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EP0123708A1 - Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use - Google Patents

Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use Download PDF

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Publication number
EP0123708A1
EP0123708A1 EP83104303A EP83104303A EP0123708A1 EP 0123708 A1 EP0123708 A1 EP 0123708A1 EP 83104303 A EP83104303 A EP 83104303A EP 83104303 A EP83104303 A EP 83104303A EP 0123708 A1 EP0123708 A1 EP 0123708A1
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EP
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Prior art keywords
neutral sizing
sizing agent
agent according
rosin
neutral
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EP83104303A
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German (de)
French (fr)
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EP0123708B1 (en
Inventor
Wolf-Stefan Dr.-Ing. Schultz
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Klebstoffwerke Collodin Drschultz & Nauth GmbH
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Klebstoffwerke Collodin Drschultz & Nauth GmbH
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Application filed by Klebstoffwerke Collodin Drschultz & Nauth GmbH filed Critical Klebstoffwerke Collodin Drschultz & Nauth GmbH
Priority to AT83104303T priority Critical patent/ATE24559T1/en
Priority to EP83104303A priority patent/EP0123708B1/en
Priority to DE8383104303T priority patent/DE3368706D1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/22—Proteins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/62—Rosin; Derivatives thereof

Definitions

  • rosin and modified or reinforced rosin have been used primarily for the mass sizing and hydrophobization of paper and other cellulose-containing fabrics.
  • the enhancement of rosin by reacting with maleic anhydride or other dienophilic compounds while increasing the number of carboxyl groups in the rosin has been e.g. by Casey in Pulp and Paper, 2nd Edition, Vol. II, pages 1043 to 1066 and in U.S. Patents 2,628-918 and 2,684,300.
  • a typical reinforced rosin should contain about 1 to 30% by weight of maleic anhydride, based on the resin, in a bound form as an adduct (maleinopimaric anhydride).
  • the rosin glue used since 1806 in the form of its various applications as liquid soap, dry glue or dispersion had the disadvantage, however, that inorganic salts such as aluminum sulfate, which had a pH of 4.5, were required to fix it on the cellulose fiber or paper fiber required. This acidic pH led to severe corrosion on the units of the paper machine and made the paper non-aging.
  • Dispersion glues based on rosins which contain casein or other proteins as a dispersant or protective colloid are also known (cf. Pulp and Paper, loc. Cit.). These dispersion glues However, had to be produced with the help of complicated inversion processes in complex devices and with greater energy consumption.
  • the invention has for its object to provide a neutral sizing agent for cellulosic fabrics in the form of a soap solution or a dry glue, in particular a paper glue based on a rosin - be it modified or unmodified, hydrogenated or disproportionated - that is easy to manufacture and not by is dependent on the use in the acidic pH range and allows the papermaker to choose the optimal pH range between 4 and 7 for his product.
  • the neutral sizing agent contains a vegetable or animal, digested protein as a fixing agent.
  • the protein content of the neutral sizing agent which surprisingly improves the retention of the glue on the paper and thus serves as a fixing agent, enables the use of normal resin glue in bulk at neutral pH. Corrosion problems are thus reduced to a minimum, and the use of aluminum sulfate or another aluminum salt can be significantly reduced or even avoided.
  • the neutral sizing agent according to the invention is particularly advantageous in paper sizing because it is not dependent on use in the acidic pH range and can be mixed with water in any desired ratio. It is in particular capable of use in a broad pH - range from 4.5 to 7, in borderline cases, in addition, to compensate for variations in the composition of matter, arising from the use of waste paper.
  • the rosin used in the neutral sizing agent of the invention can be any of the commercially available rosins, e.g. Root resin, balsam resin, tall oil resin and mixtures of two or more of these resins in the raw or refined state. Resins with a tendency to crystallize can be treated at elevated temperatures with formaldehyde or paraformaldehyde in the presence of an acid catalyst, e.g. p-toluenesulfonic acid, are treated in a known manner. So resin treated with formaldehyde can be used and falls under the term rosin resin used here.
  • an acid catalyst e.g. p-toluenesulfonic acid
  • a modified or reinforced rosin is a reaction product of rosin with an acidic, dienophilic compound that does the rest contains, which is obtained by reacting rosin with a dienophilic compound at elevated temperatures, usually about 150 to 210 ° C, as an adduct.
  • the amount of the dienophilic compound used is adjusted so that a modified rosin with a content of 1 to 30% by weight, preferably 5 to 12% by weight, of the added dienophilic compound, based on the weight of the reinforced rosin, is obtained .
  • Methods for making reinforced rosins are described in U.S. Patents 2,628,918 and 2,684,300.
  • dienophiles the rest Compounds containing that can be used to make the reinforced rosin are the ⁇ , ⁇ -unsaturated organic acids and their accessible anhydrides. Specific examples of this are maleic anhydride, fumaric acid, acrylic acid, maleic acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride as well as citric acid. Preferred modifiers are maleic anhydride or fumaric acid. If necessary, acid mixtures can be used to produce the rosin.
  • Mixtures of various reinforced rosins can also be used.
  • a mixture of the maleic anhydride adduct with rosin and the fumaric acid adduct with rosin can be used to prepare the neutral sizing agents according to the invention.
  • modified and unmodified, hydrogenated or disproportionated rosins can also be used to produce the neutral sizing agents according to the invention.
  • Such mixtures of modified or unmodified, hydrogenated or disproportionated rosins contain about 50 to 100% modified resin and about 50 to 0% unmodified, hydrogenated or disproportionated resin. If a rosin mixture is used, this mixture can contain any of the rosins listed above, whether modified or unmodified, optionally partially or practically completely hydrogenated or disproportionated or polymerized.
  • the animal or vegetable digested protein contained in the neutral sizing agent according to the invention can e.g. from soy protein, casein or starch protein, which is digested with ammonia, potassium hydroxide, sodium hydroxide, borax, metaborate, triethanolamine, lithium hydroxide or phosphates.
  • starch protein e.g. a waste product from the production of potato flour.
  • the neutral sizing agent according to the invention can optionally be a polyamm derivative, i.e. contain a cationic fixative or retention agent.
  • fixatives are polyethyleneimine derivatives.
  • the second fixing agent can be added in amounts of up to 10%, based on the finished neutral sizing agent. In this case, the use of aluminum sulfate or other aluminum salts can be dispensed with entirely.
  • the neutral sizing agent according to the invention may also contain known additives, e.g. Waxes, in particular paraffin wax and microcrystalline wax, hydrocarbon resins, including those derived from petroleum hydrocarbons and terpenes, spindle oil or polyglycols. These can be added in amounts of up to 95% by weight, preferably about 3 to 20% by weight, of additives, based on the weight of the rosin.
  • Waxes in particular paraffin wax and microcrystalline wax
  • hydrocarbon resins including those derived from petroleum hydrocarbons and terpenes, spindle oil or polyglycols.
  • extender can also be added.
  • extenders which can be used in amounts of 10 to 50% by weight, based on the weight of the rosin, are, for example Tall oil derivatives in question.
  • the neutral sizing agent according to the invention can furthermore contain stabilizers, e.g. Contain isopropanol, methanol, ethanol, glycerin, glycol or polyglycols. These stabilizers can be added in amounts of up to 5%, based on the finished neutral sizing agent.
  • stabilizers e.g. Contain isopropanol, methanol, ethanol, glycerin, glycol or polyglycols.
  • an aqueous solution of the saponified rosin resin (a) is mixed with an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or customary extenders, additives and / or stabilizers (d).
  • the ingredients can be in diluted or concentrated form, i.e. with a solids concentration between 30 and 60%.
  • a melt of the rosin (a) is saponified with the addition of a saponifying agent and an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or conventional constituents (d).
  • the finished re-sizing agent can have a solids content of 10 to 95%.
  • the solids content of the soap solution is preferably 30 to 60% and is only further diluted before use.
  • the solids content of the dry glue is preferably 85 to 95%.
  • the ratio of rosin to protein in the neutral sizing agent according to the invention is 100: 1 to 100:20.
  • 100 parts of the resin from stage a were saponified with 16 parts of sodium hydroxide solution as a 50% solution and adjusted to a dry content of 50% with water.
  • casein 29 parts were dispersed with 2 parts of 45% sodium hydroxide solution in 150 parts of water and heated to 60 ° C. for 15 minutes.
  • Example 1 The procedure of Example 1 was repeated, the amount of added casein solution from step c being varied in stage d from 2.5 to 50 parts of casein solution per 100 parts of glue solution from stage b. All the glues obtained in this way were used and tested in accordance with the procedure of Example 1d for gluing the spruce sulfite pulp, 2% glue being used absolutely dry, based on pulp, and the pH in each case being A1 2 (S0 4 ) 3 6.8 was set.
  • Example 4 The procedure of Example 4 was repeated, but instead of the casein solution c used there, a protein solution was used which was obtained by dispersing 18 parts of soy protein with 2.5 parts of KOH in 100 parts of cold water and heating to 70.degree. The glue obtained had an ink swimming time of 145 seconds.
  • This example illustrates the production of a dry glue. 100 parts of resin were melted and saponified with the addition of a mixture of 60 g of 45% NaOH and 20 g of a casein solution according to Example 1c. The ink float was 60 seconds compared to 35 seconds for the 0 sample.
  • Example 1 illustrates the use of different disintegrants for the protein.
  • the procedure of Example 1 was repeated, but different disintegrants for the casein were used in stage c.
  • the results are shown in Table II.
  • the sheet formation was carried out as in Examples 1 to 7.
  • 100 parts of the reinforced resin from stage a were saponified with 17 parts of NaOH as a 50% solution and adjusted to 50% dryness with water.
  • a glue of 100 parts of the soap solution from stage b and 10 parts of the casein solution from example 1c gave an ink floating time of 110 seconds compared to 60 seconds of the 0 sample.
  • Example 2 illustrates the use of a second fixative in the neutral sizing agent.
  • the procedure of Example 1 was repeated, but in step d instead of the 2.5 parts of the casein solution obtained in step c, 5 parts of the casein solution and additionally 5 parts of a polyethyleneimine derivative were mixed with the 100 parts of the soap solution obtained in step b.
  • an ink float of 300 seconds was measured.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

1. Neutral sizing agent for cellulose-containing flat structures, comprising (a) at least one colophonium rosin, modified by a carboxyl groups containing dienophilic compound, (b) a hydrolyzed animal or vegetable protein, (c) if indicated, a polyamine derivative as fixative, and, (d) if indicated, customary extenders, additives and/or stabilizers, whereby the weight ratio of (a) to (b) is from 100 : 1 to 100 : 20, characterized in that the colophonium rosin (a) is saponified and the sizing agent is present in the form of a soap solution or a dry glue.

Description

Die Erfindung betrifft ein Neutralleimungsmittel für cellulosehaltige Flächengebilde in Form einer Seifenlösung oder eines Trockenleimes, das

  • (a) mindestens ein mit einer carboxylgruppenhaltigen dienophilen Verbindung modifiziertes und/oder nicht-modifiziertes und/oder hydriertes und/oder disproportioniertes Kolophoniumharz,
  • (b) ein tierisches oder pflanzliches, aufgeschlossenes Protein als Fixiermittel,
  • (c) gegebenenfalls ein Polyaminderivat als zweites Fixiermittel und
  • (d) gegebenenfalls übliche Streckmittel, Zuschlagstoffe und/oder Stabilisatoren
enthält, wobei das Gewichtsverhältnis von (a) zu (b) 100:1 bis 100:20 beträgt, ein Verfahren zur Herstellung dieses Neutralleimungsmittels und seine Verwendung zur Neutralleimung cellulosehaltiger Flächengebilde, insbesondere zur Masseleimung von Papier.The invention relates to a neutral sizing agent for cellulosic fabrics in the form of a soap solution or a dry glue, the
  • (a) at least one rosin modified and / or unmodified and / or hydrogenated and / or disproportionated with a carboxyl-containing dienophile compound,
  • (b) an animal or vegetable, digested protein as a fixative,
  • (c) optionally a polyamine derivative as the second fixing agent and
  • (d) if appropriate customary extenders, additives and / or stabilizers
contains, the weight ratio of (a) to (b) being 100: 1 to 100:20, a process for the preparation of this neutral sizing agent and its use for the neutral sizing of cellulose-containing fabrics, in particular for the mass sizing of paper.

Bisher wurden zur Masseleimung und Hydrophobierung von Papier und anderen cellulosehaltigen Flächengebilden in erster Linie Kolophonium und modifiziertes bzw. verstärktes Kolophonium verwendet. Die Verstärkung von Kolophonium durch Umsetzen mit Maleinsäureanhydrid oder anderen dienophilen Verbindungen unter Erhöhung der Zahl der Carboxylgruppen im Kolophonium wurde z.B. von Casey in Pulp and Paper, 2. Auflage, Bd. II, Seiten 1043 bis 1066 und in den US-PSn 2 628-918 und 2 684 300 beschrieben. Ein typisches verstärktes Kolophoniumharz sollte etwa 1 bis 30 Gew.-% Maleinsäureanhydrid, bezogen auf das Harz, in gebundener Form als Addukt (Maleinopimarsäureanhydrid) enthalten.So far, rosin and modified or reinforced rosin have been used primarily for the mass sizing and hydrophobization of paper and other cellulose-containing fabrics. The enhancement of rosin by reacting with maleic anhydride or other dienophilic compounds while increasing the number of carboxyl groups in the rosin has been e.g. by Casey in Pulp and Paper, 2nd Edition, Vol. II, pages 1043 to 1066 and in U.S. Patents 2,628-918 and 2,684,300. A typical reinforced rosin should contain about 1 to 30% by weight of maleic anhydride, based on the resin, in a bound form as an adduct (maleinopimaric anhydride).

Der seit 1806 in Form seiner verschiedenen Anwendungsmöglichkeiten als flüssige Seife, Trockenleim oder Dispersion angewendete Kolophoniumharzleim hatte jedoch den Nachteil, daß zu seiner Fixierung auf der Cellulosefaser bzw. Papierfaser anorganische Salze, wie Aluminiumsulfat, erforderlich waren, die einen pH-Wert von 4,5 erforderten. Dieser saure pH-Wert führte zu starker Korrosion an den Aggregaten der Papiermaschine und machte das Papier alterungsunbeständig.The rosin glue used since 1806 in the form of its various applications as liquid soap, dry glue or dispersion had the disadvantage, however, that inorganic salts such as aluminum sulfate, which had a pH of 4.5, were required to fix it on the cellulose fiber or paper fiber required. This acidic pH led to severe corrosion on the units of the paper machine and made the paper non-aging.

Es sind auch bereits Dispersionsleime auf der Grundlage von Kolophoniumharzen bekannt, die als Dispergiermittel bzw. Schutzkolloid Casein oder andere Proteine enthalten (vgl. Pulp and Paper, a.a.O.). Diese Dispersionsleime mußten jedoch mit Hilfe umständlicher Inversionsverfahren in aufwendigen Vorrichtungen und unter größerem Energieverbrauch hergestellt werden.Dispersion glues based on rosins which contain casein or other proteins as a dispersant or protective colloid are also known (cf. Pulp and Paper, loc. Cit.). These dispersion glues However, had to be produced with the help of complicated inversion processes in complex devices and with greater energy consumption.

Der Erfindung liegt die Aufgabe zugrunde, ein Neutralleimungsmittel für cellulosehaltige Flächengebilde in Form einer Seifenlösung oder eines Trockenleims, insbesondere einen Papierleim, auf der Grundlage eines Kolophoniumharzes - sei es modifiziert oder nicht-modifiziert, hydriert oder disproportioniert - bereitzustellen, das einfach herzustellen und nicht von der Verwendung im sauren pH-Bereich abhängig ist und dem Papiermacher erlaubt, den für sein Produkt optimalen pH-Bereich zwischen 4 und 7 zu wählen.The invention has for its object to provide a neutral sizing agent for cellulosic fabrics in the form of a soap solution or a dry glue, in particular a paper glue based on a rosin - be it modified or unmodified, hydrogenated or disproportionated - that is easy to manufacture and not by is dependent on the use in the acidic pH range and allows the papermaker to choose the optimal pH range between 4 and 7 for his product.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Neutralleimungsmittel ein pflanzliches oder tierisches,aufgeschlossenes Protein als Fixiermittel enthält.This object is achieved in that the neutral sizing agent contains a vegetable or animal, digested protein as a fixing agent.

Durch den Gehalt des Neutralleimungsmittels an Protein, das überraschenderweise die Retention des Leimes an dem Papier verbessert und somit als Fixiermittel dient, wird die Anwendung des normalen Harzleimes in der Masse bei neutralem pH-Wert ermöglicht. Somit werden Korrosionsprobleme auf ein Minimum reduziert, und der Einsatz von Aluminiumsulfat oder einem anderen Aluminiumsalz kann wesentlich verringert oder sogar vermieden werden. Das erfindungsgemäße Neutralleimungsmittel ist bei der Papierleimung besonders vorteilhaft, weil es nicht von einer Verwendung im sauren pH-Bereich abhängig ist und sich mit Wasser in jedem gewünschten Verhältnis mischen läßt. Es ist insbesondere in der Lage, durch die Anwendung in einem breiten pH-Bereich zwischen 4,5 und 7, in Grenzfällen auch darüberhinaus, Schwankungen der Stoffzusammensetzung, die bei Verwendung von Altpapier auftreten, auszugleichen.The protein content of the neutral sizing agent, which surprisingly improves the retention of the glue on the paper and thus serves as a fixing agent, enables the use of normal resin glue in bulk at neutral pH. Corrosion problems are thus reduced to a minimum, and the use of aluminum sulfate or another aluminum salt can be significantly reduced or even avoided. The neutral sizing agent according to the invention is particularly advantageous in paper sizing because it is not dependent on use in the acidic pH range and can be mixed with water in any desired ratio. It is in particular capable of use in a broad pH - range from 4.5 to 7, in borderline cases, in addition, to compensate for variations in the composition of matter, arising from the use of waste paper.

Das im erfindungsgemäßen Neutralleimungsmittel eingesetzte Kolophoniumharz kann jedes der im Handel erhältlichen Kolophoniumharze sein, z.B. Wurzelharz, Balsamharz, Tallöl-Harz und Gemische zweier oder mehrerer dieser Harze im Roh- oder raffinierten Zustand. Harze mit einer Kristallisationstendenz können bei erhöhten Temperaturen mit Formaldehyd oder Paraformaldehyd in Gegenwart eines sauren Katalysators, z.B. p-Toluolsulfonsäure, in bekannter Weise behandelt werden. So kann mit Formaldehyd behandeltes Harz verwendet werden und fällt unter den hier verwenden Ausdruck Kolophoniumharz.The rosin used in the neutral sizing agent of the invention can be any of the commercially available rosins, e.g. Root resin, balsam resin, tall oil resin and mixtures of two or more of these resins in the raw or refined state. Resins with a tendency to crystallize can be treated at elevated temperatures with formaldehyde or paraformaldehyde in the presence of an acid catalyst, e.g. p-toluenesulfonic acid, are treated in a known manner. So resin treated with formaldehyde can be used and falls under the term rosin resin used here.

Als modifiziertes oder verstärktes Kolophoniumharz wird ein Reaktionsprodukt von Kolophonium mit einer sauren, dienophilen Verbindung, die den Rest

Figure imgb0001
enthält, verwendet, das durch Umsetzen von Kolophonium mit einer dienophilen Verbindung bei erhöhten Temperaturen, gewöhnlich etwa 150 bis 210°C, als Addukt erhalten wird. Die eingesetzte Menge der dienophilen Verbindung wird so eingestellt, daß ein modifiziertes Kolophoniumharz mit einem Gehalt von 1 bis 30 Gew.-%, bevorzugt 5 bis 12 Gew.-%, der addierten dienophilen Verbindung, bezogen auf das Gewicht des verstärkten Kolophoniumharzes, erhalten wird. Verfahren zur Herstellung verstärkter Kolophoniumharze sind in den US-PSen 2 628 918 und 2 684 300 beschrieben.A modified or reinforced rosin is a reaction product of rosin with an acidic, dienophilic compound that does the rest
Figure imgb0001
 contains, which is obtained by reacting rosin with a dienophilic compound at elevated temperatures, usually about 150 to 210 ° C, as an adduct. The amount of the dienophilic compound used is adjusted so that a modified rosin with a content of 1 to 30% by weight, preferably 5 to 12% by weight, of the added dienophilic compound, based on the weight of the reinforced rosin, is obtained . Methods for making reinforced rosins are described in U.S. Patents 2,628,918 and 2,684,300.

Beispiele für dienophile, den Rest

Figure imgb0002
enthaltende Verbindungen, die zur Herstellung des verstärkten Kolophoniumharzes verwendet werden können, sind die α,β-ungesättigten, organischen Säuren und ihre zugänglichen Anhydride. Spezielle Beispiele hierfür sind Maleinsäureanhydrid, Fumarsäure, Acrylsäure, Maleinsäure, Itaconsäure, Itaconsäureanhydrid, Citraconsäure und Citraconsäureanhydrid sowie Zitronensäure. Bevorzugte Modifizierungsmittel sind Maleinsäureanhydrid oder Fumarsäure. Gegebenenfalls können zur Herstellung des Kolophoniumharzes Säuregemische eingesetzt werden.Examples of dienophiles, the rest
Figure imgb0002
 Compounds containing that can be used to make the reinforced rosin are the α, β-unsaturated organic acids and their accessible anhydrides. Specific examples of this are maleic anhydride, fumaric acid, acrylic acid, maleic acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride as well as citric acid. Preferred modifiers are maleic anhydride or fumaric acid. If necessary, acid mixtures can be used to produce the rosin.

Auch können Gemische verschiedener verstärkter Kolophoniumharze verwendet werden. Es kann z.B. ein Gemisch des Maleinsäureanhydridadduktes an Kolophonium und des Fumarsäureadduktes an Kolophonium zur Herstellung der erfindungsgemäßen Neutralleimungsmittel verwendet werden.Mixtures of various reinforced rosins can also be used. For example, a mixture of the maleic anhydride adduct with rosin and the fumaric acid adduct with rosin can be used to prepare the neutral sizing agents according to the invention.

Zur Herstellung der erfindungsgemäßen Neutralleimungsmittel können auch Gemische von modifizierten und nicht-modifizierten, hydrierten oder disproportionierten Kolophoniumharzen verwendet werden. Derartige Gemische aus modifizierten oder nicht-modifizierten, hydrierten oder disproportionierten Kolophoniumharzen enthalten etwa 50 bis 100 % modifiziertes Harz und etwa 50 bis 0 % nicht modifiziertes, hydriertes oder disproportioniertes Harz. Wird ein Kolophoniumharzgemisch eingesetzt, so kann dieses Gemisch jedes der vorstehend aufgeführten Kolophoniumharze, ob modifiziert oder nichtmodifiziert , gegebenenfalls teilweise oder praktisch vollständig hydriert oder disproportioniert oder auch polymerisiert, enthalten.Mixtures of modified and unmodified, hydrogenated or disproportionated rosins can also be used to produce the neutral sizing agents according to the invention. Such mixtures of modified or unmodified, hydrogenated or disproportionated rosins contain about 50 to 100% modified resin and about 50 to 0% unmodified, hydrogenated or disproportionated resin. If a rosin mixture is used, this mixture can contain any of the rosins listed above, whether modified or unmodified, optionally partially or practically completely hydrogenated or disproportionated or polymerized.

Das im erfindungsgemäßen Neutralleimungsmittel enthaltene tierische oder pflanzliche, aufgeschlossene Protein kann z.B. aus Sojaprotein, Casein oder Stärkeeiweiß, das mit Ammoniak, Kaliumhydroxid, Natriumhydroxid, Borax, Metaborat, Triethanolamin, Lithiumhydroxid oder Phosphaten aufgeschlossen ist, bestehen. Als Stärkeeiweiß kann z.B. ein Abfallprodukt der Kartoffelmehlherstellung verwendet werden.The animal or vegetable digested protein contained in the neutral sizing agent according to the invention can e.g. from soy protein, casein or starch protein, which is digested with ammonia, potassium hydroxide, sodium hydroxide, borax, metaborate, triethanolamine, lithium hydroxide or phosphates. As starch protein e.g. a waste product from the production of potato flour.

Das erfindungsgemäße Neutralleimungsmittel kann ggf. als zweites Fixiermittel ein Polyammderivat, d.h. ein kationisches Fixiermittel bzw. Retentionsmittel, enthalten. Beispiele für derartige Fixiermittel sind Polyethyleniminderivate. Das zweite Fixiermittel kann in Mengen bis zu 10 %, bezogen auf das fertige Neutralleimungsmittel, zugesetzt werden. In diesem Fall kann auf die Verwendung von Aluminiumsulfat oder anderen Aluminiumsalzen vollständig verzichtet werden.The neutral sizing agent according to the invention can optionally be a polyamm derivative, i.e. contain a cationic fixative or retention agent. Examples of such fixatives are polyethyleneimine derivatives. The second fixing agent can be added in amounts of up to 10%, based on the finished neutral sizing agent. In this case, the use of aluminum sulfate or other aluminum salts can be dispensed with entirely.

Das erfindungsgemäße Neutralleimungsmittel kann weiterhin gegebenenfalls bekannte Zuschlagstoffe, z.B. Wachse, insbesondere Paraffinwachs und mikrokristallines Wachs, Kohlenwasserstoffharze einschließlich der von Erdölkohlenwasserstoffen und Terpenen abgeleiteten, Spindel- öl oder Polyglykole, enthalten. Diese können in Mengen bis zu 95 Gew.-%, vorzugsweise etwa 3. bis 20 Gew.-% Zuschlagstoffe, bezogen auf das Gewicht des Kolophoniumharzes zugemischt werden.The neutral sizing agent according to the invention may also contain known additives, e.g. Waxes, in particular paraffin wax and microcrystalline wax, hydrocarbon resins, including those derived from petroleum hydrocarbons and terpenes, spindle oil or polyglycols. These can be added in amounts of up to 95% by weight, preferably about 3 to 20% by weight, of additives, based on the weight of the rosin.

Es kann auch ein Streckmittel zugesetzt werden. Als Streckmittel, die in Mengen von 10 bis 50 Gew.-%, bezogen auf das Gewicht des Kolophoniumharzes, eingesetzt werden können, kommen z.B. Tallölderivate infrage.An extender can also be added. As extenders, which can be used in amounts of 10 to 50% by weight, based on the weight of the rosin, are, for example Tall oil derivatives in question.

Das erfindungsgemäße Neutralleimungsmittel kann weiterhin Stabilisatoren, wie z.B. Isopropanol, Methanol, Ethanol, Glycerin, Glykol oder Polyglykole enthalten. Diese Stabilisatoren können in Mengen bis zu 5 %, bezogen auf das fertige Neutralleimungsmittel, zugesetzt werden.The neutral sizing agent according to the invention can furthermore contain stabilizers, e.g. Contain isopropanol, methanol, ethanol, glycerin, glycol or polyglycols. These stabilizers can be added in amounts of up to 5%, based on the finished neutral sizing agent.

Zur Herstellung des erfindungsgemäßen Neutralleimungsmittels wird eine wäßrige Lösung des verseiften Kolophoniumharzes (a) mit einer wäßrigen Lösung des aufgeschlossenen Proteins (b) und gegebenenfalls dem zweiten Fixiermittel (c) und/oder üblichen Streckmitteln, Zuschlagsstoffen und/oder Stabilisatoren (d) vermischt. Die Bestandteile können in verdünnter oder konzentrierter Form, d.h. mit Feststoffkonzentration zwischen 30 und 60 % miteinander vermischt werden. Zur Herstellung des Trockenleimes wird eine Schmelze des Kolophoniumharzes (a) unter Zugabe eines Verseifungsmittels und einer wäßrigen Lösung des aufgeschlossenen Proteins (b) und gegebenenfalls des zweiten Fixiermittels (c) und/oder üblicher Bestandteile (d) verseift.To produce the neutral sizing agent according to the invention, an aqueous solution of the saponified rosin resin (a) is mixed with an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or customary extenders, additives and / or stabilizers (d). The ingredients can be in diluted or concentrated form, i.e. with a solids concentration between 30 and 60%. To produce the dry glue, a melt of the rosin (a) is saponified with the addition of a saponifying agent and an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or conventional constituents (d).

Das fertige Neütralleimungsmittel kann einen Feststoffgehalt von 10 bis 95 % aufweisen. Vorzugsweise liegt der Feststoffgehalt der Seifenlösung bei 30 bis 60 % und wird erst vor Anwendung weiter verdünnt. Der Feststoffgehalt des Trockenleimes liegt vorzugsweise bei 85 bis 95 %.The finished re-sizing agent can have a solids content of 10 to 95%. The solids content of the soap solution is preferably 30 to 60% and is only further diluted before use. The solids content of the dry glue is preferably 85 to 95%.

Das Verhältnis von Kolophoniumharz zu Protein beträgt im erfindungsgemäßen Neutralleimungsmittel 100:1 bis 100:20.The ratio of rosin to protein in the neutral sizing agent according to the invention is 100: 1 to 100:20.

Die folgenden Beispiele erläutern die Erfindung:The following examples illustrate the invention:

Beispiel 1example 1 a. Herstellung eines mit Maleinsäureanhydrid verstärkten Kolophoniumharzesa. Preparation of a rosin reinforced with maleic anhydride

100 Teile Kolophoniumharz wurden mit 12 Teilen Maleinsäureanhydrid unter Rühren auf 180°C erhitzt; nach 2 Stunden bei Reaktionstemperatur wurde abgekühlt.100 parts of rosin were heated to 180 ° C. with 12 parts of maleic anhydride with stirring; after 2 hours at the reaction temperature, the mixture was cooled.

b. Verseifung des verstärkten Kolophoniumharzesb. Saponification of the reinforced rosin

100 Teile des Harzes aus Stufe a wurden mit 16 Teilen Natronlauge als 50%ige Lösung verseift und mit Wasser auf einen Trockengehalt von 50% eingestellt.100 parts of the resin from stage a were saponified with 16 parts of sodium hydroxide solution as a 50% solution and adjusted to a dry content of 50% with water.

c. Aufschließen des Proteinsc. Digesting the protein

29 Teile Casein wurden mit 2 Teilen 45%iger Natronlauge in 150 Teilen Wasser dispergiert und 15 Minuten auf 60°C erhitzt.29 parts of casein were dispersed with 2 parts of 45% sodium hydroxide solution in 150 parts of water and heated to 60 ° C. for 15 minutes.

d. Leimherstellungd. Glue production

100 Teile der in Stufe b erhaltenen Seifenlösung wurden mit 2,5 Teilen der in Stufe c erhaltenen Caseinlösung versetzt und vermischt. Die so erhaltene Mischung, die einen Trockengehalt von 49,1% aufwies, wurde auf dem Blattbildner (System Rapid-Köthen der Firma Frank, , Weinheim) zur Masseleimung von Blättern aus Fichtensulfitzellstoff eingesetzt, wobei der pH-Wert mit Aluminiumsulfat auf 6,8 eingestellt wurde. Der Fichtensulfitzellstoff hatte einen Mahlgrad von 45° Schopper-Riegler (SR). Der Leim wurde in einer Menge von 2 % absolut trocken, bezogen auf Zellstoff, verwendet. Sodann wurde die Tintenschwimmdauer (vgl. Merkblatt V/15/60 des Vereins der Zellstoff- und Papier-Chemiker und -Ingenieure) bestimmt und mit derjenigen eines Leimes ohne Proteinzusatz gemäß Stufe b verglichen. Die Ergebnisse sind in der nachstehenden Tabelle I aufgeführt.100 parts of the soap solution obtained in stage b were mixed with 2.5 parts of the casein solution obtained in stage c and mixed. The mixture obtained in this way, which had a dry content of 49.1%, was used on the sheet former (System Rapid-Koethen from Frank, Weinheim) for mass sizing sheets of spruce sulfite pulp, the pH being adjusted to 6.8 with aluminum sulfate was discontinued. The spruce sulfite pulp had a freeness of 45 ° Schopper Riegler (SR). The glue was used in an amount of 2% absolutely dry, based on pulp. The ink floating time (see leaflet V / 15/60 of the Association of Pulp and Paper Chemists and Engineers) was then determined and compared with that of a glue without added protein according to stage b. The results are shown in Table I below.

Beispiele 2 bis 7Examples 2 to 7

Die Arbeitsweise von Beispiel 1 wurde wiederholt, wobei in Stufe d die Menge der zugesetzten Caseinlösung aus Stufe c variiert wurde von 2,5 bis 50 Teilen Caseinlösung pro 100 Teile Leimlösung aus Stufe b. Alle so erhaltenen Leime wurden nach der Arbeitsweise von Beispiel 1d zur Leimung des Fichtensulfitzellstoffs eingesetzt und getestet, wobei jeweils 2 % Leim absolut trocken, bezogen auf Zellstoff, verwendet wurden und der pH-Wert in jedem Fall mit A12(S04)3 auf 6,8 eingestellt wurde.The procedure of Example 1 was repeated, the amount of added casein solution from step c being varied in stage d from 2.5 to 50 parts of casein solution per 100 parts of glue solution from stage b. All the glues obtained in this way were used and tested in accordance with the procedure of Example 1d for gluing the spruce sulfite pulp, 2% glue being used absolutely dry, based on pulp, and the pH in each case being A1 2 (S0 4 ) 3 6.8 was set.

Die Versuchsergebnisse sind in der folgenden Tabelle I zusammengefaßt:The test results are summarized in Table I below:

Figure imgb0003
Figure imgb0003

Beispiel 8Example 8

Die Arbeitsweise von Beispiel 4 wurde wiederholt, wobei jedoch anstelle der dort verwendeten Caseinlösung c eine Proteinlösung verwendet wurde, die durch Dispergieren von 18 Teilen Sojaprotein mit 2,5 Teilen KOH in 100 Teilen kaltem Wasser und Erhitzen auf 70°C erhalten wurde. Der erhaltene Leim ergab eine Tintenschwimmdauer von 145 sec.The procedure of Example 4 was repeated, but instead of the casein solution c used there, a protein solution was used which was obtained by dispersing 18 parts of soy protein with 2.5 parts of KOH in 100 parts of cold water and heating to 70.degree. The glue obtained had an ink swimming time of 145 seconds.

Beispiel 9Example 9

Dieses Beispiel verdeutlicht die Herstellung eines Trockenleimes. 100 Teile Harz wurden qeschmolzen und unter Zugabe einer Mischung von 60 g NaOH 45% und 20 g einer Caseinlösung gemäß Beispiel 1c verseift. Die Tintenschwimmdauer betrug 60 sec gegenüber 35 sec der 0-Probe.This example illustrates the production of a dry glue. 100 parts of resin were melted and saponified with the addition of a mixture of 60 g of 45% NaOH and 20 g of a casein solution according to Example 1c. The ink float was 60 seconds compared to 35 seconds for the 0 sample.

Beispiele 10 bis 18Examples 10 to 18

Diese Beispiele verdeutlichen die Verwendung unterschiedlicher Aufschlußmittel für das Protein. Es wurde die Arbeitsweise von Beispiel 1 wiederholt, wobei jedoch in Stufe c unterschiedliche Aufschlußmittel für das Casein eingesetzt wurden. Die Ergebnisse sind in Tabelle II aufgeführt. Die Blattbildung erfolgte wie in den Beispielen 1 bis 7.

Figure imgb0004
These examples illustrate the use of different disintegrants for the protein. The procedure of Example 1 was repeated, but different disintegrants for the casein were used in stage c. The results are shown in Table II. The sheet formation was carried out as in Examples 1 to 7.
Figure imgb0004

Beispiel 19Example 19 a. Herstellung eines mit Fumarsäure verstärkten Harzesa. Production of a resin reinforced with fumaric acid

100 Teile Kolophoniumharz wurden mit 7,5 Teilen Fumarsäure versetzt und unter Rühren auf 210°C erhitzt. Nach 2 Stunden ließ man abkühlen.100 parts of rosin were mixed with 7.5 parts of fumaric acid and heated to 210 ° C. with stirring. After 2 hours, the mixture was allowed to cool.

b. Verseifung des fumarsäureverstärkten Harzesb. Saponification of the fumaric acid-reinforced resin

100 Teile des verstärkten Harzes aus Stufe a wurden mit 17 Teilen NaOH als 50%ige Lösung verseift und auf 50 % Trockengehalt mit Wasser eingestellt.100 parts of the reinforced resin from stage a were saponified with 17 parts of NaOH as a 50% solution and adjusted to 50% dryness with water.

c. Leimherstellungc. Glue production

Ein Leim aus 100 Teilen der Seifenlösung von Stufe b und 10 Teilender Caseinlösung von Beispiel 1c ergab eine Tintenschwimmdauer von 110 sec gegenüber 60 sec der 0-Probe.A glue of 100 parts of the soap solution from stage b and 10 parts of the casein solution from example 1c gave an ink floating time of 110 seconds compared to 60 seconds of the 0 sample.

Beispiel 20,Example 20

Dieses Beispiel verdeutlicht die Verwendung eines zweiten Fixiermittels im Neutralleimungsmittel. Die Arbeitsweise von Beispiel 1 wurde wiederholt, wobei jedoch in Stufe d anstelle der 2,5 Teile der in Stufe c erhaltenen Caseinlösung 5 Teile der Caseinlösung und zusätzlich 5 Teile eines Polyethyleniminderivates mit den 100 Teilen der in Stufe b erhaltenen Seifenlösung vermischt wurden. Bei der Leimungsprüfung bei einem pH-Wert von 7,0 wurde eine Tintenschwimmdauer von 300 sec. gemessen.This example illustrates the use of a second fixative in the neutral sizing agent. The procedure of Example 1 was repeated, but in step d instead of the 2.5 parts of the casein solution obtained in step c, 5 parts of the casein solution and additionally 5 parts of a polyethyleneimine derivative were mixed with the 100 parts of the soap solution obtained in step b. During the sizing test at a pH of 7.0, an ink float of 300 seconds was measured.

Claims (9)

1. Neutralleimungsmittel für cellulosehaltige Flächengebilde in Form einer Seifenlösung oder eines Trockenleimes, enthaltend (a) mindestens ein mit einer carboxylgruppenhaltigen dienophilen Verbindung modifiziertes und/oder nicht-modifiziertes und/oder hydriertes und/oder disproportioniertes Kolophoniumharz, (b) ein tierisches oder pflanzliches, aufgeschlossenes Protein als Fixiermittel, (c) gegebenenfalls ein Polyaminderivatals zweites Fixiermittel und (d) gegebenenfalls übliche Streckmittel, Zuschlagstoffe und/oder Stabilisatoren,
wobei das Gewichtsverhältnis von (a) zu (b) 100:1 bis 100:20 beträgt.1. Containing neutral sizing agents for cellulosic fabrics in the form of a soap solution or a dry glue (a) at least one rosin modified and / or unmodified and / or hydrogenated and / or disproportionated with a carboxyl-containing dienophile compound, (b) an animal or vegetable, digested protein as a fixative, (c) optionally a polyamine derivative as the second fixative and (d) if appropriate customary extenders, additives and / or stabilizers,
wherein the weight ratio of (a) to (b) is 100: 1 to 100:20. 2. Neutralleimungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß es einen Trockengehalt von 10 bis 95 % besitzt.2. Neutral sizing agent according to claim 1, characterized in that it has a dry content of 10 to 95%. 3. Neutralleimungsmittel nach Anspruch 2, dadurch gekennzeichnet, daß es einen Trockengehalt von 30 bis 60 % besitzt.3. neutral sizing agent according to claim 2, characterized in that it has a dry content of 30 to 60%. 4. Neutralleimungsmittel nach Anspruch 2, dadurch gekennzeichnet, daß es einen Trockengehalt von 85 bis 95 % besitzt.4. neutral sizing agent according to claim 2, characterized in that it has a dry content of 85 to 95%. 5. Neutralleimungsmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es als Fixiermittel (b) aufgeschlossenes Casein enthält.5. Neutral sizing agent according to one of claims 1 to 4, characterized in that it contains digested casein as the fixing agent (b). 6. Neutralleimungsmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es als Kolophoniumharz (a) ein mit 8 bis 12 Gew.-% Maleinsäureanhydrid modifiziertes Kolophoniumharz enthält.6. Neutral sizing agent according to one of claims 1 to 5, characterized in that it contains as rosin (a) a rosin modified with 8 to 12% by weight of maleic anhydride. 7. Neutralleimungsmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es als zweites Fixiermittel (c) ein Polyethyleniminderivat enthält.7. Neutral sizing agent according to one of claims 1 to 6, characterized in that it contains a polyethyleneimine derivative as the second fixing agent (c). 8. Verfahren zur Herstellung des Neutralleimungsmittels nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man eine wäßrige Lösung des verseiften Bestandteils (a) mit einer wäßrigen Lösung des Bestandteils (b) und gegebenenfalls Bestandteilen (c) und/oder (d) in verdünnter oder konzentrierter Form vermischt und das erhaltene Gemisch gegebenenfalls weiter mit Wasser verdünnt oder daß man eine Schmelze des Bestandteils (a) unter Zugabe eines Verseifungsmittels und einer wäßrigen Lösung des Bestandteils (b) und gegebenenfalls Bestandteilen (c) und/oder (d) verseift.8. A process for the preparation of the neutral sizing agent according to one of claims 1 to 7, characterized in that an aqueous solution of the saponified component (a) with an aqueous solution of component (b) and optionally components (c) and / or (d) mixed in dilute or concentrated form and the resulting mixture optionally further diluted with water or that a melt of component (a) with the addition of a saponifying agent and an aqueous solution of component (b) and optionally components (c) and / or (d) saponified. 9. Verwendung des Neutralleimungsmittels nach einem der Ansprüche 1 bis 7 zur Neutralleimung cellulosehaltiger Flächengebilde, insbesondere zur Masseleimung von Papier.9. Use of the neutral sizing agent according to one of claims 1 to 7 for the neutral sizing of cellulose-containing fabrics, in particular for the mass sizing of paper.
EP83104303A 1983-05-02 1983-05-02 Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use Expired EP0123708B1 (en)

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AT83104303T ATE24559T1 (en) 1983-05-02 1983-05-02 NEUTRAL SIZE FOR CELLULOSIC SHEET STRUCTURES, PROCESS FOR ITS PRODUCTION AND ITS USE.
EP83104303A EP0123708B1 (en) 1983-05-02 1983-05-02 Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use
DE8383104303T DE3368706D1 (en) 1983-05-02 1983-05-02 Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use

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EP0200002A1 (en) * 1985-04-13 1986-11-05 Chemische Fabrik Brühl Oppermann GmbH Paper-sizing agents and their use

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DE1122200B (en) * 1960-07-28 1962-01-18 Eisele & Hoffmann K G Process for the production of particularly stable, finely dispersed resin dispersions with increased sizing power for sizing paper
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US2116768A (en) * 1934-12-07 1938-05-10 Paper Chemistry Inst Sizing paper
US2288060A (en) * 1938-09-02 1942-06-30 Gustav Staelin Solid water-in-rosin paper size
US2401090A (en) * 1941-06-14 1946-05-28 Hercules Powder Co Ltd Dry size compositions
GB582157A (en) * 1945-01-05 1946-11-08 Wiggins Teape & Company 1919 L An improved water dispersible urea-formaldehyde composition and its preparation
DE820049C (en) * 1948-11-27 1951-11-08 Hanns Dr Arledter Process for producing a paper size
DE1122200B (en) * 1960-07-28 1962-01-18 Eisele & Hoffmann K G Process for the production of particularly stable, finely dispersed resin dispersions with increased sizing power for sizing paper
DE1130955B (en) * 1961-03-28 1962-06-07 Eisele & Hoffmann K G Process for the production of stable, non-crystallizing dispersions from hydrogenated rosin for sizing paper
US3186900A (en) * 1962-07-13 1965-06-01 Hercules Powder Co Ltd Sizing paper under substantially neutral conditions with a preblend of rosin and cationic polyamide-epichlorohydrin resin
GB1078648A (en) * 1963-11-14 1967-08-09 Catomance Ltd Improvements in or relating to waterproofing paper, board and the like
DE1290649B (en) * 1964-06-02 1969-03-13 American Cyanamid Co Paste-form resin glue, its manufacture and use
FR2214738A1 (en) * 1973-01-22 1974-08-19 Tenneco Chem
US3966654A (en) * 1973-08-06 1976-06-29 Hercules Incorporated Stable rosin dispersions

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Publication number Priority date Publication date Assignee Title
EP0200002A1 (en) * 1985-04-13 1986-11-05 Chemische Fabrik Brühl Oppermann GmbH Paper-sizing agents and their use

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