EP1102894B1 - The use of modified starch products as retention agents in the production of paper - Google Patents

The use of modified starch products as retention agents in the production of paper Download PDF

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Publication number
EP1102894B1
EP1102894B1 EP99938266A EP99938266A EP1102894B1 EP 1102894 B1 EP1102894 B1 EP 1102894B1 EP 99938266 A EP99938266 A EP 99938266A EP 99938266 A EP99938266 A EP 99938266A EP 1102894 B1 EP1102894 B1 EP 1102894B1
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Prior art keywords
starch
use according
moieties
methacrylamide
paper
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EP99938266A
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German (de)
French (fr)
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EP1102894A1 (en
Inventor
Johann Schulte
Joachim Werres
Ulrich Fischer
Hans-Georg Hartan
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Stockhausen GmbH and Co KG
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Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers
    • 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
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates

Definitions

  • the invention relates to the use of starch or starch derivatives with Modified polyelectrolytes based on dialkylaminoalkyl (meth) acrylamides and was digested in the presence of inorganic additives, as Retention agent for pigments, mineral fillers and fibrous fines at Papermaking.
  • Pigments and fillers are used as essential paper components in the Production of the pulp dispersion added and with the help of Retention aids bound in leaf formation.
  • drainage and the strength of the paper are e.g. B. after the Information in the weekly paper for paper manufacturing 5 (1991), pp. 149 to 154, cationic mass starches as colloidal auxiliaries to a large extent used, with the use of cationic starch ethers according to Ullmann, 4. Aufl., 1979, Vol. 17, p. 581, in particular the retention of pigments and Fine substances is improved.
  • high molecular weight polyelectrolytes are, for example, the copolymers of acrylamide and the esters of (meth) acrylic acid with di-C 1 -C 2 alkylamino-C 2 -C 6 alkyl alcohols or the copolymers of acrylamide and the amides of (meth) acrylic acid with di -C 1 -C 2 alkylamino-C 2 -C 6 alkylamines, each of which is present in protonated or quaternized form.
  • Retention agents based on such ⁇ , ⁇ -unsaturated N-substituted carboxamides are described in EP-A-0 038 573. Furthermore, cationic polyacrylamides are also described in US-A-4753710 and WO-A-91/07543 as retention aids.
  • WO-A-86/00100 a method for paper manufacture is known, in which for Improved retention added to the paper pulp colloidal binder be based on aluminum silicate modified on the surface Silicic acid and cationic or amphoteric carbohydrates, such as preferably Starch or amylo pectin are obtained.
  • pp 785 to 790 are as Retention agents continue to be known microparticle systems in which the Pulp dispersion initially with cationic starch or cationic Polyacrylamides pretreated, flocked and dispersed: and then pretreated sheet formation by silica microparticle systems or by adding bentonite or aluminum salts are flocked again.
  • the multi-stage procedure leads to improve retention values.
  • EP-B-0 227 465 describes a process for the production of paper described, in which the fibrous material and separately the mineral filler with a synthetic polyelectrolyte always the same charge and then the treated filler with a polymeric polyelectrolyte with opposite charge is treated.
  • US-A-5,126,014 is a multi-stage process for improving the Retention known, in which a pulp suspension before a possibly multi-stage shear treatment calcium carbonate as filler, cationic starch, a cationic coagulant and an anionic flocculant are added and after at least one shear treatment step bentonite or colloidal Silica is added
  • EP-A-0 803 512 a method for producing cationic starch is known, according to which the starch is dry at temperatures from 60 to 200 ° C for the duration to be roasted with cationic polymers from 10 minutes to 5 hours then to be used as a paper strengthening agent.
  • EP-B-0 282 761 WO-A-96/05373 and WO-A-96/13525 of starch with ionic, especially cationic polyelectrolytes.
  • cationic polymers are used for this Diallyldimethylammonium chloride, N-vinylamine or N-vinylimidazoline with native or Already digested potato starch is heated, while according to WO-A-96/05373 cationic polymers with preferably anionic starch and after WO-A-96/13525 preferably hydrolyzed, cationic polymers of N-vinylformamide, Polyethyleneimines or polyalkylamines with all types of starch be implemented.
  • These implementation products are just like strengths with Copolymers of (meth) acrylamide and dialkylaminoalkyl (meth) acrylamide were modified, only as a dry strength agent for papermaking recommended.
  • cationic starch which may have been siliconized, as a drainage aid and as a retention aid used in papermaking.
  • the object of the present invention was therefore without additional Process steps, d. H. without the sub-steps mentioned above, in the known Paper production, preferably using waste paper, the retention of To improve pigments, fillers and fines without the mechanical Strength of the paper is adversely affected.
  • modified starch by digesting starch, starch derivatives and / or their breakdown products in aqueous solution in the presence of at least one cationic polymer, built up from at least 20% by weight of polymerized di-alkylaminoalkyl (meth) acrylic acid amide units, those in protonated, preferably quaternized Form are present, and with the addition of at least one particulate, to one inorganic mineral based additive before or during the Digestion has been obtained as a retention agent for pigments, inorganic fillers and fines in papermaking.
  • at least one cationic polymer built up from at least 20% by weight of polymerized di-alkylaminoalkyl (meth) acrylic acid amide units, those in protonated, preferably quaternized Form are present, and with the addition of at least one particulate, to one inorganic mineral based additive before or during the Digestion has been obtained as a retention agent for pigments, inorganic fillers and fines in papermaking.
  • native starch such as potato starch, wheat starch, Cereal flour, corn starch, tapioca starch, sago starch and starch with increased Hydrolysis content, rice starch, pea starch and / or mixtures thereof
  • Starch degradation products especially dextrins or oxidized starches, such as Dialdehyde starch, starch derivatives, such as chemically modified starches, in particular anionic starches, such as carboxy starch and starch degraded by persulfate, anionic starch esters, such as.
  • anionic starch esters such as.
  • anionic starch esters such as.
  • anionic starch esters such as.
  • anionic starch esters such as.
  • B. starch phosphoric acid mono- or diester Starch acetates and starch citrates
  • anionic starch ethers such as. B.
  • Native starches such as potato starch, wheat starch, corn starch, Rice starch, pea starch and / or their mixtures and anionic starch and / or cationic N-containing starch ethers are used.
  • Cationic polymers used are homo- or copolymers of dialkylaminoalkyl (meth) acrylic acid amides which contain at least 20% by weight of polymerized units of amides of (meth) acrylic acid and / or acrylic acid and preferably di-C 1 -C 2 -alkylamino-C 2 -C 6 alkylamines contain, each in protonated or quaternized form.
  • Their production is specified, for example, in EP-A-0 013 416 or in EP-A-0 113 038, the corresponding disclosure of these publications being introduced as a reference.
  • Such polymerized units are preferably derived from protonated or quaternized N-dialkyl-substituted (meth) acrylic acid amides, such as, for example Dimethylaminoethyl acrylamide or methacrylamide, dimethylaminopropyl acrylamide or methacrylamide, diethylaminopropyl acrylamide or methacrylamide, Diethylaminoethyl acrylamide or methacrylamide, diethylaminomethyl acrylamide or methacrylamide and N ', N', dimethylamino-2,2-dimethylpropyl-acrylamide or methacrylamide or mixtures thereof with known quaternizing agents have been implemented.
  • suitable quaternizing agents are: Dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride, preferably dimethyl sulfate or methyl chloride in question.
  • the polyelectrolytes can still further units of monounsaturated monomers, such as. B. diallyldimethylammonium chloride.
  • Such copolymerized monomers can also be water-soluble, nonionic monomers, such as acrylamide, methacrylamide, NC 1 -C 2 alkylated (meth) acrylamides, N-vinylamide, vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone.
  • Suitable water-soluble monomers are also N-methylolacrylamide, N-methylol methacrylamide and with monohydric C 1 - to C 4 -alcohols partially or fully etherified N-methylol (meth) acryl-amides.
  • the copolymers can be used to a limited extent, preferably up to 10 % By weight, sparingly soluble and / or water-insoluble in water, simply ethylenic contain unsaturated monomers, such as (meth) acrylic acid alkyl esters and vinyl acetate, as far as the solubility of the copolymers is preserved in water.
  • unsaturated monomers such as (meth) acrylic acid alkyl esters and vinyl acetate
  • the polymers to be used according to the invention preferably have a molecular weight MG (g / mol) in the range from 1.0 ⁇ 10 5 to 40 ⁇ 10 6 , particularly preferably in the range from 2.0 ⁇ 10 6 to 15 ⁇ 10 6 and very particularly preferably from 5 x 10 6 to 15 x 10 6 .
  • the viscosity was determined using a 1% polymer solution in one 10% NaCl solution with a Brookfield RVT viscometer, spindle 1-3 / 10 Revolutions per minute at 20 ° C and resulted in> 10 mPas for use upcoming polymers.
  • particulate additives based on inorganic minerals can also consist of clay, preferably swellable, silica, preferably silica sol and / or polysilicates modified with aluminum, Polyorthosilicic acid or modified with aluminum Polyorthosilicic acid, bentonite, titanium dioxide or talc in question. Preferably these substances are present as microparticles or microgels. Is particularly preferred Bentonite, talc, titanium dioxide or silica sol used.
  • the starch component can be converted using the cationic homo- or Copolymers of preferably protonated or quaternized Dialkylaminoalkyl (meth) acrylic acid amides in aqueous dispersion discontinuously in a reaction vessel or in a continuous flow process, for example in the jet cooker under the influence of heat at temperatures of 70-130 ° C, preferably from 90 - 100 ° C, with the addition of the inorganic additive and if necessary, under pressure with the starch component digested.
  • the Reaction conditions and the appropriate equipment conditions correspond the information in the weekly paper for paper 4, 1991, pp. 127-130, its disclosure is introduced as a reference.
  • the aqueous dispersion of the modification used, not yet digested starch component preferably has a content of 0.5 to 20% by weight, preferably from 0.5 to 10% by weight and particularly preferably from 2.0 up to 10% by weight of the starch component.
  • the aqueous solution for modification polyelectrolyte used has a content of 0.1 to 2.0% by weight, preferably 0.1 to 0.5% by weight and particularly preferably 0.1 to 0.3% by weight cationic homo- or copolymers.
  • the weight ratio of Starch component to cationic polyelectrolyte lies in the modification Range from 4: 1 to 25: 1, preferably in the range from 10: 1 to 25: 1 and especially preferably in the range from 14: 1 to 20: 1.
  • the modified starch products together with the inorganic additives can, preferably in the form of an aqueous solution, as a retention agent in the Production of all types of paper and cardboard can be used.
  • this Fiber material can consist of up to 100% by weight of ground wood and / or waste paper, and therefore a high proportion of mineral fillers, pigments and fibrous fines.
  • the retention aid according to the invention becomes aqueous according to the invention Pulp dispersion in an amount of 0.1 to 10 wt.% Solid, preferably from 0.5 to 5% by weight and particularly preferably 1.0 to 3% by weight, based on the Dry matter or pulp, before the headbox of the paper machine, preferably added as an aqueous solution with stirring.
  • the addition is made to the aqueous dispersion, which already contains calcium carbonate, kaolin, Aluminum silicate and oxide hydrates, satin white, talc, gypsum, barite, calcium silicate and lithopone, diatomaceous earth and synthetic, organic fillers from the Recycled material may or may have been added.
  • the retention agent according to the invention is advantageously added to the Dispersion of material in the machine chest, before the vertical classifier and before or after Feed pump before sheet formation.
  • the retention agent according to the invention based on modified starch and inorganic additives will have an excellent retention of the fillers reached and an impairment of the strength values despite the increase in Filler and thus the ash content of the paper surprisingly avoided.
  • the total retention gives the relationship to the paper production amount of dry substance used to the remaining in the finished paper Amount of substance again. This is done by weighing the respective amounts of substance determinable.
  • the ash retention gives the ratio of the ash content to the Paper production used (dry) amount of substance to the ash content of the finished paper again. This is determined by determining each Ash content determined.
  • the retention of fines indicates the ratio of the fines content to the Paper production used (dry) amount of substance to the proportion of fines of the finished paper again.
  • the coarse fraction corresponds to the amount of fiber that is on the filter.
  • Fine fraction 100 - Coarse fraction in g 0.5 gx 0.01 (%)
  • Comparative Example 1 or Examples 1 to 4 Ash retention% by weight Total retention% by weight Burst pressure kPa mod. Starch without added minerals 93.3 89.1 95 mod. Starch 9.7 bentonite 0.3 95.3 90.7 104 mod. Strength 9.5 bentonite 0.5 95.2 92.1 106 mod. Starch 9.0 bentonite 1.0 97.6 96.7 92 mod. Starch 9.0 talc 1.0 95.3 94.0 -

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  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention relates to the use of modified starches as retention agents for pigments, inorganic fillers and fines in the production of paper. Said modified starches are obtained by decomposing starch, starch derivatives and/or breakdown products thereof in aqueous solution in the presence of at least one cationic polymer made up of at least 20 wt. % polymerised, protonised or quarternised dialkylaminoalkyl(meth)acrylic acid amide units and at least one inorganic mineral substance.

Description

Die Erfindung betrifft den Einsatz von Stärke bzw. Stärkederivaten, die mit Polyelektrolyten auf der Basis von Dialkylaminoalkyl(meth)acrylamiden modifiziert und in Gegenwart von anorganischen Zusatzstoffen aufgeschlossen wurde, als Retentionsmittel für Pigmente, mineralische Füllstoffe und faserige Feinstoffe bei der Papierherstellung.The invention relates to the use of starch or starch derivatives with Modified polyelectrolytes based on dialkylaminoalkyl (meth) acrylamides and was digested in the presence of inorganic additives, as Retention agent for pigments, mineral fillers and fibrous fines at Papermaking.

Pigmente und Füllstoffe werden als wesentliche Papierbestandteile bei der Herstellung der Papierstoffdispersion zugesetzt und mit Hilfe von Retentionshilfsmitteln bei der Blattbildung gebunden. Zur Verbesserung der Retention, Entwässerung und der Festigkeit des Papieres werden z. B. nach den Angaben im Wochenblatt für Papierfabrikationen 5 (1991), S. 149 bis 154, kationische Massenstärken als kolloidale Hilfsstoffe in umfangreichem Maße eingesetzt, wobei durch den Einsatz von kationischen Stärkeethem nach Ullmann, 4. Aufl., 1979, Bd. 17, S. 581, insbesondere die Retention von Pigmenten und Feinstoffen verbessert wird.Pigments and fillers are used as essential paper components in the Production of the pulp dispersion added and with the help of Retention aids bound in leaf formation. To improve the Retention, drainage and the strength of the paper are e.g. B. after the Information in the weekly paper for paper manufacturing 5 (1991), pp. 149 to 154, cationic mass starches as colloidal auxiliaries to a large extent used, with the use of cationic starch ethers according to Ullmann, 4. Aufl., 1979, Vol. 17, p. 581, in particular the retention of pigments and Fine substances is improved.

Die Retentionswirkung der Stärkeether ist jedoch begrenzt, so daß auch hochmolekulare, kationische Polyelektrolyte mit höherer Ladungsdichte als Retentionsmittel zum Einsatz kommen. Solche hochmolekularen Polyelektrolyte sind beispielsweise die Copolymerisate aus Acrylamid und den Estern der (Meth)acrylsäure mit Di-C1-C2-alkylamino-C2-C6-alkylalkoholen oder die Copolymerisate aus Acrylamid und den Amiden der (Meth)acrylsäure mit Di-C1-C2alkylamino-C2-C6-alkylaminen, die jeweils in protonierter oder quaternierter Form vorliegen. Retentionsmittel auf der Basis solcher α, β-ungesättigten N-substituierter Carbonsäureamide sind in EP-A-0 038 573 beschrieben. Weiterhin werden auch in US-A-4753710 bzw. WO-A-91/07543 kationische Polyacrylamide als Retentionshilfsmittel beschrieben.However, the retention effect of the starch ethers is limited, so that high molecular weight, cationic polyelectrolytes with a higher charge density can also be used as retention agents. Such high molecular weight polyelectrolytes are, for example, the copolymers of acrylamide and the esters of (meth) acrylic acid with di-C 1 -C 2 alkylamino-C 2 -C 6 alkyl alcohols or the copolymers of acrylamide and the amides of (meth) acrylic acid with di -C 1 -C 2 alkylamino-C 2 -C 6 alkylamines, each of which is present in protonated or quaternized form. Retention agents based on such α, β-unsaturated N-substituted carboxamides are described in EP-A-0 038 573. Furthermore, cationic polyacrylamides are also described in US-A-4753710 and WO-A-91/07543 as retention aids.

Nach WO-A-86/00100 ist ein Verfahren zur Papierherstellung bekannt, bei dem zur Verbesserung der Retention dem Papierfaserstoff kolloidale Bindemittel zugesetzt werden, die auf der Basis von an der Oberfläche mit Aluminiumsilikat modifizierter Kieselsäure und kationischen oder amphoteren Kohlehydraten, wie vorzugsweise Stärke oder Amylo pektin sind, erhalten werden.According to WO-A-86/00100 a method for paper manufacture is known, in which for Improved retention added to the paper pulp colloidal binder be based on aluminum silicate modified on the surface Silicic acid and cationic or amphoteric carbohydrates, such as preferably Starch or amylo pectin are obtained.

In EP-A-0 703 314 und WO-A-97/04168 wird die Verwendung spezieller kationischer Amylopektinstärken zur Verbesserung der Retention unter optionaler Verwendung von kolloidaler Kieselsäure, anionischen Polyacrylamiden oder Bentonit vorgeschlagen.In EP-A-0 703 314 and WO-A-97/04168 the use of special cationic is Amylopectin starches to improve retention with optional use of colloidal silica, anionic polyacrylamides or bentonite proposed.

Aus dem Wochenblatt für Papierfabrikationen 20, 1994, S. 785 bis 790 sind als Retentionsmittel weiterhin Mikropartikelsysteme bekannt, bei denen die Papierstoffdispersion zunächst mit kationischer Stärke oder kationischen Polyacrylamiden vorbehandelt, geflockt und dispergiert : und anschließend vor der Blattbildung durch Silika-Mikropartikelsysteme oder durch Zugabe von Bentonit oder Aluminiumsalze erneut geflockt wird Die mehrstufige Verfahrensweise führt zu einer Verbesserung der Retentionswerte.From the weekly paper for paper manufacturing 20, 1994, pp 785 to 790 are as Retention agents continue to be known microparticle systems in which the Pulp dispersion initially with cationic starch or cationic Polyacrylamides pretreated, flocked and dispersed: and then pretreated sheet formation by silica microparticle systems or by adding bentonite or aluminum salts are flocked again. The multi-stage procedure leads to improve retention values.

Weiterhin wird in EP-B-0 227 465 ein Verfahren zur Herstellung von Papier beschrieben, bei dem in aufwendigen Teilschritten zunächst der Faserstoff und separat dazu der mineralische Füllstoff mit einem synthetischen Polyelektrolyten jeweils gleicher Ladung und nachfolgend der behandelte Füllstoff mit einem polymeren Polyelektrolyten mit entgegengesetzter Ladung behandelt wird.Furthermore, EP-B-0 227 465 describes a process for the production of paper described, in which the fibrous material and separately the mineral filler with a synthetic polyelectrolyte always the same charge and then the treated filler with a polymeric polyelectrolyte with opposite charge is treated.

Ebenso ist nach US-A-5,126,014 ein mehrstufiges Verfahren zur Verbesserung der Retention bekannt, bei welchem eine Papierstoffsuspension vor einer ggf. mehrstufigen Scherbehandlung Kalziumcarbonat als Füllmittel, kationische Stärke, ein kationisches Koagulierungsmittel und ein anionisches Flockungsmittel zugegeben und nach mindestens einer Scherbehandlungsstufe Bentonit oder kolloidale Kieselsäure zugesetzt wirdLikewise, according to US-A-5,126,014 is a multi-stage process for improving the Retention known, in which a pulp suspension before a possibly multi-stage shear treatment calcium carbonate as filler, cationic starch, a cationic coagulant and an anionic flocculant are added and after at least one shear treatment step bentonite or colloidal Silica is added

Aus dem Stande der Technik ist auch die Modifizierung von Stärkeprodukten mit kationischen Polyelektrolyten bekannt.The modification of starch products is also part of the prior art known cationic polyelectrolytes.

Nach EP-A-0 803 512 ist ein Verfahren zur Herstellung kationischer Stärke bekannt, gemäß dem die Stärke trocken bei Temperaturen vom 60 bis 200°C für die Dauer von 10 Minuten- 5 Stunden mit kationischen Polymeren geröstet werden, um dann als Papierverfestigungsmittel verwendet zu werden.According to EP-A-0 803 512, a method for producing cationic starch is known, according to which the starch is dry at temperatures from 60 to 200 ° C for the duration to be roasted with cationic polymers from 10 minutes to 5 hours then to be used as a paper strengthening agent.

Weiterhin wird in EP-B-0 282 761, WO-A-96/05373 und WO-A-96/13525 die Modifizierung von Stärke mit ionischen, insbesondere kationischen Polyelektrolyten beschrieben. Nach EP-B-0 282 761 werden hierzu kationische Polymerisate aus Diallyldimethylammoniumchlorid, N-Vinylamin oder N-Vinylimidazolin mit nativer oder bereits aufgeschlossener Kartoffelstärke erhitzt, während nach WO-A-96/05373 kationische Polymerisate mit vorzugsweise anionischer Stärke und nach WO-A-96/13525 vorzugsweise hydrolysierte, kationische Polymerisate aus N-Vinylformamid, Polyethyleniminen oder Polyalkylaminen mit Stärke jeder Art umgesetzt werden. Diese Umsetzungsprodukte werden ebenso wie Stärken, die mit Copolymerisaten aus (Meth)acrylamid und Dialkylaminoalkyl(meth)acrylamid modifiziert wurden, nur als Trockenverfestigungsmittel für die Papierherstellung empfohlen.Furthermore, the modification is described in EP-B-0 282 761, WO-A-96/05373 and WO-A-96/13525 of starch with ionic, especially cationic polyelectrolytes. According to EP-B-0 282 761, cationic polymers are used for this Diallyldimethylammonium chloride, N-vinylamine or N-vinylimidazoline with native or Already digested potato starch is heated, while according to WO-A-96/05373 cationic polymers with preferably anionic starch and after WO-A-96/13525 preferably hydrolyzed, cationic polymers of N-vinylformamide, Polyethyleneimines or polyalkylamines with all types of starch be implemented. These implementation products are just like strengths with Copolymers of (meth) acrylamide and dialkylaminoalkyl (meth) acrylamide were modified, only as a dry strength agent for papermaking recommended.

In der US-A-5185206, FR-A-2396831 bzw. US-A-4388150 wird kationische Stärke, die ggf. auch silikonisiert worden ist, als Entwässerungshilfe und als Retentionsmittel bei der Papierherstellung verwendet.In US-A-5185206, FR-A-2396831 and US-A-4388150, cationic starch, which may have been siliconized, as a drainage aid and as a retention aid used in papermaking.

Weiterhin wird in US-A-4097427 die Kationisierung von Stärke durch Aufschluß der Stärke in Gegenwart von quaternisierter ammoniumgruppenhaltige Polymere gelehrt, wobei die so kationisierte Stärke als Füllstoffretentionsmittel bei der Papierherstellung verwendet wird.Furthermore, in US-A-4097427 the cationization of starch by digesting the Taught starch in the presence of quaternized polymers containing ammonium groups, the starch thus cationized as a filler retention agent in the Papermaking is used.

Wegen der zunehmenden Verarbeitung von Altpapier und Holzstoffdispersionen bei der Papierherstellung steigt der Anteil von Feinstoffen, wie kurzen Zellstoffasern, und mineralischen Füllstoffen in den Papierstoffdispersionen. Außerdem muß in aller Regel der Anteil an anorganischen Füllstoffen und Pigmenten noch weiter erhöht werden, um Papier mit marktüblichem Aussehen zu erhalten. Es ist aber bekannt, daß mit steigendem Anteil an Feinstoffen und insbesondere mineralischen Füllstoffen und Pigmenten die Festigkeit des Papiers nachteilig beeinflußt wird. So geht u. a. aus der Publikation von K. Ritter und H. Forkel "Papierfaserstofftechnik" Symposium 1997 21, Seite 4 hervor, daß der Durchreißwiderstand von Papier als Maß für dessen Festigkeit mit steigendem Aschegehalt, der als Maß für den Gehalt an mineralischen Füllstoffen und Pigmenten im Papier gilt, abnimmt.Because of the increasing processing of waste paper and wood pulp dispersions In papermaking, the proportion of fine materials, such as short cellulose fibers, and mineral fillers in the pulp dispersions. In addition, in everything Usually the proportion of inorganic fillers and pigments increased even further to obtain paper with a market appearance. But it is known that with increasing proportion of fine substances and especially mineral fillers and pigments adversely affect the strength of the paper. So u. a. from the publication by K. Ritter and H. Forkel "paper fiber technology" symposium 1997 21, page 4 shows that the tear resistance of paper as a measure of this Strength with increasing ash content, which is a measure of the mineral content Fillers and pigments in paper apply, decreases.

Aufgabe der vorliegenden Erfindung war es daher, ohne zusätzliche Verfahrensschritte, d. h. ohne die oben genannten Teilschritte, bei der bekannten Papierherstellung, vorzugsweise unter Einsatz von Altpapier, die Retention von Pigmenten, Füllstoffen und Feinstoffen zu verbessern, ohne daß die mechanische Festigkeit des Papiers nachteilig beeinflußt wird. The object of the present invention was therefore without additional Process steps, d. H. without the sub-steps mentioned above, in the known Paper production, preferably using waste paper, the retention of To improve pigments, fillers and fines without the mechanical Strength of the paper is adversely affected.

Erfindungsgemäß gelingt dies durch die Verwendung von modifizierter Stärke, die durch Aufschluß von Stärke, Stärkederivaten und/oder deren Abbauprodukten in wässriger Lösung in Gegenwart wenigstens eines kationischen Polymerisats, aufgebaut aus mindestens 20 Gew.% von polymerisierten Di-alkylaminoalkyl(meth)acrylsäureamid-Einheiten, die in protonierter, vorzugsweise quaternisierter Form vorliegen, und unter Zusatz wenigstens eines partikelförmigen, auf einen anorganischen Mineralstoff basierenden Zusatzstoff vor oder während des Aufschlußes erhalten worden ist, als Retentionsmittel für Pigmente, anorganische Füllstoffe und Feinstoffen bei der Papierherstellung.According to the invention this is achieved by using modified starch by digesting starch, starch derivatives and / or their breakdown products in aqueous solution in the presence of at least one cationic polymer, built up from at least 20% by weight of polymerized di-alkylaminoalkyl (meth) acrylic acid amide units, those in protonated, preferably quaternized Form are present, and with the addition of at least one particulate, to one inorganic mineral based additive before or during the Digestion has been obtained as a retention agent for pigments, inorganic fillers and fines in papermaking.

Als Stärkekomponente werden native Stärke, wie Kartoffelstärke, Weizenstärke, Getreidemehl, Maisstärke, Tapiokastärke, Sagostärke sowie Stärke mit erhöhtem Hydrolysegehalt, Reisstärke, Erbsenstärke und/oder deren Mischungen, Stärkeabbauprodukte, insbesondere Dextrine oder oxidierte Stärken, wie Dialdehydstärke, Stärkederivate, wie chemisch-modifizierte Stärken, insbesondere anionische Stärken, wie Carboxystärke und durch Persulfat abgebaute Stärke, anionische Stärkeester, wie z. B. Stärkephosphorsäuremono- oder -diester, Stärkeacetate und Stärkecitrate, anionische Stärkeether, wie z. B. Carboxymethylstärke, Carboxymethyl-2-hydroxyethyl-stärke oder Carboxymethyl-3-hydroxy-propyl-stärke, oder kationische Stärkederivate, wie z. B. N-haltige Stärkeether, insbesondere Stärken mit primären oder sekundären Amino- oder Iminogruppen und tertiären Aminogruppen, die durch Protonierung mit Säuren positiv geladen sind und quaternisierte Ammoniumgruppen enthalten, eingesetzt.As a starch component, native starch, such as potato starch, wheat starch, Cereal flour, corn starch, tapioca starch, sago starch and starch with increased Hydrolysis content, rice starch, pea starch and / or mixtures thereof, Starch degradation products, especially dextrins or oxidized starches, such as Dialdehyde starch, starch derivatives, such as chemically modified starches, in particular anionic starches, such as carboxy starch and starch degraded by persulfate, anionic starch esters, such as. B. starch phosphoric acid mono- or diester, Starch acetates and starch citrates, anionic starch ethers, such as. B. Carboxymethyl starch, carboxymethyl-2-hydroxyethyl starch or carboxymethyl-3-hydroxypropyl starch, or cationic starch derivatives, such as. B. N-containing Starch ethers, especially starches with primary or secondary amino or Imino groups and tertiary amino groups, which are positive by protonation with acids are charged and contain quaternized ammonium groups.

Vorzugsweise werden native Stärken wie Kartoffelstärke, Weizenstärke, Maisstärke, Reisstärke, Erbsenstärke und/oder deren Mischungen sowie anionische Stärke und/oder kationische N-haltige Stärkeether verwendet.Native starches such as potato starch, wheat starch, corn starch, Rice starch, pea starch and / or their mixtures and anionic starch and / or cationic N-containing starch ethers are used.

Als kationische Polymerisate kommen Homo- oder Copolymerisate von Dialkylaminoalkyl(meth)acrylsäureamiden zum Einsatz, die mindestens 20 Gew.% polymerisierte Einheiten von Amiden aus (Meth)acrylsäure und/oder Acrylsäure und vorzugsweise Di-C1-C2-alkylamino-C2-C6-alkylaminen enthalten, die jeweils in protonierter oder quaternisierter Form vorliegen. Ihre Herstellung ist beispielsweise in EP-A-0 013 416 oder in EP-A-0 113 038 angegeben, wobei die entsprechende Offenbarung dieser Publikationen als Referenz eingeführt wird.Cationic polymers used are homo- or copolymers of dialkylaminoalkyl (meth) acrylic acid amides which contain at least 20% by weight of polymerized units of amides of (meth) acrylic acid and / or acrylic acid and preferably di-C 1 -C 2 -alkylamino-C 2 -C 6 alkylamines contain, each in protonated or quaternized form. Their production is specified, for example, in EP-A-0 013 416 or in EP-A-0 113 038, the corresponding disclosure of these publications being introduced as a reference.

Vorzugsweise leiten sich solche polymerisierten Einheiten von protonierten oder quaternisierten N-dialkylsubstituierten (Meth)acrylsäureamiden, wie beispielsweise Dimethylaminoethyl-acrylamid oder -methacrylamid, Dimethylaminopropyl-acrylamid oder -methacrylamid, Diethylaminopropyl-acrylamid oder -methacrylamid, Diethylaminoethyl-acrylamid oder -methacrylamid, Diethylaminomethyl-acrylamid oder -methacrylamid sowie N',N',Dimethylamino-2,2-dimethylpropyl-acrylamid oder -methacrylamid oder deren Mischungen ab, die mit bekannten Quaternisierungsmitteln umgesetzt wurden. Als Quaternisierungsmittel kommen beispielsweise Dimethylsulfat, Diethylsulfat, Methylchlorid, Ethylchlorid, vorzugsweise Dimethylsulfat oder Methylchlorid in Frage.Such polymerized units are preferably derived from protonated or quaternized N-dialkyl-substituted (meth) acrylic acid amides, such as, for example Dimethylaminoethyl acrylamide or methacrylamide, dimethylaminopropyl acrylamide or methacrylamide, diethylaminopropyl acrylamide or methacrylamide, Diethylaminoethyl acrylamide or methacrylamide, diethylaminomethyl acrylamide or methacrylamide and N ', N', dimethylamino-2,2-dimethylpropyl-acrylamide or methacrylamide or mixtures thereof with known quaternizing agents have been implemented. Examples of suitable quaternizing agents are: Dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride, preferably dimethyl sulfate or methyl chloride in question.

Die Polyelektrolyte können noch weitere Einheiten von einfach ungesättigten Monomeren, wie z. B. Diallyldimethylammoniumchlorid aufweisen. Solche einpolymerisierte Monomere können auch wasserlösliche, nichtionogene Monomeren, wie Acrylamid, Methacrylamid, N-C1-C2 alkylierte (Meth)acrylamide, N-Vinylamid, Vinylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinylpyrrolidon sein. Geeignete wasserlösliche Monomere sind außerdem N-Methylolacrylamid, N-Methylol-methacrylamid sowie die mit einwertigen C1- bis C4-Alkoholen partiell oder vollständig veretherten N-Methylol(meth)acryl-amide.The polyelectrolytes can still further units of monounsaturated monomers, such as. B. diallyldimethylammonium chloride. Such copolymerized monomers can also be water-soluble, nonionic monomers, such as acrylamide, methacrylamide, NC 1 -C 2 alkylated (meth) acrylamides, N-vinylamide, vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone. Suitable water-soluble monomers are also N-methylolacrylamide, N-methylol methacrylamide and with monohydric C 1 - to C 4 -alcohols partially or fully etherified N-methylol (meth) acryl-amides.

Ebenso können die Copolymerisate in begrenztem Maße, vorzugsweise bis 10 Gew.%, in Wasser schwer lösliche und/oder wasserunlösliche, einfach ethylenisch ungesättigte Monomere, wie (Meth)acrylsäurealkylester und Vinylacetat enthalten, soweit die Löslichkeit der Copolymerisate in Wasser erhalten bleibt.Likewise, the copolymers can be used to a limited extent, preferably up to 10 % By weight, sparingly soluble and / or water-insoluble in water, simply ethylenic contain unsaturated monomers, such as (meth) acrylic acid alkyl esters and vinyl acetate, as far as the solubility of the copolymers is preserved in water.

Die erfindungsgemäß einzusetzenden Polymerisate besitzen vorzugsweise ein Molgewicht MG (g/mol) im Bereich von 1,0 x 105 bis 40 x 106, besonders bevorzugt im Bereich von 2,0 x 106 bis 15 x 106 und ganz besonders bevorzugt von 5 x 106 bis 15 x 106. The polymers to be used according to the invention preferably have a molecular weight MG (g / mol) in the range from 1.0 × 10 5 to 40 × 10 6 , particularly preferably in the range from 2.0 × 10 6 to 15 × 10 6 and very particularly preferably from 5 x 10 6 to 15 x 10 6 .

Die Viskositätsbestimmung erfolgte mit einer 1%igen Polymerlösung in einer 10%igen NaCl-Lösung mit einem Brookfield RVT-Viskosimeter, Spindel 1-3/10 Umdrehungen pro Minute bei 20°C und ergab > 10 mPas für die zum Einsatz kommenden Polymeren.The viscosity was determined using a 1% polymer solution in one 10% NaCl solution with a Brookfield RVT viscometer, spindle 1-3 / 10 Revolutions per minute at 20 ° C and resulted in> 10 mPas for use upcoming polymers.

Als partikelförmige Zusatzstoffe, die auf anorganischen Mineralstoffen basieren, d. h. auch daraus bestehen können, kommen Ton, vorzugsweise quellbar, Kieselsäure, vorzugsweise Kieselsäuresol und/oder mit Aluminium-modifizierte Polysilikate, Polyorthokieselsäure oder mit Aluminium-modifzierte Polyorthokieselsäure, Bentonit, Titandioxid oder Talkum in Frage. Vorzugsweise liegen diese Stoffe als Mikropartikel bzw. Mikrogele vor. Besonders bevorzugt wird Bentonit, Talkum, Titandioxid oder Kieselsäuresol verwendet.As particulate additives based on inorganic minerals, d. H. can also consist of clay, preferably swellable, silica, preferably silica sol and / or polysilicates modified with aluminum, Polyorthosilicic acid or modified with aluminum Polyorthosilicic acid, bentonite, titanium dioxide or talc in question. Preferably these substances are present as microparticles or microgels. Is particularly preferred Bentonite, talc, titanium dioxide or silica sol used.

Die Umsetzung der Stärkekomponente kann mit den kationischen Homo- bzw. Copolymerisaten von vorzugsweise protonierten oder quaternisierten Dialkylaminoalkyl(meth)acrylsäureamiden in wässriger Dispersion diskontinuierlich in einem Reaktionsbehälter oder in kontinuierlichem Durchflußverfahren, beispielsweise im Jet-Kocher unter Wärmeeinwirkung bei Temperaturen von 70-130 °C, vorzugsweise von 90 - 100 °C, unter Zusatz des anorganischen Zusatzstoffes und ggf. unter Druck unter Aufschluß der Stärkekomponente erfolgen. Die Reaktionsbedingungen und die geeigneten apparativen Bedingungen entsprechen den Angaben im Wochenblatt für Papier 4, 1991, S. 127 - 130, dessen Offenbarung als Referenz eingeführt wird.The starch component can be converted using the cationic homo- or Copolymers of preferably protonated or quaternized Dialkylaminoalkyl (meth) acrylic acid amides in aqueous dispersion discontinuously in a reaction vessel or in a continuous flow process, for example in the jet cooker under the influence of heat at temperatures of 70-130 ° C, preferably from 90 - 100 ° C, with the addition of the inorganic additive and if necessary, under pressure with the starch component digested. The Reaction conditions and the appropriate equipment conditions correspond the information in the weekly paper for paper 4, 1991, pp. 127-130, its disclosure is introduced as a reference.

Die Zugabe von auf anorganischen Mineralstoffen basierenden Zusatzstoffen in Mengen von 0,1 bis 15 Gew.%, vorzugsweise 3 bis 15 Gew.%, besonders bevorzugt 5 bis 13 Gew.%, bezogen auf die modifizierte Stärkekomponente, bei der Herstellung der modifizierten Stärkekomponenten vor dem Stärkeaufschluß oder während des Stärkeaufschlußes, vorzugsweise vor der modifizierenden Umsetzung und dem Aufschluß mit dem kationischen Homo- oder Copolymerisat, ergibt ein Retentionsmittel mit verbesserter Wirksamkeit im Rückhaltevermögen von Füll- und Feinstoffen. The addition of additives based on inorganic minerals in Amounts of 0.1 to 15% by weight, preferably 3 to 15% by weight, particularly preferably 5 to 13 wt.%, Based on the modified starch component, in the production the modified starch components before the starch digestion or during the Starch digestion, preferably before the modifying implementation and the Digestion with the cationic homo- or copolymer gives a Retention agent with improved effectiveness in the retention of filling and Fines.

Die wässrige Dispersion der zur Modifizierung eingesetzten, noch nicht aufgeschlossenen Stärkekomponente besitzt vorzugsweise einen Gehalt von 0,5 bis 20 Gew.%, vorzugsweise von 0,5 bis 10 Gew.% und besonders bevorzugt von 2,0 bis 10 Gew.% der Stärkekomponente. Die wässrige Lösung des zur Modifizierung verwendeten Polyelektrolyten besitzt einen Gehalt von 0,1 bis 2,0 Gew.%, vorzugsweise 0,1 bis 0,5 Gew.% und besonders bevorzugt 0,1 bis 0,3 Gew.% an kationischen Homo- oder Copolymerisaten. Das Gewichtsverhältnis von Stärkekomponente zu kationischem Polyelektrolyten liegt bei der Modifizierung im Bereich von 4:1 bis 25:1, vorzugsweise im Bereich von 10:1 bis 25:1 und besonders bevorzugt im Bereich von 14:1 bis 20:1.The aqueous dispersion of the modification used, not yet digested starch component preferably has a content of 0.5 to 20% by weight, preferably from 0.5 to 10% by weight and particularly preferably from 2.0 up to 10% by weight of the starch component. The aqueous solution for modification polyelectrolyte used has a content of 0.1 to 2.0% by weight, preferably 0.1 to 0.5% by weight and particularly preferably 0.1 to 0.3% by weight cationic homo- or copolymers. The weight ratio of Starch component to cationic polyelectrolyte lies in the modification Range from 4: 1 to 25: 1, preferably in the range from 10: 1 to 25: 1 and especially preferably in the range from 14: 1 to 20: 1.

Die modifizierten Stärkeprodukte zusammen mit den anorganischen Zusatzstoffen können, vorzugsweise in Form einer wässrigen Lösung, als Retentionsmittel bei der Herstellung von allen Papiersorten und Kartonen verwendet werden. Vorzugsweise eignen sie sich zum Einsatz bei der Herstellung von Papier auf Sulfit- oder Sulfatzellstoff im gebleichten oder ungebleichten Zustand, wobei dieses Fasermaterial bis zu 100 Gew.% aus Holzschliff und/oder Altpapier bestehen kann, und schon deshalb einen hohen Anteil an mineralischen Füllstoffen, Pigmenten und fasrigen Feinstoffen aufweist.The modified starch products together with the inorganic additives can, preferably in the form of an aqueous solution, as a retention agent in the Production of all types of paper and cardboard can be used. Preferably they are suitable for use in the manufacture of paper on sulfite or Sulphate pulp in the bleached or unbleached state, this Fiber material can consist of up to 100% by weight of ground wood and / or waste paper, and therefore a high proportion of mineral fillers, pigments and fibrous fines.

Das erfindungsgemäße Retentionsmittel wird erfindungsgemäß der wässrigen Papierstoffdispersion in einer Menge von 0,1 bis 10 Gew.% Feststoff, vorzugsweise von 0,5 bis 5 Gew.% und besonders bevorzugt 1,0 bis 3 Gew.%, bezogen auf die Trockenmasse bzw. Papierstoffmasse, vor dem Stoffauflauf der Papiermaschine, vorzugsweise als wässrige Lösung unter Rührung, zugesetzt. Der Zusatz erfolgt zu der wässrigen Dispersion, die als Füllstoffe bereits Kalziumcarbonat, Kaolin, Aluminiumsilikat und -oxidhydrate, Satinweiß, Talkum, Gips, Baryt, Kalziumsilikat und Lithopone, Kieselgur sowie synthetische, organische Füllstoffe aus dem Recyclingmaterial enthalten kann oder zugesetzt wurde.The retention aid according to the invention becomes aqueous according to the invention Pulp dispersion in an amount of 0.1 to 10 wt.% Solid, preferably from 0.5 to 5% by weight and particularly preferably 1.0 to 3% by weight, based on the Dry matter or pulp, before the headbox of the paper machine, preferably added as an aqueous solution with stirring. The addition is made to the aqueous dispersion, which already contains calcium carbonate, kaolin, Aluminum silicate and oxide hydrates, satin white, talc, gypsum, barite, calcium silicate and lithopone, diatomaceous earth and synthetic, organic fillers from the Recycled material may or may have been added.

Die Zugabe des erfindungsgemäßen Retentionsmittels erfolgt vorteilhaft zur Stoffdispersion in der Maschinenbütte, vor dem Vertikalsichter und vor oder nach der Stofflaufpumpe vor der Blattbildung. The retention agent according to the invention is advantageously added to the Dispersion of material in the machine chest, before the vertical classifier and before or after Feed pump before sheet formation.

Durch das erfindungsgemäße Retentionsmittel auf Basis von modifizierter Stärke und anorganischen Zusatzstoffen wird eine ausgezeichnete Retention der Füllstoffe erreicht und eine Beeinträchtigung der Festigkeitswerte trotz der Erhöhung des Füllstoff und damit des Aschegehaltes des Papiers überraschenderweise vermieden. Insbesondere gilt dies beim Einsatz von Papierstoffdispersionen, die Anteile von Altpapier oder Holzstoffen, wie Holzschliff und thermomechanischem Stoff (TMP) enthalten oder daraus bestehen.By means of the retention agent according to the invention based on modified starch and inorganic additives will have an excellent retention of the fillers reached and an impairment of the strength values despite the increase in Filler and thus the ash content of the paper surprisingly avoided. This applies in particular when using pulp dispersions, the proportions of Waste paper or wood materials, such as sanded wood and thermomechanical material (TMP) contain or consist of.

Es wurde auch festgestellt, daß durch die Verwendung des erfindungsgemäßen Retentionsmittels die Wirkung von optischen Aufhellern, die zur Verbesserung des Weißgrades dem Papierstoff zugesetzt werden, nicht beeinträchtigt wird. It has also been found that by using the invention Retention agent the effect of optical brighteners, which improve the Whiteness added to the paper stock is not affected.

Die Erfindung wird durch die nachfolgenden Beispiele weiter erläutert:The following examples further illustrate the invention:

Beispiele 1 bis 4:Examples 1 to 4:

  • A In einem beheizbaren Gefäß wurden 250 g einer wässrigen, 4,0 Gew.%igen Dispersion von nativer Kartoffelstärke, Produktbezeichnung C*Gel 30002, Fa. Cerestar Holding B.V., unter Rühren mit 250 g einer 0,25 Gew.%igen Lösung eines wasserlöslichen kationischen Polymerisats gemischt, mit unterschiedlichen Mengen Bentonit bzw. unter Zusatz von Talkum versehen und auf eine Temperatur von 95 bis 100°C erhitzt. In Vergleichsbeispiel 1 wurde kein Mineralstoff zugesetzt. Die Mischung wurde 15 bis 20 Minuten in diesem Temperaturbereich gehalten, danach abgekühlt und als Retentionsmittel verwendet. Als wasserlösliche kationische Polymerisate wurden Copolymerisate aus Trimethylammoniumpropylacrylamid-chlorid und Acrylamid mit einem Anteil des quatemisierten Monomeren von 70 Gew.% eingesetzt.A 250 g of an aqueous 4.0% by weight solution were placed in a heatable vessel Dispersion of native potato starch, product name C * Gel 30002, Fa. Cerestar Holding B.V., with stirring, with 250 g of a 0.25% by weight solution of a water-soluble cationic polymer mixed with different amounts of bentonite or with the addition of talc and heated to a temperature of 95 to 100 ° C. In Comparative Example 1 no mineral was added. The mixture was in for 15 to 20 minutes kept in this temperature range, then cooled and as Retention agent used. As water-soluble cationic polymers were copolymers of trimethylammonium propylacrylamide chloride and Acrylamide with a quaternized monomer content of 70% by weight used.
  • B Eine 4,0 Gew.%ige Stoffsuspension aus 100 Gew.% Altpapierstoff wurde nach dem Verdünnen mit Wasser auf einen Gehalt von 1 Gew.% unter Rühren mit dem nach A hergestellten Retentionsmittel versetzt, das in einer Menge von 2,125 Gew.% Feststoff, bezogen auf den Trockengehalt der Stoffsuspension, zugesetzt wurde.B A 4.0% by weight stock suspension made from 100% by weight waste paper stock was used dilution with water to a content of 1% by weight with stirring added to the retention aid prepared according to A, in an amount of 2.125% by weight solids, based on the dry content of the stock suspension, was added.
  • C Mit der nach B erhaltenen Stoffsuspension wurde im Labor nach dem Rapid-Köthen-Verfahren gemäß DIN 54358 mit dem Blattbildungsgerät Modell 20-12 MC der Fa. Haage Prüfblätter mit einem Flächengewicht von ca. 100 g/m2 hergestellt. Die Blätter wurden getrocknet und über Nacht unter Normalbedingungen bei 23°C und 50 % rel. Luftfeuchtigkeit gelagert.C With the stock suspension obtained according to B, test sheets with a basis weight of approx. 100 g / m 2 were produced in the laboratory according to the Rapid Koethen method according to DIN 54358 with the sheet forming device model 20-12 MC from Haage. The leaves were dried and overnight under normal conditions at 23 ° C and 50% rel. Humidity stored.

    • Nach dem Auswiegen der Papiere wurden Flächengewicht, Aschegehalt nach DIN 54373 und Berstdruck nach DIN 63141 bestimmt.After the papers had been weighed out, basis weight and ash content were reduced DIN 54373 and burst pressure determined according to DIN 63141.

    Die Gesamtretention gibt das Verhältnis der zur Papierherstellung eingesetzten trockenen Stoffmenge zu der im fertigen Papier verbliebenen Stoffmenge wieder. Dies ist durch Auswiegen der jeweiligen Stoffmengen bestimmbar.The total retention gives the relationship to the paper production amount of dry substance used to the remaining in the finished paper Amount of substance again. This is done by weighing the respective amounts of substance determinable.

    Die Ascheretention gibt das Verhältnis der Aschegehaltes der zur Papierherstellung eingesetzten (trockenen) Stoffmenge zu dem Aschegehalt des fertigen Papiers wieder. Dies wird durch Bestimmung des jeweiligen Aschegehaltes ermittelt.The ash retention gives the ratio of the ash content to the Paper production used (dry) amount of substance to the ash content of the finished paper again. This is determined by determining each Ash content determined.

    Die Feinstoffretention gibt das Verhältnis von Feinstoffanteil der zur Papierherstellung eingesetzten (trockenen) Stoffmenge zu dem Feinstoffanteil des fertigen Papiers wieder.The retention of fines indicates the ratio of the fines content to the Paper production used (dry) amount of substance to the proportion of fines of the finished paper again.

    Die entsprechenden Feinstoffanteile werden mit Hilfe eines Britt Dynamic Drainage Jar wie folgt bestimmt:The appropriate proportion of fines is determined using a Britt Dynamic Drainage Jar determined as follows:

    Eine wässrige Papierstoff-Suspension mit 0,5 g trockenen Papierstoff, aus der das Papier erzeugt wird, (StWG) wird auf ca. 1 Gew.% mit Leitungswasser verdünnt. Diese Suspension wird bei 750 UpM einige Sekunden gerührt, danach unter Rühren entwässert. Der Rückstand wird erneut mit 500 ml Wasser versetzt, gerührt und entwässert. Der Vorgang wird 4-5 mal wiederholt, bis das Filtrat völlig klar ist, d. h. es können keine feinen Fasern mehr ausgewaschen werden. Der Rückstand auf dem Sieb wird über einen tarierten Filter gegeben und gravimetrisch bestimmt (Trocknung bei 110°C). Berechnung des Feinanteils: Feinanteil = 100 - Grobanteil (%) An aqueous paper stock suspension with 0.5 g dry paper stock, from which the paper is made, (StWG) is diluted to approx. 1% by weight with tap water. This suspension is stirred at 750 rpm for a few seconds, then dewatered with stirring. The residue is mixed again with 500 ml of water, stirred and drained. The process is repeated 4-5 times until the filtrate is completely clear, ie fine fibers can no longer be washed out. The residue on the sieve is passed through a tared filter and determined gravimetrically (drying at 110 ° C.). Calculation of the fine fraction: fine fraction = 100 - coarse fraction (%)

    Der Grobanteil entspricht der Fasermenge, die auf dem Filter ist. Feinanteil = 100 - Grobanteil in g 0,5 g x 0,01 (%) The coarse fraction corresponds to the amount of fiber that is on the filter. Fine fraction = 100 - Coarse fraction in g 0.5 gx 0.01 (%)

    Die entsprechenden Werte aus dem Vergleichsbeispiel 1 bzw den Beispielen 1 bis 4 sind in Tabelle 1 angegeben. Vergleichsbeispiel
    1/
    Beispiele 1 bis 4     Ascheretention Gew.% Gesamtretention Gew.% Berstdruck kPa     mod. Stärke ohne Mineralstoffzusatz 93,3 89,1 95 mod. Stärke 9,7 Bentonit 0,3 95,3 90,7 104 mod. Stärke 9,5 Bentonit 0,5 95,2 92,1 106 mod. Stärke 9,0 Bentonit 1,0 97,6 96,7 92 mod. Stärke 9,0 Talkum 1,0 95,3 94,0 -     The corresponding values from Comparative Example 1 or Examples 1 to 4 are given in Table 1. Comparative example
    1/
    Examples 1 to 4     Ash retention% by weight Total retention% by weight Burst pressure kPa     mod. Starch without added minerals 93.3 89.1 95 mod. Starch 9.7 bentonite 0.3 95.3 90.7 104 mod. Strength 9.5 bentonite 0.5 95.2 92.1 106 mod. Starch 9.0 bentonite 1.0 97.6 96.7 92 mod. Starch 9.0 talc 1.0 95.3 94.0 -

    Vergleichsbeispiel 2Comparative Example 2

    Die Arbeitsweisen A, B und C der Beispiele 1 bis 4 wurden beibehalten, jedoch wurde das in A der Beispiele 1 bis 4 genannte kationische Polymerisat als solches als Retentionshilfsmittel bei der Blattbildung getestet.The procedures A, B and C of Examples 1 to 4 were retained, however was the cationic polymer mentioned in A of Examples 1 to 4 as such tested as a retention aid in leaf formation.

    Die entsprechenden Werte sind in Tabelle 2 angegeben. Vergleichs-Beispiel kation. Anteil im Copolymerisat Gew.% Ascheretention Gew.% Gesamtretention Gew.% Berstdruck kPa 2 70 0 44,8 60 The corresponding values are given in Table 2. Comparative Example cation. Proportion in the copolymer% by weight Ash retention% by weight Total retention% by weight Burst pressure kPa 2 70 0 44.8 60

    Claims (16)

    1. Use of modified starch as retention agent for pigments, inorganic fillers and fines in paper manufacturing, said modified starch being obtained by pulping starch, starch derivatives and/or degradation products thereof in aqueous solution and in the presence of at least one cationic polymer constituted of at least 20 wt.-% of polymerized dialkylaminoalkyl(meth)acrylic acid amide moieties and with addition of at least one particulate additive prior to or during pulping which is based on an inorganic mineral substance.
    2. The use according to claim 1, characterized in that protonated or quaternized di(C1-C2)alkylamino(C2-C6)alkyl(meth)acrylamide moieties are present as dialkylaminoalkyl(meth)acrylic acid amide moieties.
    3. The use according to claim 1 or 2, characterized in that quaternized moieties of dimethylaminoethylacrylamide or -methacrylamide, diethylaminopropylacrylamide or -methacrylamide, diethylaminoethylacrylamide or -methacrylamide, diethylaminomethylacrylamide or -methacrylamide, dimethylaminopropylacrylamide or -methacrylamide, dimethylaminomethylacrylamide or -methacrylamide, N,N-dimethylamino-2,2-dimethylpropylacrylamide or -methacrylamide or mixtures thereof are present as quaternized di(C1-C2)-alkylamino(C2-C6)alkyl(meth)acrylamide moieties.
    4. The use according to claim 3, characterized in that the moieties have been reacted with dimethyl sulfate or methyl chloride as quaternizing compounds.
    5. The use according to one or more of claims 1 to 4, characterized in that trimethylammoniumpropylacrylamide chloride moieties are present as quaternized dialkylaminoalkylacrylic acid amide moieties.
    6. The use according to one or more of claims 1 to 5, characterized in that the cationic polymers include additional polymerized moieties of water-soluble, unsaturated monomers, preferably of α,β-unsaturated amides, N-vinyl-amides, N-hydroxyalkylamides optionally etherified partially or completely, N-vinylpyrrolidone and/or dialkyldimethylammonium chloride.
    7. The use according to claim 6, characterized in that the amide moieties are derived from acrylamide or methacrylamide, preferably from acrylamide.
    8. The use according to one or more of claims 1 to 7, characterized in that the cationic polymers include up to 10 wt.-% of moieties of α,β-unsaturated monomers sparingly soluble or insoluble in water, preferably of (meth)acrylic acid alkyl ester or vinyl acetate.
    9. The use according to one or more of claims 1 to 8, characterized in that the cationic polymer has a molecular weight m.w. (g/mol) of from 0.1 to 20 millions.
    10. The use according to one or more of claims 1 to 9, characterized in that native starches, preferably potato starch, cereal flour, wheat starch, corn starch, rice starch, pea starch, and/or mixtures thereof, anionic starches, preferably starch mono- or diphosphates, anionic starch ethers, preferably carboxymethylstarch, or cationic starch derivatives, preferably N-containing starch ethers, are used as starch.
    11. The use according to one or more of claims 1 to 10, characterized in that the starch component is pulped in the presence of microparticles or microgels of at least one additive based on an inorganic mineral substance, preferably clay, silica sol, silica optionally modified with aluminum, polysilicates optionally modified with aluminum, or polyorthosilicic acid, bentonite, titanium dioxide, or talc.
    12. The use according to one or more of claims 1 to 11, characterized in that the inorganic additive is employed in amounts of from 0.1 to 15 wt.-%, preferably from 3 to 15 wt.-%, relative to the modified starch component.
    13. The use according to one or more of claims 1 to 12, characterized in that the weight ratio of starch component to cationic homo- or copolymer ranges from 4:1 to 25:1, preferably from 10:1 to 25:1, more preferably from 14:1 to 20:1 when performing the modification.
    14. The use according to one or more of claims 1 to 13, characterized in that the starch component has been pulped at temperatures of from 70 to 150° C, preferably from 90 to 100°C.
    15. The use according to one or more of claims 1 to 14, characterized in that the retention agent is added in amounts of from 0.1 to 10 wt.-%, preferably from 0.5 to 5 wt.-% solids, relative to the paper pulp.
    16. The use according to one or more of claims 1 to 15, characterized in that waste paper is used in paper manufacturing.
    EP99938266A 1998-07-17 1999-07-15 The use of modified starch products as retention agents in the production of paper Expired - Lifetime EP1102894B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19832241A DE19832241A1 (en) 1998-07-17 1998-07-17 Modified starch used as retention aid in paper production, obtained by digesting starch material in water in presence of a cationic polymer based on dialkylaminoalkylacrylamide and a particulate mineral additive
    DE19832241 1998-07-17
    PCT/EP1999/005054 WO2000004229A1 (en) 1998-07-17 1999-07-15 The use of modified starch products as retention agents in the production of paper

    Publications (2)

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    EP1102894A1 EP1102894A1 (en) 2001-05-30
    EP1102894B1 true EP1102894B1 (en) 2002-10-23

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    CN (1) CN1309737A (en)
    AT (1) ATE226663T1 (en)
    AU (1) AU5283599A (en)
    BR (1) BR9912832A (en)
    CA (1) CA2336660A1 (en)
    DE (2) DE19832241A1 (en)
    NO (1) NO20010286D0 (en)
    WO (1) WO2000004229A1 (en)

    Families Citing this family (8)

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    EP1176254A1 (en) 2000-07-24 2002-01-30 The Dow Chemical Company Use of dispersions of crosslinked cationic starch in papermaking
    DE10121418A1 (en) * 2001-05-02 2003-01-23 Stockhausen Chem Fab Gmbh Process for the production of molded fiber articles
    JP4712322B2 (en) * 2004-06-30 2011-06-29 日本製紙株式会社 Printability improver and paper coated with the same
    CN100572434C (en) * 2007-06-05 2009-12-23 内江市春江纸业有限公司 A kind of preparation method of modified starch composition
    CN102852038A (en) * 2012-09-24 2013-01-02 济南晨光纸业有限公司 Method for improving vividness of colorized parchment and effectively preventing fading
    CN105964887A (en) * 2016-06-22 2016-09-28 马鞍山市创诚铸造有限公司 High-breathability moulding sand using thermoplastic oxidized-starch modified gelatin as adhesive and preparation method thereof
    CN107217528B (en) * 2017-06-21 2018-06-29 合肥龙发包装有限公司 A kind of oil resistant fat foods wrapping paper
    CN115818655B (en) * 2022-11-01 2024-03-26 江西广源化工有限责任公司 Flaky talcum powder and preparation method thereof and application of flaky talcum powder in preparation of laminating base paper

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    US4097427A (en) * 1977-02-14 1978-06-27 Nalco Chemical Company Cationization of starch utilizing alkali metal hydroxide, cationic water-soluble polymer and oxidant for improved wet end strength
    FR2396831A1 (en) * 1977-07-04 1979-02-02 Scholten Honig Research Nv Paper and cardboard prodn. using filler - coated with quat. cationic starch-ether, giving improved pulp filler retention
    SE432951B (en) * 1980-05-28 1984-04-30 Eka Ab PAPER PRODUCT CONTAINING CELLULOSA FIBERS AND A BINDING SYSTEM CONTAINING COLOIDAL MILIC ACID AND COTIONIC STARCH AND PROCEDURE FOR PREPARING THE PAPER PRODUCT
    GB8602121D0 (en) * 1986-01-29 1986-03-05 Allied Colloids Ltd Paper & paper board
    US5185206A (en) * 1988-09-16 1993-02-09 E. I. Du Pont De Nemours And Company Polysilicate microgels as retention/drainage aids in papermaking
    SE8903752D0 (en) * 1989-11-09 1989-11-09 Eka Nobel Ab PROCEDURES FOR PREPARING PAPER
    GB9123683D0 (en) * 1991-11-07 1992-01-02 Sandoz Ltd Improvements in or relating to organic compounds
    DE4438708A1 (en) * 1994-10-29 1996-05-02 Basf Ag Process for the cationic modification of starch and use of the cationically modified starch
    JPH09291103A (en) * 1996-04-25 1997-11-11 Sanwa Kosan Kk Papermaking starch
    DE19701523A1 (en) * 1997-01-17 1998-07-23 Basf Ag Polymer modified anionic starch, process for its preparation and its use
    DE19701524A1 (en) * 1997-01-17 1998-07-23 Basf Ag Polymer modified starch, process for its preparation and its use
    US5859128A (en) * 1997-10-30 1999-01-12 E. I. Du Pont De Nemours And Company Modified cationic starch composition for removing particles from aqueous dispersions

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    AU5283599A (en) 2000-02-07
    DE59903194D1 (en) 2002-11-28
    BR9912832A (en) 2001-05-02
    JP2002520510A (en) 2002-07-09
    CN1309737A (en) 2001-08-22
    ATE226663T1 (en) 2002-11-15
    CA2336660A1 (en) 2000-01-27
    DE19832241A1 (en) 2000-01-27
    EP1102894A1 (en) 2001-05-30
    NO20010286L (en) 2001-01-17
    NO20010286D0 (en) 2001-01-17

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