 2 und 3.To increase the suction speed, the products C, D, E and F were added, C being identical to the products C from examples 2 and 3.

Produkt D: Ester aus Nonylphenolethoxylat mit 9 EO und gehärteter TalgfettsäureProduct D: Ester from nonylphenol ethoxylate with 9 EO and hardened tallow fatty acid

Produkt E: Ester aus Nonylphenolethoxylat mit 12 EO und gehärteter TalgfettsäureProduct E: Ester from nonylphenol ethoxylate with 12 EO and hardened tallow fatty acid

Produkt F: Polyäther aus Nonylphenolethoxylat mit 9 EO und C18-EpoxydProduct F: Polyether from nonylphenol ethoxylate with 9 EO and C 18 epoxy

Die Ergebnisse sind in der Tabelle IV zusammengefaßt.

Figure imgb0006
The results are summarized in Table IV.
Figure imgb0006

Beispiel 5:Example 5:

Rohstoff: 70 % Fichtensulfatzellstoff 30 % BuchensulfatzellstoffRaw material: 70% spruce sulfate pulp 30% beech sulfate pulp

Mahlgrad: 39 °SR Stofftemperatur: 20 °C weiteres Hilfsmittel: Na2CO3 pH am Stoffauflauf: 7,9 Flächengewicht der Papiere: ca. 50 g/m2 Freeness: 39 ° SR fabric temperature: 20 ° C other aids: Na 2 CO 3 pH at the headbox: 7.9 basis weight of the papers: approx. 50 g / m 2

Verglichen wurde das Produkt C aus den Beispielen 2, 3 und 4 mit einem Handelsprodukt, das mit dem in Beispiel 1 herangezogenen Vergleichsmittel 2 identisch ist. Tabelle V zeigt die Ergebnisse.

Figure imgb0007
Product C from Examples 2, 3 and 4 was compared with a commercial product which is identical to Comparative Agent 2 used in Example 1. Table V shows the results.
Figure imgb0007

Claims (10)

1. Verwendung von Carbonsäureestern aus Carbonsäuren mit 8 bis 30 C-Atomen und ethoxilierten und/oder propoxilierten primären und/oder sekundären Alkoholen mit 12 bis 40 C-Atomen, ethoxilierten und/oder propoxilierten Alkyl-Phenolen, ethoxilierten und/oder propoxilierten Aminen und/oder ethoxilierten und/oder propoxilierten Amiden mit einem Eth- bzw. Propoxilierungsgrad von 3 bis 50 bei der Herstellung von Papieren, insbesondere von trocken- oder naßgekreppten Papieren, zur Erhöhung der Sauggeschwindigkeit.1. Use of carboxylic acid esters from carboxylic acids with 8 to 30 carbon atoms and ethoxylated and / or propoxylated primary and / or secondary alcohols with 12 to 40 carbon atoms, ethoxylated and / or propoxylated alkyl phenols, ethoxylated and / or propoxylated amines and / or ethoxylated and / or propoxylated amides with a degree of eth- or propoxylation of 3 to 50 in the manufacture of papers, in particular dry or wet creped papers, to increase the suction speed. 2. Verwendung von Polyäthern, erhalten aus der Umsetzung von eth- und/oder propoxilierten primären und/oder sekundären Alkoholen mit 12 bis 40 C-Atomen, eth- und/oder propoxilierten Alkyl-Phenolen, eth- und/oder propoxilierten Aminen und/ oder eth- und/oder propoxilierten Amiden mit einem Eth- bzw. Propoxilierungsgrad von 3 bis 50 und langkettigen 1,2-Epoxiden mit 8 bis 30 C-Atomen bei der Herstelung von Papieren, insbesondere von trocken- oder naßgekreppten Papieren, zur Erhöhung der Sauggeschwindigkeit.2. Use of polyethers obtained from the reaction of eth- and / or propoxylated primary and / or secondary alcohols with 12 to 40 carbon atoms, eth- and / or propoxylated alkyl phenols, eth- and / or propoxylated amines and / or ethoxylated and / or propoxylated amides with a degree of ethoxylation or propoxylation of 3 to 50 and long-chain 1,2-epoxides with 8 to 30 carbon atoms in the manufacture of papers, in particular dry or wet-creped papers, to increase the Suction speed. 3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Alkylgruppe des eth- und/oder propoxilierten AlkylPhenols 8 bis 16 C-Atome enthält.3. Use according to claim 1 or 2, characterized in that the alkyl group of the ethoxylated and / or propoxylated alkyl phenol contains 8 to 16 carbon atoms. 4. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Carbonsäure 12 bis 20 C-Atome enthält.4. Use according to claim 1, characterized in that the carboxylic acid contains 12 to 20 carbon atoms. 5. Verwendung nach Anspruch 2, dadurch gekennzeichnet, daß das langkettige 1,2-Epoxid 12 bis 18 C-Atome enthält.5. Use according to claim 2, characterized in that the long-chain 1,2-epoxide contains 12 to 18 carbon atoms. 6. Verwendung nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß der Carbonsäureester und/oder Polyäther in einer Menge von 0,05 bis 0,5 Gew.-%, bezogen auf atro Zellstoff dem Papier zugegeben wird.6. Use according to claims 1 to 5, characterized in that the carboxylic acid ester and / or polyether is added to the paper in an amount of 0.05 to 0.5% by weight, based on dry cellulose. 7. Verwendung nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die Zugabe der Carbonsäureester und/oder Polyäther im Holländer, Pulper und/oder bei der Blattbildung erfolgt.7. Use according to claims 1 to 6, characterized in that the addition of the carboxylic acid ester and / or polyether is carried out in the Dutch, pulper and / or in the sheet formation. 8. Verwendung nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß die Zugabe der Carbonsäureester und/oder Polyäther in einer Wirkstoffkonzentration von mehr als 80 Gew.-% flüssig erfolgt.8. Use according to claims 1 to 7, characterized in that the addition of the carboxylic acid ester and / or polyether is carried out in a liquid concentration of more than 80 wt .-%. 9. Verwendung nach den Ansprüchen 2, 3, 5, 6, 7, dadurch gekennzeichnet, daß die Zugabe des Polyäthers in einer wäßrigen Dispersion oder Lösung erfolgt.9. Use according to claims 2, 3, 5, 6, 7, characterized in that the polyether is added in an aqueous dispersion or solution. 10. Verwendung nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß der Eth- bzw. Propoxilierungsgrad 5 bis 15 beträgt.10. Use according to claims 1 to 9, characterized in that the degree of ethoxylation or propoxylation is 5 to 15.
EP85103781A 1984-04-30 1985-03-29 Manufacture of dry or wet crepe papers Expired EP0161443B1 (en)

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