EP0123708B1 - 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 PDFInfo
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- EP0123708B1 EP0123708B1 EP83104303A EP83104303A EP0123708B1 EP 0123708 B1 EP0123708 B1 EP 0123708B1 EP 83104303 A EP83104303 A EP 83104303A EP 83104303 A EP83104303 A EP 83104303A EP 0123708 B1 EP0123708 B1 EP 0123708B1
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- Prior art keywords
- sizing agent
- rosin
- neutral sizing
- colophonium
- agent according
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Classifications
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- 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 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 described e.g. B. from Casey in Pulp and Paper, 2nd edition, vol. II, pages 1043 to 1066 and in US Pat. Nos. 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).
- Dispersion glues based on rosin resins which contain casein or other proteins as a dispersant or protective colloid are also known (cf. Pulp and Paper, loc. Cit., DE-B1-1 130 955, DE-B1-1 122 200, US-A-2 401 090, US-A-2 116 768, US-A-2 288 060, DE-C-820 049).
- these dispersion glues have to be produced with the help of complicated inversion processes in complex devices and with greater energy consumption.
- a sizing agent for paper in the absence of aluminum sulfate which consists of an aqueous dispersion of a rosin modified with a carboxyl group-containing dienophile resin.
- This dispersion contains, for example, casein digested with ammonia as a protective colloid and can also contain a polyamine derivative.
- the dispersed modified rosin must be at least 90% unsaponified. The preparation of this dispersion requires intensive stirring.
- the object of the invention is to provide a neutral sizing agent for cellulosic fabrics, in particular a paper glue, on the basis of a rosin resin modified with a carboxyl group-containing dienophilic compound, which is simple to produce and is not dependent on use in the acidic pH range and which allows the papermaker to choose the optimal pH range between 4 and 7 for his product.
- the rosin (a) is saponified and the sizing agent is in the form of a soap solution or a dry glue.
- the content of the neutral sizing agent in the saponified, mofidified rosin and in the digested protein which surprisingly improves the retention of the glue on the paper and thus serves as a fixing agent, makes the sizing agent very easy to produce in the form of a soap solution or a dry glue and its use of the resin glue in the mass 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 itself can be mixed with water in any desired ratio. In particular, it is able to compensate for fluctuations in the composition of the material that occur when using waste paper by using it in a wide pH range between 4.5 and 7, and also in borderline cases.
- the modified rosin used in the neutral sizing agent according to the invention can be made from any of the commercially available rosins, e.g. B. 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 acidic catalyst, e.g. B. 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 acidic catalyst e.g. B. 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 as an adduct by reacting rosin with a dienophilic compound at elevated temperatures, usually about 150 to 210 "C.
- the amount of the dienophilic compound used is adjusted so that a modified rosin resin containing 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, and processes for making reinforced rosins are described in U.S. Patents 2,628,918 and 2,684,300 .
- Examples of dienophiles, the rest Compounds containing which can be used to prepare the reinforced rosin are the a, (3-unsaturated organic acids and their accessible anhydrides. Specific examples include maleic anhydride, fumaric acid, acrylic acid, maleic acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride and citric acid Preferred modifiers are maleic anhydride or fumaric acid, and acid mixtures can optionally be used to prepare the rosin.
- Mixtures of various reinforced rosins can also be used. It can e.g. B. a mixture of the maleic anhydride adduct with rosin and the fumaric acid adduct with rosin can be used to produce the neutral sizes according to the invention.
- digested protein can e.g. B. 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 z. B. a waste product of potato flour production can be used.
- the neutral sizing agent according to the invention can optionally be a polyamine derivative, ie. H. contain a cationic fiction 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 can also optionally known additives, for. B. waxes, especially 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.
- 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. B. Tall oil derivatives in question.
- the neutral sizing agent according to the invention can also stabilizers, such as. B. isopropanol, methanol, ethanol, glycerol, glycol or polyglycols. These stabilizers can be added in amounts of up to 5%, based on the finished neutral sizing agent.
- an aqueous solution of the saponified modified rosin (a) is mixed with an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or conventional extenders, additives and / or stabilizers (d).
- the ingredients can be in diluted or concentrated form, e.g. H. with a solids concentration between 30 and 60%.
- a melt of the modified 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 neutral 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 matter 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 glues obtained in this way were used and tested according to the procedure of Example 1d for gluing the spruce sulfite pulp, 2% glue absolutely dry, based on pulp, being used and the pH value in each case with Al 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. however, 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 1 c gave an ink swimming 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.
Abstract
Description
Die Erfindung betrifft ein Neutralleimungsmittel für cellulosehaltige Flächengebilde, enthaltend
- (a) mindestens ein mit einer carboxylgruppenhaltigen dienophilen Verbindung modifiziertes Kolophoniumharz,
- (b) ein tierisches oder pflanzliches, aufgeschlossenes Protein,
- (c) gegebenenfalls ein Polyaminderivat als Fixiermittel und
- (d) gegebenenfalls übliche Streckmittel, Zuschlagstoffe und/oder Stabilisatoren, wobei das Gewichtsverhältnis von (a) zu (b) 100 : 1 bis 100:20 beträgt, das dadurch gekennzeichnet ist, daß das Kolophoniumharz (a) verseift ist und das Leimungsmittel in Form einer Seifenlösung oder eines Trockenleimes vorliegt, sowie ein Verfahren zur Herstellung dieses Neutralleimungsmittels und seine Verwendung zur Neutralleimung cellulosehaltiger Flächengebilde, insbesondere zur Masseleimung von Papier.
- (a) at least one rosin modified with a carboxyl group-containing dienophile compound,
- (b) an animal or vegetable, digested protein,
- (c) optionally a polyamine derivative as the fixing agent and
- (d) if appropriate conventional extenders, additives and / or stabilizers, the weight ratio of (a) to (b) being 100: 1 to 100:20, which is characterized in that the rosin (a) is saponified and the sizing agent in Form of a soap solution or a dry glue is present, as well as a method for producing 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 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 described e.g. B. from Casey in Pulp and Paper, 2nd edition, vol. II, pages 1043 to 1066 and in US Pat. Nos. 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.However, the rosin glue used in the form of its various possible uses as liquid soap, dry glue or dispersion since 1806 had the disadvantage that inorganic salts, such as aluminum sulfate, were required to fix it on the cellulose fiber or paper fiber, and these had a pH of 4.5 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. 0., DE-B1-1 130 955, DE-B1-1 122 200, US-A-2 401 090, US-A-2 116 768, US-A-2 288 060, DE-C-820 049). Diese Dispersionsleime müssen jedoch mit Hilfe umständlicher Inversionsverfahren in aufwendigen Vorrichtungen und unter größerem Energieverbrauch hergestellt werden.Dispersion glues based on rosin resins which contain casein or other proteins as a dispersant or protective colloid are also known (cf. Pulp and Paper, loc. Cit., DE-B1-1 130 955, DE-B1-1 122 200, US-A-2 401 090, US-A-2 116 768, US-A-2 288 060, DE-C-820 049). However, these dispersion glues have to be produced with the help of complicated inversion processes in complex devices and with greater energy consumption.
Aus der FR-A-2214738 ist ein Leimungsmittel für Papier in Abwesenheit von Aluminiumsulfat bekannt, welches aus einer wäßrigen Dispersion eines mit einer carboxylgruppenhaltigen dienophilen Verbindung modifizierten Kolophoniumharzes besteht. Dieses Dispersion enthält beispielsweise mit Ammoniak aufgeschlossenes Casein als Schutzkolloid und kann auch ein Polyaminderivat enthalten. Das dispergierte modifizierte Kolophoniumharz muß zu mindestens 90% unverseift sein. Die Herstellung dieser Dispersion erfordert intensives Rühren.From FR-A-2214738 a sizing agent for paper in the absence of aluminum sulfate is known, which consists of an aqueous dispersion of a rosin modified with a carboxyl group-containing dienophile resin. This dispersion contains, for example, casein digested with ammonia as a protective colloid and can also contain a polyamine derivative. The dispersed modified rosin must be at least 90% unsaponified. The preparation of this dispersion requires intensive stirring.
Der Erfindung liegt die Aufgabe zugrunde, ein Neutralleimungsmittel für cellulosehaltige Flächengebilde, insbesondere einen Papierleim, auf der Grundlage eines mit einer carboxylgruppenhaltigen dienophilen Verbindung modifizierten Kolophoniumharzes 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 object of the invention is to provide a neutral sizing agent for cellulosic fabrics, in particular a paper glue, on the basis of a rosin resin modified with a carboxyl group-containing dienophilic compound, which is simple to produce and is not dependent on use in the acidic pH range and which allows the papermaker to choose the optimal pH range between 4 and 7 for his product.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Kolophoniumharz (a) verseift ist und das Leimungsmittel in Form einer Seifenlösung oder eines Trockenleimes vorliegt.This object is achieved in that the rosin (a) is saponified and the sizing agent is in the form of a soap solution or a dry glue.
Durch den Gehalt des Neutralleimungsmittels an dem verseiften, mofidizierten Kolophoniumharz und an dem aufgeschlossenen Protein, das überraschenderweise die Retention des Leimes an dem Papier verbessert und somit als Fixiermittel dient, wird eine sehr einfache Herstellung des Leimungsmittels in Form einer Seifenlösung oder eines Trockenleimes und die Anwendung des 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 content of the neutral sizing agent in the saponified, mofidified rosin and in the digested protein, which surprisingly improves the retention of the glue on the paper and thus serves as a fixing agent, makes the sizing agent very easy to produce in the form of a soap solution or a dry glue and its use of the resin glue in the mass 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 itself can be mixed with water in any desired ratio. In particular, it is able to compensate for fluctuations in the composition of the material that occur when using waste paper by using it in a wide pH range between 4.5 and 7, and also in borderline cases.
Das im erfindungsgemäßen Neutralleimungsmittel eingesetzte modifizierte Kolophoniumharz kann aus jedem der im Handel erhältlichen Kolophoniumharze, z. B. Wurzelharz.Balsamharz.Tallöl-Harz und Gemischen zweier oder mehrerer dieser Harze im Roh- oder raffinierten Zustand hergestellt werden. 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 modified rosin used in the neutral sizing agent according to the invention can be made from any of the commercially available rosins, e.g. B. 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 acidic catalyst, e.g. B. 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
Beispiele für dienophile, den Rest
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. It can e.g. B. a mixture of the maleic anhydride adduct with rosin and the fumaric acid adduct with rosin can be used to produce the neutral sizes according to the invention.
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 contained in the neutral sizing agent according to the invention. digested protein can e.g. B. 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 z. B. a waste product of potato flour production can be used.
Das erfindungsgemäße Neutralleimungsmittel kann ggf. als zweites Fixiermittel ein Polyaminderivat, d. h. ein kationisches Fikiermittel 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 polyamine derivative, ie. H. contain a cationic fiction 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, Spindelöl 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 can also optionally known additives, for. B. waxes, especially 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. B. 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 also stabilizers, such as. B. isopropanol, methanol, ethanol, glycerol, glycol or polyglycols. These stabilizers can be added in amounts of up to 5%, based on the finished neutral sizing agent.
Zur Herstellung der erfindungsgemäßen Neutralleimungsmittels wird eine wäßrige Lösung des verseiften modifizierten 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 modifizierten 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 modified rosin (a) is mixed with an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or conventional extenders, additives and / or stabilizers (d). The ingredients can be in diluted or concentrated form, e.g. H. with a solids concentration between 30 and 60%. To produce the dry glue, a melt of the modified 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 Neutralleimungsmittel 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 neutral 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:
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 with 12 parts of maleic anhydride to 180 ° C. with stirring; after 2 hours at the reaction temperature, the mixture was cooled.
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 matter content of 50% with water.
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.
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 the mass sizing of sheets of spruce sulfite pulp, the pH being adjusted to 6.8 with aluminum sulfate has been. 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.
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 Al2(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 glues obtained in this way were used and tested according to the procedure of Example 1d for gluing the spruce sulfite pulp, 2% glue absolutely dry, based on pulp, being used and the pH value in each case with Al 2 (S0 4 ) 3 6.8 was set.
Die Versuchsergebnisse sind in der folgenden Tabelle I zusammengefaßt :
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.
Dieses Beispiel verdeutlicht die Herstellung eines Trockenleimes. 100 Teile Harz wurden geschmolzen 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.
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.These examples illustrate the use of different disintegrants for the protein. The procedure of Example 1 was repeated. however, 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.
100Teile Kolophoniumharz wurden 7.5 Teilen Fumarsäure versetzt und unter Rühren auf 210 °C erhitzt. Nach 2 Stunden ließ man abkühlen.100 parts of rosin were added to 7.5 parts of fumaric acid and heated to 210 ° C. with stirring. After 2 hours, the mixture was allowed to cool.
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.
Ein Leim aus 100 Teilen der Seifenlösung von Stufe b und 10 Teilen der Caseinlösung von Beispiel 1 c 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 1 c gave an ink swimming time of 110 seconds compared to 60 seconds of the 0 sample.
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)
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.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE8383104303T DE3368706D1 (en) | 1983-05-02 | 1983-05-02 | Neutral sizing agent for flat cellulose-comprising products, process for its manufacture 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 |
| AT83104303T ATE24559T1 (en) | 1983-05-02 | 1983-05-02 | NEUTRAL SIZE FOR CELLULOSIC SHEET STRUCTURES, PROCESS FOR ITS PRODUCTION AND ITS USE. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP83104303A EP0123708B1 (en) | 1983-05-02 | 1983-05-02 | Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0123708A1 EP0123708A1 (en) | 1984-11-07 |
| EP0123708B1 true EP0123708B1 (en) | 1986-12-30 |
Family
ID=8190440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83104303A Expired EP0123708B1 (en) | 1983-05-02 | 1983-05-02 | Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0123708B1 (en) |
| AT (1) | ATE24559T1 (en) |
| DE (1) | DE3368706D1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE40429T1 (en) * | 1985-04-13 | 1989-02-15 | Chem Fab Bruehl Oppermann Gmbh | PAPER SIZES AND THEIR USE. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0037055A1 (en) * | 1980-03-31 | 1981-10-07 | Klebstoffwerke Collodin Dr.Schultz & Nauth GmbH | Hydrophobic agent for flat cellulosic substrate, process for its manufacture and its use |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| GB1108035A (en) * | 1964-06-02 | 1968-03-27 | American Cyanamid Co | Rosin size and paper sized therewith |
| GB1444751A (en) * | 1973-01-22 | 1976-08-04 | Tenneco Chem | Paper sizing |
| US3966654A (en) * | 1973-08-06 | 1976-06-29 | Hercules Incorporated | Stable rosin dispersions |
-
1983
- 1983-05-02 AT AT83104303T patent/ATE24559T1/en not_active IP Right Cessation
- 1983-05-02 EP EP83104303A patent/EP0123708B1/en not_active Expired
- 1983-05-02 DE DE8383104303T patent/DE3368706D1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0037055A1 (en) * | 1980-03-31 | 1981-10-07 | Klebstoffwerke Collodin Dr.Schultz & Nauth GmbH | Hydrophobic agent for flat cellulosic substrate, process for its manufacture and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0123708A1 (en) | 1984-11-07 |
| DE3368706D1 (en) | 1987-02-05 |
| ATE24559T1 (en) | 1987-01-15 |
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