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EP1792010A1 - Method for the production of paper, paperboard and cardboard - Google Patents

Method for the production of paper, paperboard and cardboard

Info

Publication number
EP1792010A1
EP1792010A1 EP05783030A EP05783030A EP1792010A1 EP 1792010 A1 EP1792010 A1 EP 1792010A1 EP 05783030 A EP05783030 A EP 05783030A EP 05783030 A EP05783030 A EP 05783030A EP 1792010 A1 EP1792010 A1 EP 1792010A1
Authority
EP
European Patent Office
Prior art keywords
cationic
paper
million
weight
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05783030A
Other languages
German (de)
French (fr)
Other versions
EP1792010B1 (en
Inventor
Marc Leduc
Rainer Blum
Peter Leifert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1792010A1 publication Critical patent/EP1792010A1/en
Application granted granted Critical
Publication of EP1792010B1 publication Critical patent/EP1792010B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • D21H17/33—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
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765—Addition of all compounds to the pulp

Definitions

  • the invention relates to a process for the production of paper, paperboard and cardboard by dewatering a paper stock on a wire in the presence of at least one polymer as a retention agent with sheet formation and drying of the sheets.
  • US Pat. No. 4,421,602 discloses the use of partially hydrolyzed homopolymers of N-vinylformamide as retention, drainage and flocculation agents in the production of paper.
  • the K value of the hydrolyzed poly mers of N-vinylformamide is at most 150 (measured in 5% aqueous sodium chloride solution at a polymer concentration of 0.5 wt .-% and a temperature of 25 0 C) corresponding to a molecular weight M w of approx 900,000.
  • retention aids are, for example, polyamidoamines obtainable by condensation of adipic acid and diethylenetriamine, grafting of the condensation products with ethyleneimine and crosslinking of the reaction products thus obtainable with bischlorohydrin ethers of polyethylene glycols, high molecular weight polyethyleneimines, high molecular weight polyacrylamides and copolymers of acrylamide and dimethylaminoethyl acrylate -methochloride having a molecular weight M w of at least 3 Millio ⁇ NEN, see. Examples of EP-A 438 707.
  • the deposition of contaminants in the paper machine is e.g. on metallic surfaces, screening and felts by adding to the stock a water-soluble copolymer containing at least 5% by mole of an N-vinylcarboxamide or a hydrolyzate thereof.
  • the degree of hydrolysis of the N-vinylcarboxamides is, according to the information in the examples, from 5 to 20 mol%.
  • the retention agents used are various combinations of polymers and a finely divided, inorganic solid, such as bentonite, which acts as flocculant. nit, colloidal silica or silica.
  • bentonite a finely divided, inorganic solid
  • nit colloidal silica or silica.
  • a paper material initially a synthetic cationic African polymer having a molecular weight of more than 500,000 in an amount of more than 0.03 wt .-%, based on dry pulp, to form flakes zu ⁇ set, which are then cut in a subsequent shearing step to microflakes. Then bentonite is then added and the resulting paper pulp is dewatered under Blattbil ⁇ .
  • the pulp is successively mixed with two different water-soluble, cationic polymers, namely a fixing agent and a retention agent, then subjected to at least one shear stage and then treated with bentonite. Only then is the drainage of the pulp under sheet formation.
  • EP-A 910 701 describes a process for the production of paper and board, wherein a low molecular weight or medium molecular weight cationic polymer based on polyethylenimine or polyvinylamine and subsequently with a high molecular weight cationic polymer, such as polyacrylamide, polythiol, is successively added to the paper pulp vinylamine or cationic starch. After this pulp has been subjected to at least one shear stage, it is flocculated by addition of bentonite and the pulp is dewatered.
  • a low molecular weight or medium molecular weight cationic polymer based on polyethylenimine or polyvinylamine and subsequently with a high molecular weight cationic polymer, such as polyacrylamide, polythiol
  • EP-A 608 986 It is known from EP-A 608 986 that a cationic retention agent is metered into the thick stock in papermaking.
  • a further process for the production of paper and paperboard is known from US Pat. No. 5,393,381, WO 99/66130 and WO 99/63159, which also teaches a microparticle system composed of a cationic polymer and bentonite used.
  • the cationic polymer used is a water-soluble, branched polyacrylamide.
  • WO 01/34910 describes a process for the production of paper in which a polysaccharide or a synthetic, high molecular weight polymer is metered into the paper stock suspension. Subsequently, a mechanical shear of the pulp must take place. The reflocculation is carried out by dosing an inorganic component such as silica, bentonite or clay and a water-soluble polymer.
  • an inorganic component such as silica, bentonite or clay and a water-soluble polymer.
  • US Pat. No. 6,103,065 discloses a process for improving the retention and the removal of debris from paper materials, in which a cationic polymer having a molecular weight of 100,000 to 2 million and a charge density of more than 4 is added to a paper stock after the last shearing , 0 meq./g, simultaneously or after adding a polymer having a molecular weight of at least 2 million and a charge density of less than 4.0 meq./g and then dosed bentonite. It is not necessary in this method to shear the stock after the addition of the polymers. After addition of the polymers and the bentonite, the pulp can be dewatered without further action of shear forces to form sheets.
  • WO 04/15200 likewise discloses a microparticle system comprising a cationic polymer and a finely divided inorganic component as retention agent in the production of paper.
  • Suitable cationic polymers are, for example, cationic polyacrylamides, polymers comprising vinylamine units and / or polydiallyldimethylammonium chloride having an average molecular weight M w of at least 500 000 and a charge density of at most 4.0 meq / g.
  • microparticle systems described above are technically complicated because special devices are required for the metering of the finely divided inorganic flocculants.
  • the object is achieved in accordance with the invention by a process for the production of paper, paperboard and paperboard by dewatering a paper stock on a wire in the presence of at least one polymer as a retention agent with formation of sheets and drying of the sheets, if the sheet formation is in the absence of finely divided inorganic Flocculants and as a retention agent (a) polymers containing vinylamine units and / or polyvinylformamide having a molecular weight M w of at least 1 million each
  • Vinylamine-containing polymers and / or polyvinylformamide having a molar mass M w of at least 1 million are known. They are prepared, for example, by homopolymerization of N-vinylformamide to poly-N-vinylformamide or by copolymerizing N-vinylformamide with at least one other ethylenically unsaturated monomer and subsequent hydrolysis of the copolymerized vinylformamide units to vinylamine units.
  • Preferred polymers containing vinylamine units are the cationic polymers obtainable by hydrolysis of poly-N-vinylformamides. The degree of hydrolysis of these polymers is for example 0.5 to 100%, preferably 1 to 50% and is usually in the range of 2 to 40, in particular from 2 to 30%.
  • the polymers of component (a) have for example a charge density (determined at pH 7) of 0 to 18 meq / g, preferably 0.1 to 7 meq / g and in particular from 0.2 to 4 meq / g.
  • a charge density determined at pH 7
  • the vinylamine units containing polymers and poly-N-vinylformamide the
  • Component (a) of the retention agent preferably has a molecular weight M w of at least 1.2 million.
  • M w molecular weight of at least 1.2 million.
  • Component (a) can be either a vinylamine units-containing polymer or poly-N-vinylformamide alone or a mixture of polymers from the two classes of compounds. However, preference is given to polymers containing cationic vinylamine units as compounds of component (a).
  • cationic polyacrylamides As component (b) of the retention agent system, cationic polyacrylamides, nonionic polyacrylamides, cationic polymethacrylamides, nonionic polymethacrylamides and mixtures of the compounds mentioned come into consideration, if they each have a molecular weight M w of at least 3 million.
  • Polymers of this type are described in the prior art EP-A 335 575.
  • such polymers are commercially available products. They are known to be prepared by polymerizing acrylamide or methacrylamide each alone to homopolymers or by polymerizing acrylamide or methacrylamide in the presence of cationic monomers.
  • Suitable cationic monomers are, for example, the esters and amides of ethylenically unsaturated C 3 - to C 5 -carboxylic acids with amino alcohols.
  • Examples of cationic monomers are dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminoethylacrylamide, diethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminopropyl
  • the cationic monomers can be used in the copolymerization in the form of the free bases, the salts with mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid, benzenesulfonic acid or p-toluenesulfonic acid and / or in quaternized Form are used.
  • Quatem istsstoff come for example Cr to C
  • the cationic polyacrylamides or the cationic polymethacrylamides contain, for example, copolymerized 5 to 40 mol%, preferably 7 to 30 mol% of at least one cationic monomer.
  • the molecular weights of the cationic polymers and those of the nonionic polymers are at least 2.5 million, preferably at least 3 million, and are usually in the range of 5 million to 15 million.
  • Hydrolysis degree of vinylformamide units is 0.5 to 100%
  • the retention agent contains in particular as a component
  • the cationic polyacrylamides and the cationic polymethacrylamides preferably contain copolymerized as cationic monomer dimethylaminoethyl acrylate methochloride or dimethylaminoethylacrylamide methochloride. These methochlorides are readily accessible by alkylation of dimethylaminoethyl acrylate or of dimethylaminoethyl acrylamide with methyl chloride.
  • the components (a) and (b) of the retention agent are added to the paper stock, based on dry paper stock, in an amount of
  • the retention agent may be added to the paper stock - as a rule the metering of the retention agent is carried out according to the invention in the thin material - for example in the form of a mixture of components (a) and (b).
  • the component (a) and then the component (b) first, for example, after the last shear stage in front of the headbox.
  • both components can also be introduced into the thin material separately from one another before or after a shear stage.
  • At least one compound of component (a) is first metered, followed by at least one compound. fertil the component (b).
  • the compound of component (a) can be supplied to the paper stock before the headbox example before a shear stage and the compound of component (b) after the last shear stage before the headbox.
  • both Verbindun ⁇ conditions can be dosed before the last shear stage before the headbox or after the last stage before the headbox for pulp.
  • a cationic polyacrylamide is preferably used as the compound of component (b), while if component (a) is selected as a vinylamine polymer-containing polymer, the use of a cationic polyacrylamide or a cationic one is preferred Polymethyacrylamids preferred, but then you can also as component (b) a nonionic polyacrylamide and / or a nonionic Polymethacrylamid einset ⁇ zen.
  • the invention is also the use of combinations of
  • all paper grades, paperboard and cardboard can be produced, for example papers for newspaper printing, so-called medium-fine writing and printing papers, natural gravure papers and also lightweight coating base papers.
  • wood pulp, thermo-mechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure pulp (PGW) and sulphite and sulphate pulp can be used.
  • TMP thermo-mechanical pulp
  • CMP chemo-thermo-mechanical pulp
  • PGW pressure pulp
  • sulphite and sulphate pulp can be used.
  • Pulp and zeolite are mainly used in the so-called integrated paper mills in more or less less moist form directly without prior thickening or drying further processed into paper. Due to the impurities not completely removed from them, these fiber materials still contain substances which severely disturb the usual papermaking process. If such pulps are used, it is advisable to work in the presence of a fixative.
  • both unfilled and filler-containing papers can be produced.
  • the filler content in the paper can be up to a maximum of 40% by weight and is preferably in the range from 5 to 30% by weight.
  • Suitable fillers are, for example, clay, kaolin, native and precipitated circles, titanium dioxide, talc, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the stated fillers.
  • the papermaking can be carried out in the presence of the usual process chemicals in the usual amounts, e.g. of engine sizing agents such as, in particular, alkyldiketene dispersions, rosin size, alkenylsuccinimide dispersions or adhesive polymer dispersions, solidifying agents such as polyamidoamines crosslinked with epichlorohydrin, polyvinylamines of average molecular weight or strength, fixing agents, biocides, dyes and fillers.
  • engine sizing agents such as, in particular, alkyldiketene dispersions, rosin size, alkenylsuccinimide dispersions or adhesive polymer dispersions, solidifying agents such as polyamidoamines crosslinked with epichlorohydrin, polyvinylamines of average molecular weight or strength, fixing agents, biocides, dyes and fillers.
  • engine sizing agents such as, in particular, alkyldiketene dispersions, rosin size, alkenyls
  • the process of the invention gives, compared to the products which are prepared by known processes, papers having an improved formation, an improved filler distribution, a better opacity and an improved printability.
  • the process according to the invention is simpler to carry out than the microparticle processes and results in improved filler retention and formation compared with the prior art.
  • the percentages for the starting materials always mean weight percent.
  • the molar masses Mw of the polymers were determined by means of the static light scattering.
  • the drainage time was determined by dewatering a sample of the stock in a Schopper-Riegler tester and determining the time in seconds within the 300 ml of filtrate.
  • Ash retention was determined by calculating the difference between the ash concentration of the paper stock in the headbox and the ash concentration in the white water divided by the ash concentration of the paper stock in the headbox and multiplying by 100. It is reported as a percentage.
  • Formation evaluation on-line formation index was performed by measuring the sheets to be tested using Measure IT Optical Properties Measurement OP 4255 (formation sensor from ABB). The lower the measured value, the better the formation.
  • PVAm 1 polyvinylamine with a molecular weight M w of 1.2 million and a charge density of 3.0 meq / g
  • PAM 1 copolymer of 70% by weight of acrylamide and 30% by weight of dimethylaminoethyl acrylate methochloride having a molecular weight M w of 8 million and a charge density of 1.7 meq / g
  • the bentonite used had been activated with aqueous sodium carbonate solution.
  • Example 1 and Comparative Examples 1 dehydrated to 3 specified Zu ⁇ additives.
  • the solids content of the white water was always 0.55%.
  • the filler content of the paper was 30%.
  • the paper had a basis weight of 52-56 g / m 2 .
  • PAM 1 was metered after the last shear stage and before the headbox.
  • the drainage time of this stock was 41 seconds, the ash retention 36% and the index for the formation 7.4.
  • PVAm 1 0.05% PVAm 1 was metered to the stock described above after the last shear stage in front of the headbox.
  • the drainage time of this stock was 38 seconds, the ash retention 39% and the index for the formation 6.4.

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  • Paper (AREA)

Abstract

The invention relates to a method for the production of paper, paperboard and cardboard by dripping a paper material onto a sieve, by forming sheets and then drying the sheets. The sheets are formed in the absence of fine-particled, inorganic, flocculating agents and the retention agent is used as (a) polymers containing vinylamine units and/or polyvinylformamide having a molar mass M<SUB>w</SUB> of, respectively, at least 1 million and (b) at least one cationic or non-ionic polyacrylamide and/or a cationic or non-ionic polymethacrylamide having a molar mass M<SUB>w</SUB> of, respectively, at least 2.5 million.

Description

Verfahren zur Herstellung von Papier, Pappe und Karton Process for the production of paper, cardboard and cardboard
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Papierstoffs auf einem Sieb in Gegenwart mindestens eines Polymeren als Retentionsmittel unter Blattbildung und Trocknen der Blätter.The invention relates to a process for the production of paper, paperboard and cardboard by dewatering a paper stock on a wire in the presence of at least one polymer as a retention agent with sheet formation and drying of the sheets.
Aus der US-A 4,421,602 ist die Verwendung von partiell hydrolysierten Homopolymeri- säten des N-Vinylformamids als Retentions-, Entwässerungs- und Flockungsmittel bei der Herstellung von Papier bekannt.US Pat. No. 4,421,602 discloses the use of partially hydrolyzed homopolymers of N-vinylformamide as retention, drainage and flocculation agents in the production of paper.
Außerdem ist es bekannt, bei der Herstellung von Papier aus Störstoffe enthaltenden Papierstoffen Fixiermittel zu verwenden, vgl. Tappi Journal, August 1988, Seiten 131 - 134. Bekannte Fixiermittel sind beispielsweise Kondensate aus Dicyandiamid und Formaldehyd oder Kondensate aus Dimethylamin und Epichlorhydrin. Aus der EP-A 438 707 ist weiterhin bekannt, hydrolysierte Homo- und/oder Copolymerisate des N-Vinylformamids mit einem Hydrolysegrad von mindestens 60 % als Fixiermittel bei der Herstellung von Papier zu verwenden. Sie können auch in Kombination mit einem kationischen Retentionsmittel eingesetzt werden. Der K-Wert der hydrolysierten Poly¬ meren des N-Vinylformamids beträgt höchstens 150 (gemessen in 5 %iger wässriger Kochsalzlösung bei einer Polymerkonzentration von 0,5 Gew.-% und einer Temperatur von 250C) entsprechend einer Molmasse Mw von ca. 900 000.It is also known to use in the production of paper from contaminants containing pulps fixer, cf. Tappi Journal, August 1988, pages 131-134. Known fixing agents are, for example, condensates of dicyandiamide and formaldehyde or condensates of dimethylamine and epichlorohydrin. From EP-A 438 707 it is also known to use hydrolyzed homopolymers and / or copolymers of N-vinylformamide having a degree of hydrolysis of at least 60% as a fixing agent in the production of paper. They can also be used in combination with a cationic retention agent. The K value of the hydrolyzed poly mers of N-vinylformamide is at most 150 (measured in 5% aqueous sodium chloride solution at a polymer concentration of 0.5 wt .-% and a temperature of 25 0 C) corresponding to a molecular weight M w of approx 900,000.
Weitere bekannte Retentionsmittel sind beispielsweise Polyamidoamine, die durch Kondensation von Adipinsäure und Diethylentriamin, Pfropfen der Kondensationspro¬ dukte mit Ethylenimin und Vernetzen der so erhältlichen Reaktionsprodukte mit Bischlorhydrinethem von Polyethylenglykolen erhältlich sind, hochmolekulare Polyethy- lenimine, hochmolekulare Polyacrylamide und Copolymerisate aus Acrylamid und Di- methylaminoethylacrylat-methochlorid mit einer Molmasse Mw von mindestens 3 Millio¬ nen, vgl. Beispiele der EP-A 438 707.Further known retention aids are, for example, polyamidoamines obtainable by condensation of adipic acid and diethylenetriamine, grafting of the condensation products with ethyleneimine and crosslinking of the reaction products thus obtainable with bischlorohydrin ethers of polyethylene glycols, high molecular weight polyethyleneimines, high molecular weight polyacrylamides and copolymers of acrylamide and dimethylaminoethyl acrylate -methochloride having a molecular weight M w of at least 3 Millio¬ NEN, see. Examples of EP-A 438 707.
Gemäß der Lehre der EP-A 649 941 wird die Ablagerung von Störstoffen in der Pa¬ piermaschine z.B. auf metallischen Oberflächen, Sieben und Filzen dadurch reduziert, dass man zum Papierstoff ein wasserlösliches Copolymerisat zusetzt, das mindestens 5 Moi-% eines N-Vinylcarbonsäureamids oder eines Hydrolysates davon enthält. Der Hydrolysegrad der N-Vinylcarbonsäureamide beträgt nach den Angaben in den Bei¬ spielen 5 bis 20 Mol-%.According to the teaching of EP-A 649 941, the deposition of contaminants in the paper machine is e.g. on metallic surfaces, screening and felts by adding to the stock a water-soluble copolymer containing at least 5% by mole of an N-vinylcarboxamide or a hydrolyzate thereof. The degree of hydrolysis of the N-vinylcarboxamides is, according to the information in the examples, from 5 to 20 mol%.
Außerdem sind als Retentionsmittel verschiedene Kombinationen aus Polymeren und einem als Flockungsmittel wirkenden, feinteiligen, anorganischen Feststoff wie Bento- nit, kolloidale Kieselsäure oder Silica bekannt. So wird beispielsweise in Wochenblatt für Papierfabrikation, Band 13, 493-592 (1979) die Verwendung von kationischen PoIy- elektrolyten in Kombination mit Bentonit beschrieben. Bei diesem Verfahren dosiert man zunächst Bentonit zum Papierstoff und anschließend den kationischen Polyelekt- rolyten, wobei der Papierstoff gegebenenfalls einem Schergefälle unterworfen werden kann.In addition, the retention agents used are various combinations of polymers and a finely divided, inorganic solid, such as bentonite, which acts as flocculant. nit, colloidal silica or silica. Thus, for example, Wochenblatt für Papierfabrikation, Vol. 13, 493-592 (1979) describes the use of cationic polyelectrolytes in combination with bentonite. In this process, first of all bentonite is metered into the paper stock and then the cationic polyelectrolyte, wherein the paper stock can optionally be subjected to a shear rate.
Aus der EP-B 235 893 ist bekannt, einem Papierstoff zunächst ein synthetisches katio¬ nisches Polymer mit einer Molmasse von mehr als 500 000 in einer Menge von mehr als 0,03 Gew.-%, bezogen auf trockenen Papierstoff, unter Bildung von Flocken zuzu¬ setzen, die dann in einem anschließenden Scherschritt zu Mikroflocken zerteilt werden. Danach wird dann Bentonit zugegeben und der so erhaltene Papierstoff unter Blattbil¬ dung entwässert.From EP-B 235 893 is known, a paper material initially a synthetic cationic African polymer having a molecular weight of more than 500,000 in an amount of more than 0.03 wt .-%, based on dry pulp, to form flakes zu¬ set, which are then cut in a subsequent shearing step to microflakes. Then bentonite is then added and the resulting paper pulp is dewatered under Blattbil¬.
Nach dem aus der EP-A 335 575 bekannten Verfahren zur Herstellung von Papier wird die Pulpe nacheinander mit zwei verschiedenen wasserlöslichen, kationischen Poly¬ meren, und zwar einem Fixiermittel und einem Retentionsmittel versetzt, anschließend mindestens einer Scherstufe unterworfen und danach mit Bentonit behandelt. Erst dann erfolgt die Entwässerung des Pulpe unter Blattbildung.According to the process for producing paper known from EP-A 335 575, the pulp is successively mixed with two different water-soluble, cationic polymers, namely a fixing agent and a retention agent, then subjected to at least one shear stage and then treated with bentonite. Only then is the drainage of the pulp under sheet formation.
Aus der EP-A 711 371 ist ein weiteres Verfahren zur Herstellung von Papier bekannt. Bei diesem Verfahren wird ein synthetisches, kationisches, hochmolekulares Polymer zu einer Dickstoff-Cellulose-Suspension gegeben. Nach dem Verdünnen des flockulier- ten Dickstoffs wird vor dem Entwässern ein Koagulationsmittel, das aus einem anorga- nischen Koagulationsmittel und/oder einem zweiten, niedermolekularen und hochkatio- nischen wasserlöslichen Polymer besteht, zugegeben.From EP-A 711 371 a further method for the production of paper is known. In this process, a synthetic, cationic, high molecular weight polymer is added to a thick stock cellulose suspension. After dilution of the flocculated thick stock, a coagulant consisting of an inorganic coagulant and / or a second, low molecular weight and highly cationic water soluble polymer is added prior to dewatering.
In der EP-A 910 701 wird ein Verfahren zur Herstellung von Papier und Karton be¬ schrieben, wobei man zur Papierpulpe nacheinander ein niedrigmolekulares oder mit- telmolekulares kationisches Polymer auf Basis Polyethylenimin oder Polyvinylamin und anschließend mit ein hochmolekulares kationisches Polymer wie Polyacrylamid, Poly¬ vinylamin oder kationische Stärke zusetzt. Nachdem diese Pulpe mindestens einer Scherstufe unterworfen wurde, wird sie durch Zugabe von Bentonit geflockt und der Papierstoff entwässert.EP-A 910 701 describes a process for the production of paper and board, wherein a low molecular weight or medium molecular weight cationic polymer based on polyethylenimine or polyvinylamine and subsequently with a high molecular weight cationic polymer, such as polyacrylamide, polythiol, is successively added to the paper pulp vinylamine or cationic starch. After this pulp has been subjected to at least one shear stage, it is flocculated by addition of bentonite and the pulp is dewatered.
Aus der EP-A 608 986 ist bekannt, daß man bei der Papierherstellung ein kationisches Retentionsmittel zum Dickstoff dosiert. Ein weiteres Verfahren zur Herstellung von Pa¬ pier' und Karton ist aus der US-A 5,393,381 , der WO 99/66130 und der WO 99/63159 bekannt, wobei man ebenfalls ein Mikropartikelsystem aus einem kationischen Polymer und Bentonit verwendet. Als kationisches Polymer wird ein wasserlösliches, verzweig¬ tes Polyacrylamid eingesetzt.It is known from EP-A 608 986 that a cationic retention agent is metered into the thick stock in papermaking. A further process for the production of paper and paperboard is known from US Pat. No. 5,393,381, WO 99/66130 and WO 99/63159, which also teaches a microparticle system composed of a cationic polymer and bentonite used. The cationic polymer used is a water-soluble, branched polyacrylamide.
In der WO 01/34910 wird ein Verfahren zur Herstellung von Papier beschrieben, bei dem zu der Papierstoffsuspension ein Polysaccharid oder ein synthetisches, hochmo¬ lekulares Polymer dosiert wird. Anschließend muß eine mechanische Scherung des Papierstoffs erfolgen. Die Reflockulation erfolgt durch Dosage einer anorganischen Komponente wie Kieselsäure, Bentonit oder Clay und eines wasserlöslichen Polymers.WO 01/34910 describes a process for the production of paper in which a polysaccharide or a synthetic, high molecular weight polymer is metered into the paper stock suspension. Subsequently, a mechanical shear of the pulp must take place. The reflocculation is carried out by dosing an inorganic component such as silica, bentonite or clay and a water-soluble polymer.
Aus der US 6,103,065 ist ein Verfahren zur Verbesserung der Retention und der Ent¬ wässerung von Papierstoffen bekannt, wobei man zu einem Papierstoff nach dem letz¬ ten Scheren ein kationisches Polymer mit einer Molmasse von 100 000 bis 2 Millionen und einer Ladungsdichte von mehr als 4,0 meq./g zusetzt, gleichzeitig oder danach ein Polymer mit einer Molmasse von mindestens 2 Millionen und einer Ladungsdichte von weniger als 4,0 meq./g zugibt und danach Bentonit dosiert. Es ist bei diesem Verfahren nicht erforderlich, den Papierstoff nach der Zugabe der Polymeren einer Scherung zu unterwerfen. Nach Zugabe der Polymeren und des Bentonits kann die Pulpe ohne wei¬ tere Einwirkung von Scherkräften unter Blattbildung entwässert werden.US Pat. No. 6,103,065 discloses a process for improving the retention and the removal of debris from paper materials, in which a cationic polymer having a molecular weight of 100,000 to 2 million and a charge density of more than 4 is added to a paper stock after the last shearing , 0 meq./g, simultaneously or after adding a polymer having a molecular weight of at least 2 million and a charge density of less than 4.0 meq./g and then dosed bentonite. It is not necessary in this method to shear the stock after the addition of the polymers. After addition of the polymers and the bentonite, the pulp can be dewatered without further action of shear forces to form sheets.
Aus der WO 04/15200 ist ebenfalls ein Mikropartikelsystem aus einem kationischen Polymer und einer feinteiligen anorganischen Komponente als Retentionsmittel bei der Herstellung von Papier bekannt. Als kationische Polymere kommen beispielsweise kationische Polyacrylamide, Vinylamineinheiten enthaltende Polymere und/oder PoIy- diallyldimethylammoniumchlorid mit einer mittleren Molmasse Mw von jeweils mindes- tens 500 000 und einer Ladungsdichte von höchstens 4,0 meq/g in Betracht.WO 04/15200 likewise discloses a microparticle system comprising a cationic polymer and a finely divided inorganic component as retention agent in the production of paper. Suitable cationic polymers are, for example, cationic polyacrylamides, polymers comprising vinylamine units and / or polydiallyldimethylammonium chloride having an average molecular weight M w of at least 500 000 and a charge density of at most 4.0 meq / g.
Die oben beschriebenen Mikropartikelsysteme sind technisch aufwendig, weil man für die Dosierung der feinteiligen anorganischen Flockungsmittel spezielle Vorrichtungen benötigt.The microparticle systems described above are technically complicated because special devices are required for the metering of the finely divided inorganic flocculants.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein weiteres Verfahren zur Herstellung von Papier zur Verfügung zu stellen, wobei man gegenüber dem Stand der Technik eine kürzere Entwässerungszeit, eine verbesserte Füllstoffretention und Pa¬ piere mit einer verbesserten Formation erhält.It is an object of the present invention to provide a further process for the production of paper, wherein a shorter dewatering time, an improved filler retention and papers having an improved formation are obtained compared to the prior art.
Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Papierstoffs auf einem Sieb in Ge¬ genwart mindestens eines Polymeren als Retentionsmittel unter Blattbildung und Trocknen der Blätter, wenn man die Blattbildung in Abwesenheit von feinteiligen anor- ganischen Flockungsmitteln vornimmt und als Retentionsmittel (a) Vinylamineinheiten enthaltende Polymere und/oder Polyvinylformamid mit einer Molmasse Mw von jeweils mindestens 1 MillionThe object is achieved in accordance with the invention by a process for the production of paper, paperboard and paperboard by dewatering a paper stock on a wire in the presence of at least one polymer as a retention agent with formation of sheets and drying of the sheets, if the sheet formation is in the absence of finely divided inorganic Flocculants and as a retention agent (a) polymers containing vinylamine units and / or polyvinylformamide having a molecular weight M w of at least 1 million each
undand
(b) mindestens ein kationisches oder nichtionisches Polyacrylamid und/oder ein katio¬ nisches oder nichtionisches Polymethacrylamid mit einer Molmasse Mwvon jeweils mindestens 2,5 Millionen(b) at least one cationic or nonionic polyacrylamide and / or a cationic or nonionic polymethacrylamide having a molecular weight M w of at least 2.5 million each
einsetzt.starts.
Vinylamineinheiten enthaltende Polymere und/oder Polyvinylformamid mit einer Mol¬ masse Mw von jeweils mindestens 1 Million sind bekannt. Sie werden beispielsweise durch Homopolymerisation von N-Vinylformamid zu Poly-N-vinylformamid oder durch Copolymerisieren von N-Vinylformamid mit mindestens ein,em anderen ethylenisch ungesättigten Monomeren und anschließende Hydrolyse der einpolymerisierten Vinylformamideinheiten zu Vinylamineinheiten hergestellt. Bevorzugte Vinylamineinheiten enthaltende Polymere sind die durch Hydrolyse von PoIy-N- vinylformamiden erhältlichen kationischen Polymeren. Der Hydrolysegrad dieser Polymeren beträgt beispielsweise 0,5 bis 100 %, vorzugsweise 1 bis 50 % und liegt meistens in dem Bereich von 2 bis 40, insbesondere von 2 bis 30 %. Die Polymeren der Komponente (a) haben beispielsweise eine Ladungsdichte (bestimmt bei pH 7) von 0 bis 18 meq/g, vorzugsweise 0,1 bis 7 meq/g und insbesondere von 0,2 bis 4 meq/g. Die Vinylamineinheiten enthaltenden Polymere und Poly-N-vinylformamide derVinylamine-containing polymers and / or polyvinylformamide having a molar mass M w of at least 1 million are known. They are prepared, for example, by homopolymerization of N-vinylformamide to poly-N-vinylformamide or by copolymerizing N-vinylformamide with at least one other ethylenically unsaturated monomer and subsequent hydrolysis of the copolymerized vinylformamide units to vinylamine units. Preferred polymers containing vinylamine units are the cationic polymers obtainable by hydrolysis of poly-N-vinylformamides. The degree of hydrolysis of these polymers is for example 0.5 to 100%, preferably 1 to 50% and is usually in the range of 2 to 40, in particular from 2 to 30%. The polymers of component (a) have for example a charge density (determined at pH 7) of 0 to 18 meq / g, preferably 0.1 to 7 meq / g and in particular from 0.2 to 4 meq / g. The vinylamine units containing polymers and poly-N-vinylformamide the
Komponente (a) des Retentionsmittels haben vorzugsweise eine Molmasse Mw von mindestens 1 ,2 Millionen. Die Herstellung von Homo- und Copolymerisaten von N- Vinylformamid mit den obengenannten Spezifikationen wird beispielsweise in der US 6,132,558, Spalte 2, Zeile 36 bis Spalte 5, Zeile 25 ausführlich beschrieben. Die dort gemachten Ausführungen werden hiermit durch Bezugnahme zum Offenbarungs¬ gehalt der vorliegenden Erfindung gemacht.Component (a) of the retention agent preferably has a molecular weight M w of at least 1.2 million. The preparation of homopolymers and copolymers of N-vinylformamide having the abovementioned specifications is described in detail, for example, in US Pat. No. 6,132,558, column 2, line 36 to column 5, line 25. The statements made there are hereby made by reference to the disclosure of the present invention.
Als Komponente (a) kann man entweder ein Vinylamineinheiten enthaltendes Polymer oder Poly-N-vinylformamid allein oder auch eine Mischung von Polymeren aus den beiden Verbindungsklassen einsetzen. Bevorzugt sind jedoch kationische Vinylami¬ neinheiten enthaltende Polymere als Verbindungen der Komponente (a).Component (a) can be either a vinylamine units-containing polymer or poly-N-vinylformamide alone or a mixture of polymers from the two classes of compounds. However, preference is given to polymers containing cationic vinylamine units as compounds of component (a).
Als Komponente (b) des Retentionsmittelsystems kommen kationische Polyacrylamide, nichtionische Polyacrylamide, kationische Polymethacrylamide, nichtionische PoIy- methacrylamide sowie Mischungen der genannten Verbindungen in Betracht, sofern sie jeweils eine Molmasse Mwvon mindestens 3 Millionen haben. Polymerisate dieser Art werden in der zum Stand der Technik genannten EP-A 335 575 beschrieben. Dar¬ über hinaus sind solche Polymere handelsübliche Produkte. Sie werden bekanntlich durch Polymerisieren von Acrylamid oder Methacrylamid jeweils allein zu Homopoly- merisaten oder durch Polymerisieren von Acrylamid oder Methacrylamid in Gegenwart von kationischen Monomeren hergestellt.As component (b) of the retention agent system, cationic polyacrylamides, nonionic polyacrylamides, cationic polymethacrylamides, nonionic polymethacrylamides and mixtures of the compounds mentioned come into consideration, if they each have a molecular weight M w of at least 3 million. Polymers of this type are described in the prior art EP-A 335 575. In addition, such polymers are commercially available products. They are known to be prepared by polymerizing acrylamide or methacrylamide each alone to homopolymers or by polymerizing acrylamide or methacrylamide in the presence of cationic monomers.
Geeignete kationische Monomere sind beispielsweise die Ester und Amide von ethyle- nisch ungesättigten C3- bis C5-Carbonsäuren mit Aminoalkoholen. Beispiele für kationi- sehe Monomere sind Dimethylaminoethylacrylat, Diethylaminoethylacrylat, Dimethyl- aminoethylmethacrylat, Diethylaminoethylmethacrylat, Dimethylaminopropylacrylat, Diethylaminopropylacrylat, Dimethylaminopropylmethyacrylat, Diethylaminopropyl- methacrylat, Dimethylaminoethylacrylamid, Diethylaminoethylacrylamid, Dimethylami- noethylmethacrylamid, Diethylaminoethylmethacrylamid, Dimethylaminopropylacryla- mid, Dimethylaminopropylmethacrylamid und Diethylaminopropylmethacrylamid.Suitable cationic monomers are, for example, the esters and amides of ethylenically unsaturated C 3 - to C 5 -carboxylic acids with amino alcohols. Examples of cationic monomers are dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminoethylacrylamide, diethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide.
Die kationischen Monomeren können bei der Copolymerisation in Form der freien Ba¬ sen, der Salze mit Mineralsäuren wie Schwefelsäure, Salzsäure oder Phosphorsäure, der Salze mit organischen Säuren wie Ameisensäure, Essigsäure, Propionsäure, Ben- zolsulfonsäure oder p-Toluolsulfonsäure und/oder in quaternierter Form eingesetzt werden. Als Quatemierungsmittel kommen beispielsweise Cr bis C-|8-Alkylhalogenide wie Methylchlorid, Ethylchlorid, n-Propylchlorid, Isopropylchlorid und/oder Stearylchlo- rid sowie Benzylchlorid in Betracht.The cationic monomers can be used in the copolymerization in the form of the free bases, the salts with mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid, benzenesulfonic acid or p-toluenesulfonic acid and / or in quaternized Form are used. As Quatemierungsmittel come for example Cr to C | 8- Alkyl halides such as methyl chloride, ethyl chloride, n-propyl chloride, isopropyl chloride and / or stearyl chloride and benzyl chloride into consideration.
Die kationischen Polyacrylamide bzw. die kationischen Polymethacrylamide enthalten beispielsweise 5 bis 40 Mol-%, vorzugsweise 7 bis 30 Mol-% mindestens eines kationi¬ schen Monomers einpolymerisiert. Die Molmassen der kationischen Polymeren und die der nichtionischen Polymeren betragen mindestens 2,5 Millionen, vorzugsweise min¬ destens 3 Millionen und liegen meistens in dem Bereich von 5 Millionen bis 15 MiIHo- nen.The cationic polyacrylamides or the cationic polymethacrylamides contain, for example, copolymerized 5 to 40 mol%, preferably 7 to 30 mol% of at least one cationic monomer. The molecular weights of the cationic polymers and those of the nonionic polymers are at least 2.5 million, preferably at least 3 million, and are usually in the range of 5 million to 15 million.
Erfindungsgemäß verwendet man als Retentionsmittel beispielsweiseAccording to the invention used as a retention agent, for example
(a) mindestens ein Vinylamineinheiten enthaltendes Polymer, das durch Hydrolyse von Vinylformamideinheiten enthaltenden Polymeren erhältlich ist und wobei der(a) at least one vinylamine units-containing polymer obtainable by hydrolysis of vinylformamide units containing polymers, and wherein the
Hydrolysegrad der Vinylformamideinheiten 0,5 bis 100 % beträgtHydrolysis degree of vinylformamide units is 0.5 to 100%
und (b) ein Copolymerisat aus (i) 95 bis 60 Mol-% Acrylamid und/oder Methacrylamid und (ii) 5 bis 40 Mol-% mindestens eines kationischen Monomeren.and (b) a copolymer of (i) 95 to 60 mole percent acrylamide and / or methacrylamide and (ii) 5 to 40 mole percent of at least one cationic monomer.
Das Retentionsmittel enthält insbesondere als KomponenteThe retention agent contains in particular as a component
(a) ein hydrolysiertes Polyvinylformamid mit einem Hydrolysegrad von 1 bis 40 % und einer Molmasse Mw von mindestens 1 ,2 Millionen(a) a hydrolyzed polyvinylformamide having a degree of hydrolysis of 1 to 40% and a molecular weight M w of at least 1.2 million
und als Komponenteand as a component
(b) ein Copolymerisat aus 93 bis 70 Mol-% Acrylamid und 7 bis 30 Mol-% mindestens eines kationischen Monomeren mit einer Molmasse Mw von mindestens 2,5 Millio¬ nen.(B) a copolymer of 93 to 70 mol% acrylamide and 7 to 30 mol% of at least one cationic monomer having a molecular weight M w of at least 2.5 Millio¬ NEN.
Die kationischen Polyacrylamide und die kationischen Polymethacrylamide enthalten vorzugsweise als kationisches Monomer Dimethylaminoethylacrylat-methochlorid oder Dimethylaminoethylacrylamid-methochlorid einpolymerisiert. Diese Methochloride sind durch Alkylierung von Dimethylaminoethylacrylat bzw. von Dimethylaminoethylacryla- mid mit Methylchlorid leicht zugänglich.The cationic polyacrylamides and the cationic polymethacrylamides preferably contain copolymerized as cationic monomer dimethylaminoethyl acrylate methochloride or dimethylaminoethylacrylamide methochloride. These methochlorides are readily accessible by alkylation of dimethylaminoethyl acrylate or of dimethylaminoethyl acrylamide with methyl chloride.
Die Komponenten (a) und (b) des Retentionsmittels werden dem Papierstoff, bezogen auf trockenen Papierstoff, in einer Menge vonThe components (a) and (b) of the retention agent are added to the paper stock, based on dry paper stock, in an amount of
(a) 0,001 bis 0,8 Gew.-%, vorzugsweise 0,01 bis 0,5 Gew.-%(a) 0.001 to 0.8% by weight, preferably 0.01 to 0.5% by weight
undand
(b) 0,001 bis 0,8 Gew.-%, vorzugsweise 0,01 bis 0,2 Gew.-%(b) 0.001 to 0.8% by weight, preferably 0.01 to 0.2% by weight
zugesetzt. Obwohl das Verhältnis der Komponenten (a) und (b) beliebig gewählt wer¬ den kann, verwendet man vorzugsweise pro Gewichtsteil der Komponente (a) 0,1 bis 1 ,0, vorzugsweise 0,25 bis 0,4 Gewichtsteile der Komponente (b). Das Retentionsmittel kann dem Papierstoff - in aller Regel erfolgt die Dosierung des Retentionsmittels erfin¬ dungsgemäß in den Dünnstoff - beispielsweise in Form einer Mischung aus den Kom- ponenten (a) und (b) zugeführt werden. Man kann jedoch auch so vorgehen, dass man zunächst beispielsweise nach der letzten Scherstufe vor dem Stoffauflauf die Kompo¬ nente (a) und anschließend die Komponente (b) dosiert. Beide Komponenten können jedoch auch getrennt voneinander aber gleichzeitig vor oder nach einer Scherstufe in den Dünnstoff eingebracht werden. Am vorteilhaftesten dosiert man zunächst mindes- tens eine Verbindung der Komponente (a) und anschließend mindestens eine Verbin- düng der Komponente (b). Die Verbindung der Komponente (a) kann dabei beispiels¬ weise vor einer Scherstufe und die Verbindung der Komponente (b) nach der letzten Scherstufe vor dem Stoffauflauf dem Papierstoff zugeführt werden. Beide Verbindun¬ gen können jedoch auch vor der letzten Scherstufe vor dem Stoffauflauf oder nach der letzten Stufe vor dem Stoffauflauf zum Papierstoff dosiert werden. Man kann jedoch auch die Komponente (a) an verschiedenen Stellen in den Dünnstoff dosieren und Scherkräfte auf das System einwirken lassen und die Komponente vor der letzten Scherstufe vor dem Stoffauflauf oder danach zufügen. Ebenso ist es möglich, zunächst die Komponente (b) dem Papierstoff zuzugeben und danach die Komponente (a) des Retentionsmittels zu dosieren.added. Although the ratio of components (a) and (b) can be chosen arbitrarily, it is preferable to use, per part by weight of component (a), 0.1 to 1.0 part by weight, preferably 0.25 to 0.4 part by weight of component (b ). The retention agent may be added to the paper stock - as a rule the metering of the retention agent is carried out according to the invention in the thin material - for example in the form of a mixture of components (a) and (b). However, it is also possible to proceed by metering the component (a) and then the component (b) first, for example, after the last shear stage in front of the headbox. However, both components can also be introduced into the thin material separately from one another before or after a shear stage. Most advantageously, at least one compound of component (a) is first metered, followed by at least one compound. fertil the component (b). The compound of component (a) can be supplied to the paper stock before the headbox example before a shear stage and the compound of component (b) after the last shear stage before the headbox. However, both Verbindun¬ conditions can be dosed before the last shear stage before the headbox or after the last stage before the headbox for pulp. However, it is also possible to meter the component (a) into the thin material at various points and to allow shearing forces to act on the system and to add the component before or after the last shear stage before the headbox. It is likewise possible first to add component (b) to the paper stock and then to meter component (a) of the retention agent.
Wenn man als Verbindung der Komponente (a) Polyvinylformamid einsetzt, verwendet man vorzugsweise als Verbindung der Komponente (b) ein kationisches Polyacrylamid, wählt man dagegen als Komponente (a) ein Vinylamineinheiten enthaltendes Polymer, so ist zwar der Einsatz eines kationischen Polyacrylamids oder eines kationischen Po- lymethyacrylamids bevorzugt, man kann dann jedoch auch als Komponente (b) ein nichtionisches Polyacrylamid und/oder ein nichtionisches Polymethacrylamid einset¬ zen.When polyvinylformamide is used as the compound of component (a), a cationic polyacrylamide is preferably used as the compound of component (b), while if component (a) is selected as a vinylamine polymer-containing polymer, the use of a cationic polyacrylamide or a cationic one is preferred Polymethyacrylamids preferred, but then you can also as component (b) a nonionic polyacrylamide and / or a nonionic Polymethacrylamid einset¬ zen.
Gegenstand der Erfindung ist auch die Verwendung von Kombinationen ausThe invention is also the use of combinations of
(a) Vinylamineinheiten enthaltenden Polymeren und/oder Polyvinylformamid mit einer Molmasse Mw von jeweils mindestens 1 Million(a) polymers containing vinylamine units and / or polyvinylformamide having a molecular weight M w of at least 1 million each
undand
(b) mindestens eines kationischen oder nichtionischen Polyacrylamids und/oder ein kationisches oder nichtionisches Polymethacrylamid mit einer Molmasse Mwvon jeweils mindestens 2,5 Millionen(B) at least one cationic or nonionic polyacrylamide and / or a cationic or nonionic polymethacrylamide having a molecular weight M w of at least 2.5 million
als alleiniges Retentionsmittel bei der Herstellung von Papier, Pappe und Karton.as sole retention agent in the production of paper, cardboard and cardboard.
Erfindungsgemäß, können sämtliche Papierqualitäten, Pappe und Karton hergestellt werden, beispielsweise Papiere für den Zeitungsdruck, sogenannte mittelfeine Schreib- und Druckpapiere, Naturtiefdruckpapiere und auch leichtgewichtige Streichrohpapiere. Man kann beispielsweise Holzschliff, thermomechanischen Stoff (TMP), chemo- thermomechanischen Stoff (CTMP), Druckschliff (PGW) sowie Sulfit- und Sulfatzellstoff einsetzen. Als Rohstoffe für die Herstellung der Pulpe kommen auch Zellstoff und Holzstoff sowie Altpapier und gestrichener Ausschuss in Betracht. Holzstoff und ZeII- stoff werden vor allem in den sogenannten integrierten Papierfabriken in mehr oder weniger feuchter Form direkt ohne vorherige Eindickung bzw. Trocknung weiter zu Papier verarbeitet. Aufgrund der nicht vollständig daraus entfernten Verunreinigungen enthalten diese Fasermaterialien noch Stoffe, die den üblichen Papierherstellungspro- zess stark stören. Wenn solche Papierstoffe eingesetzt werden, empfiehlt es sich, in Gegenwart eines Fixiermittels zu arbeiten.According to the invention, all paper grades, paperboard and cardboard can be produced, for example papers for newspaper printing, so-called medium-fine writing and printing papers, natural gravure papers and also lightweight coating base papers. For example, wood pulp, thermo-mechanical pulp (TMP), chemo-thermo-mechanical pulp (CTMP), pressure pulp (PGW) and sulphite and sulphate pulp can be used. As raw materials for the production of pulp and pulp and mechanical pulp as well as waste paper and coated broke into consideration. Pulp and zeolite are mainly used in the so-called integrated paper mills in more or less less moist form directly without prior thickening or drying further processed into paper. Due to the impurities not completely removed from them, these fiber materials still contain substances which severely disturb the usual papermaking process. If such pulps are used, it is advisable to work in the presence of a fixative.
Nach dem erfindungsgemäßen Verfahren können sowohl füllstofffreie als auch füll- stoffhaltige Papiere hergestellt werden. Der Füllstoffgehalt im Papier kann bis zu ma¬ ximal 40 Gew.-% betragen und liegt vorzugsweise in dem Bereich von 5 bis 30 Gew.- %. Geeignete Füllstoffe sind beispielsweise Clay, Kaolin, native und präzipitierte Krei¬ de, Titandioxid, Talkum, Calciumsulfat, Bariumsulfat, Aluminiumoxid, Satinweiß oder Mischungen der genannten Füllstoffe.According to the method of the invention, both unfilled and filler-containing papers can be produced. The filler content in the paper can be up to a maximum of 40% by weight and is preferably in the range from 5 to 30% by weight. Suitable fillers are, for example, clay, kaolin, native and precipitated circles, titanium dioxide, talc, calcium sulfate, barium sulfate, aluminum oxide, satin white or mixtures of the stated fillers.
Die Papierherstellung kann in Gegenwart der üblichen Prozesschemikalien in den übli- chen Mengen vorgenommen werden z.B. von Masseleimungsmitteln wie insbesondere Alkyldiketen-Dispersionen, Harzleim, Alkenylsuccinimid-Dispersionen oder leimend wirkenden Polymerdispersionen, Verfestigungsmitteln wie mit Epichlorhydrin vernetz¬ ten Polyamidoaminen, Polyvinylaminen eines mittleren Molekulargewichts oder Stärke, Fixiermitteln, Bioziden, Farbstoffen und Füllstoffen. Die Dosierung der üblichen Pro- zesshilfsmittel erfolgt vorzugsweise in den Dünnstoff.The papermaking can be carried out in the presence of the usual process chemicals in the usual amounts, e.g. of engine sizing agents such as, in particular, alkyldiketene dispersions, rosin size, alkenylsuccinimide dispersions or adhesive polymer dispersions, solidifying agents such as polyamidoamines crosslinked with epichlorohydrin, polyvinylamines of average molecular weight or strength, fixing agents, biocides, dyes and fillers. The dosage of the customary process auxiliaries is preferably carried out in the thin material.
Nach dem erfindungsgemäßen Verfahren erhält man, verglichen mit den Erzeugnis¬ sen, die nach bekannten Verfahren hergestellt werden, Papiere mit einer verbesserten Formation, einer verbesserten Füllstoffverteilung, einer besseren Opazität und einer verbesserten Bedruckbarkeit. Das erfindungsgemäße Verfahren ist gegenüber den Mikropartikel-Verfahren einfacher in der Durchführung und ergibt eine gegenüber dem Stand der Technik verbesserte Füllstoffretention und Formation.The process of the invention gives, compared to the products which are prepared by known processes, papers having an improved formation, an improved filler distribution, a better opacity and an improved printability. The process according to the invention is simpler to carry out than the microparticle processes and results in improved filler retention and formation compared with the prior art.
In den Beispielen bedeuten die Prozentangaben für die Einsatzstoffe immer Gewichts- prozent. Die Molmassen Mw der Polymeren wurden mit Hilfe der statischen Lichtstreu¬ ung bestimmt.In the examples, the percentages for the starting materials always mean weight percent. The molar masses Mw of the polymers were determined by means of the static light scattering.
Die Entwässerungszeit wurde bestimmt, indem man eine Probe des Papierstoffs in einem Schopper-Riegler-Testgerät entwässerte und die Zeit in Sekunden bestimmte, innerhalb der 300 ml Filtrat anfielen.The drainage time was determined by dewatering a sample of the stock in a Schopper-Riegler tester and determining the time in seconds within the 300 ml of filtrate.
Die Bestimmung der Ascheretention (First Pass Ash Retention) erfolgte durch Berech¬ nung der Differenz zwischen der Aschekonzentration des Papierstoffs in der Headbox und der Aschekonzentration im Siebwasser geteilt durch die Aschekonzentration des Papierstoffs in der Headbox und Multiplikation mit 100. Sie wird in Prozent angegeben. Die Beurteilung der Formation (On-Iine Formation Index) erfolgte durch Messung der zu prüfenden Blätter mit Hilfe des Measure IT Optical Properties Measurement OP 4255 (Formationssensor von der Firma ABB). Je niedriger der gemessene Wert, desto besser ist die Formation.Ash retention (first pass ash retention) was determined by calculating the difference between the ash concentration of the paper stock in the headbox and the ash concentration in the white water divided by the ash concentration of the paper stock in the headbox and multiplying by 100. It is reported as a percentage. Formation evaluation (on-line formation index) was performed by measuring the sheets to be tested using Measure IT Optical Properties Measurement OP 4255 (formation sensor from ABB). The lower the measured value, the better the formation.
In den Beispielen wurden folgende Polymere verwendet:The following polymers were used in the examples:
PVAm 1 : Polyvinylamin mit einer Molmasse Mw von 1 ,2 Millionen und einer Ladungs¬ dichte von 3,0 meq/gPVAm 1: polyvinylamine with a molecular weight M w of 1.2 million and a charge density of 3.0 meq / g
PAM 1 : Copolymerisat aus 70 Gew.-% Acrylamid und 30 Gew.-% Dimethylami- noethylacrylat- methochlorid mit einer Molmasse Mw von 8 Millionen und ei¬ ner Ladungsdichte von 1,7 meq/gPAM 1: copolymer of 70% by weight of acrylamide and 30% by weight of dimethylaminoethyl acrylate methochloride having a molecular weight M w of 8 million and a charge density of 1.7 meq / g
Der verwendete Bentonit war mit wässriger Natriumcarbonatlösung aktiviert worden.The bentonite used had been activated with aqueous sodium carbonate solution.
BeispieleExamples
Auf einer Doppelsiebpapiermaschine, die mit einer Geschwindigkeit von 1500 m/min holzhaltiges Druckpapier produzierte, wurde jeweils ein Papierstoff aus 50 % TMP, 30 % deinktem Altpapier, 20 % gebleichtem Kraftzellstoff und Calciumcarbonat als Füll¬ stoff sowie den im Beispiel 1 und den Vergleichsbeispielen 1 bis 3 angegebenen Zu¬ satzstoffen entwässert. Der Feststoffgehalt des Siebwassers betrug immer 0,55 %. Der Füllstoffgehalt des Papiers betrug 30 %. Das Papier hatte ein Flächengewicht von 52 - 56 g/m2.On a twin-wire paper machine which produced wood-containing printing paper at a speed of 1500 m / min, in each case one paper stock consisting of 50% TMP, 30% deinked waste paper, 20% bleached kraft pulp and calcium carbonate as filling material and that in Example 1 and Comparative Examples 1 dehydrated to 3 specified Zu¬ additives. The solids content of the white water was always 0.55%. The filler content of the paper was 30%. The paper had a basis weight of 52-56 g / m 2 .
Beispiel 1example 1
Dem oben angegebenen Papierstoff wurden nach der letzten Scherstufe und vor dem Stoffauflauf 0,03 % PVAm 1 und 0,01 % PAM 1 zugesetzt. Die Entwässerungszeit be¬ trug 31 Sekunden, die Ascheretention 42 % und der Index für die Formation 5,9.0.03% PVAm 1 and 0.01% PAM 1 were added to the stock indicated above after the last shear stage and before the headbox. The dewatering time was 31 seconds, the ash retention 42% and the formation index 5.9.
Vergleichsbeispiel 1Comparative Example 1
Gemäß der Lehre der EP-A 235 893 dosierte man 0,04 % PVAm 1 und 0,015 % PAM 1 zum oben beschriebenen Papierstoff vor der letzten Scherstufe und danach 0,3 % Bentonit vor dem Stoffauflauf. Die Entwässerungszeit einer den Bentonit enthaltenden Probe betrug 38 Sekunden, die Ascheretention 37 % und der Index für die Formation 6,9. Vergleichsbeispiel 2According to the teaching of EP-A 235 893, 0.04% PVAm 1 and 0.015% PAM 1 were metered into the above-described paper stock before the last shear stage and then 0.3% bentonite before the headbox. The dewatering time of a sample containing the bentonite was 38 seconds, the ash retention 37%, and the formation index 6.9. Comparative Example 2
Zu dem oben beschriebenen Papierstoff wurden nach der letzten Scherstufe und vor dem Stoffauflauf 0,025 % PAM 1 dosiert. Die Entwässerungszeit dieses Papierstoffs betrug 41 Sekunden, die Ascheretention 36 % und der Index für die Formation 7,4.To the paper stock described above 0.025% PAM 1 was metered after the last shear stage and before the headbox. The drainage time of this stock was 41 seconds, the ash retention 36% and the index for the formation 7.4.
Vergleichsbeispiel 3Comparative Example 3
Zu dem oben beschriebenen Papierstoff dosierte man nach der letzten Scherstufe vor dem Stoffauflauf 0,05 % PVAm 1. Die Entwässerungszeit dieses Papierstoffs betrug 38 Sekunden, die Ascheretention 39 % und der Index für die Formation 6,4. 0.05% PVAm 1 was metered to the stock described above after the last shear stage in front of the headbox. The drainage time of this stock was 38 seconds, the ash retention 39% and the index for the formation 6.4.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Papier, Pappe und Karton durch Entwässern eines Papierstoffs auf einem Sieb in Gegenwart mindestens eines Polymeren als Reten- tionsmittel unter Blattbildung und Trocknen der Blätter, dadurch gekennzeichnet, dass man die Blattbildung in Abwesenheit von feinteiligen anorganischen Flo¬ ckungsmitteln vornimmt und als Retentionsmittel1. A process for the production of paper, paperboard and cardboard by dewatering a paper stock on a wire in the presence of at least one polymer as a retention agent with sheet formation and drying the sheets, characterized in that one carries out the sheet formation in the absence of finely divided inorganic flocculants and as a retention aid
(a) Vinylamineinheiten enthaltende Polymere und/oder Polyvinylformamid mit ei- ner Molmasse Mw von jeweils mindestens 1 Million(a) polymers containing vinylamine units and / or polyvinylformamide having a molecular weight M w of at least 1 million each
undand
(b) mindestens ein kationisches oder nichtionisches Polyacrylamid und/oder ein kationisches oder nichtionisches Polymethacrylamid mit einer Molmasse Mw von jeweils mindestens 2,5 Millionen(B) at least one cationic or nonionic polyacrylamide and / or a cationic or nonionic polymethacrylamide having a molecular weight M w of at least 2.5 million
einsetzt.starts.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man als Retentionsmit¬ tel2. The method according to claim 1, characterized in that as Retentionsmit¬ tel
(a) mindestens ein Vinylamineinheiten enthaltendes Polymer, das durch Hydroly¬ se von Vinylformamideinheiten enthaltenden Polymeren erhältlich ist und wo- bei der Hydrolysegrad der Vinylformamideinheiten 0,5 bis 100 % beträgt(a) at least one polymer comprising vinylamine units which is obtainable by hydrolysis of vinylformamide units containing polymers and wherein the degree of hydrolysis of the vinylformamide units is 0.5 to 100%
undand
(b) ein Copolymerisat aus (i) 95 bis 60 Mol-% Acrylamid und/oder Methacrylamid und (ii) 5 bis 40 Mol-% mindestens eines kationischen Monomeren(b) a copolymer of (i) 95 to 60 mole percent acrylamide and / or methacrylamide and (ii) 5 to 40 mole percent of at least one cationic monomer
einsetzt.starts.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man als Reten- tionsmittel3. The method according to claim 1 or 2, characterized in that as a retention agent
(a) ein hydrolysiertes Polyvinylformamid mit einem Hydrolysegrad von 1 bis 50 % und einer Molmasse Mw von mindestens 1,2 Millionen(a) a hydrolyzed polyvinylformamide having a degree of hydrolysis of from 1 to 50% and a molecular weight M w of at least 1.2 million
und (b) ein Copolymerisat aus 93 bis 70 Mol-% Acrylamid und 7 bis 30 Mol-% min¬ destens eines kationischen Monomerenand (b) a copolymer of 93 to 70 mol% of acrylamide and 7 to 30 mol% of at least one cationic monomer
einsetzt.starts.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die kationischen Poly(meth)acrylamide mindestens ein kationisches Monomer aus der Gruppe Dimethylaminoethylacrylat, Diethylaminoethylacrylat, Dimethylaminoethyl- methacrylat, Diethylaminoethylrnethacrylat, Dimethylaminopropylacrylat, Diethyla- minopropylacrylat, Dimethylaminopropylmethyacrylat,4. The method according to any one of claims 1 to 3, characterized in that the cationic poly (meth) acrylamides at least one cationic monomer from the group dimethylaminoethyl, Diethylaminoethylacrylat, Dimethylaminoethyl- methacrylate, Diethylaminoethylrnethacrylat, Dimethylaminopropylacrylat, Diethyla- minopropylacrylat, Dimethylaminopropylmethyacrylat,
Diethylaminopropylmethacrylat, Dimethylaminoethylacrylamid, Diethylaminoethylacrylamid, Dimethylamino-ethylmethacrylamid, Diethylaminoethylmethacrylamid, Dimethylaminopropylacrylamid, Dimethylami- nopropylmethacrylamid und Diethylaminopropylmethacrylamid in Form der freien Basen, Salze und/oder in quaternierter Form einpolymerisiert enthalten.Diethylaminopropyl methacrylate, dimethylaminoethylacrylamide, diethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and diethylaminopropylmethacrylamide in copolymerized form in the form of the free bases, salts and / or in quaternized form.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass die kationischen Poly¬ acrylamide und kationischen Polymethacrylamide als kationisches Monomer Di- methylaminoethylacrylat-methochlorid oder Dimethylaminoethylacrylamidmethoch- lorid einpolymerisiert enthalten.5. Process according to Claim 4, characterized in that the cationic polyacrylamides and cationic polymethacrylamides contain copolymerized dimethylaminoethyl acrylate methochloride or dimethylaminoethylacrylamide methochloride as cationic monomer in copolymerized form.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man die Komponenten (a) und (b) des Retentionsmittels, bezogen auf trockenen Pa¬ pierstoff, in einer Menge von6. The method according to any one of claims 1 to 5, characterized in that the components (a) and (b) of the retention agent, based on dry Pa¬ pierstoff, in an amount of
(a) 0,001 bis 0,8 Gew.-%, vorzugsweise 0,01 bis 0,5 Gew.-%(a) 0.001 to 0.8% by weight, preferably 0.01 to 0.5% by weight
undand
(b) 0,001 bis 0,8 Gew.-%, vorzugsweise 0,01 bis 0,2 Gew.-%(b) 0.001 to 0.8% by weight, preferably 0.01 to 0.2% by weight
einsetzt.starts.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das_ Retentionsmittel pro Gewichtsteil der Komponente (a) 0,1 bis 1 ,0, vorzugsweise 0,25 bis 0,4 Ge- •wichtsteile der Komponente (b) enthält. 7. The method according to claim 6, characterized in that das_ retention agent per part by weight of component (a) from 0.1 to 1, 0, preferably 0.25 to 0.4 • overall weight parts of component (b).
8. Verwendung von Kombinationen aus8. Using combinations of
(a) Vinylamineinheiten enthaltenden Polymeren und/oder Polyvinylformamid mit einer Molmasse Mw von jeweils mindestens 1 Million(a) polymers containing vinylamine units and / or polyvinylformamide having a molecular weight M w of at least 1 million each
undand
(b) mindestens eines kationischen oder nichtionischen Polyacrylamids und/oder ein kationisches oder nichtionisches Polymethacrylamid mit einer Molmasse Mwvon jeweils mindestens 3 Millionen(B) at least one cationic or nonionic polyacrylamide and / or a cationic or nonionic polymethacrylamide having a molecular weight M w of at least 3 million
als alleiniges Retentionsmittel bei der Herstellung von Papier, Pappe und Karton. as sole retention agent in the production of paper, cardboard and cardboard.
EP05783030.9A 2004-09-10 2005-09-08 Method for the production of paper, paperboard and cardboard Active EP1792010B1 (en)

Applications Claiming Priority (2)

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DE102004044379A DE102004044379B4 (en) 2004-09-10 2004-09-10 Process for the production of paper, paperboard and cardboard and use of a retention agent combination
PCT/EP2005/009653 WO2006027242A1 (en) 2004-09-10 2005-09-08 Method for the production of paper, paperboard and cardboard

Publications (2)

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EP1792010B1 EP1792010B1 (en) 2015-11-11

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WO (1) WO2006027242A1 (en)

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EP1792010B1 (en) 2015-11-11
CN101014741A (en) 2007-08-08
CA2576611C (en) 2014-12-23
CN101014741B (en) 2010-05-26
US8029647B2 (en) 2011-10-04
WO2006027242A1 (en) 2006-03-16
DE102004044379A1 (en) 2006-03-30
US20080000601A1 (en) 2008-01-03
DE102004044379B4 (en) 2008-01-10

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