EP0438755B1 - Paper and board-paper making process from paper materials containing perturbating compounds - Google Patents
Paper and board-paper making process from paper materials containing perturbating compounds Download PDFInfo
- Publication number
- EP0438755B1 EP0438755B1 EP90125089A EP90125089A EP0438755B1 EP 0438755 B1 EP0438755 B1 EP 0438755B1 EP 90125089 A EP90125089 A EP 90125089A EP 90125089 A EP90125089 A EP 90125089A EP 0438755 B1 EP0438755 B1 EP 0438755B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper
- polymers
- units
- formula
- mol
- 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.)
- Expired - Lifetime
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
- 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
Definitions
- US Pat. No. 4,421,602 discloses hydrolyzed homopolymers of N-vinylformamide which contain 90 to 10 mol% of vinylamine units and 10 to 90 mol% of N-vinylformamide units.
- the hydrolyzed polyvinylformamides are used as retention and drainage agents in the manufacture of paper. Because of the vinylamine units, the polymers have a positive charge in aqueous solution. They are therefore adsorbed by the negatively charged surfaces of the solid particles in the paper stock and thus facilitate the binding of the originally negatively charged particles to one another. As a result, an increased drainage rate and improved retention are observed.
- the effectiveness of the cationic products is known to be significantly adversely affected by the presence of contaminants in the paper stock. Interfering substances are understood to mean oligomeric or polymeric substances with an anionic charge character, which worsen the drainage rate and the retention in the manufacture of paper. Such contaminants accumulate increasingly in the water cycles of paper machines because the used water is recycled to an increasing extent.
- EP-A-0 249 891 discloses a process for the production of paper, cardboard and cardboard, in which paper materials containing impurities are dewatered in the presence of nonionic polymers, such as homopolymers of N-vinylformamide or of N-vinylpyrrolidone.
- nonionic polymers such as homopolymers of N-vinylformamide or of N-vinylpyrrolidone.
- the polymers mentioned act as retention aids and drainage aids.
- Their effectiveness is considerably increased if non-ionic condensation products, e.g. Condensation products of phenol and formaldehyde of the resol and novolak type are present.
- EP-A-0071050 describes a method according to the preamble of claim 1.
- the present invention has for its object to provide dewatering, retention and flocculants for the papermaking process, which have a better effectiveness in paper containing impurities than the polymers described above.
- a paper stock containing interfering substances is dewatered, for the production of which all fiber qualities are considered either alone or in a mixture with one another.
- Inorganic fillers such as clay, chalk, gypsum or titanium dioxide and mixtures of these fillers can be added to the fibrous materials in customary amounts.
- water is used for the production of the paper stock, which is at least partially or completely returned from the paper machine. These are clarified or untreated white water as well as mixtures of such water qualities.
- the returned water contains more or less large amounts of so-called contaminants, which - as mentioned - severely impair the effectiveness of the previously used cationic retention and drainage aids.
- Such effects are described for example in the technical literature, cf.
- the content of such contaminants in the paper stock can be characterized, for example, with the sum parameter "Chemical oxygen demand” (COD value).
- COD value the sum parameter
- this sum parameter also includes nonionic or low molecular weight substances that do not directly interfere with dewatering or retention, but which, for example, as degradation products of wood constituents, always occur as accompanying substances for contaminants.
- the COD values of the pulp-containing paper stock to be dewatered according to the invention are 300 to 30,000, preferably 1,000 to 20,000 mg oxygen / kg of the aqueous phase of the pulp-containing paper.
- Fibers for the production of pulps that contain contaminants are, for example, wood pulp, unbleached pulp, waste paper pulp and paper pulp from all annual plants.
- wood pulps include wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP).
- TMP thermomechanical material
- CMP chemo-thermomechanical material
- RMP refiner mechanical pulp
- unbleached pulp the unbleached kraft pulp is particularly suitable, but also the unbleached sulfite pulp.
- waste paper all qualities are suitable, both sorted and unsorted. Are particularly suitable deinked waste paper.
- Usable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf.
- the following compounds are to be regarded as interfering substances: sodium silicate, which comes from deinking and the peroxide bleaching of waste paper materials, polyphosphates and polyacrylates from filler dispersions that are used in paper manufacture, humic acids from raw water, carboxymethyl cellulose from waste paper or coated scrap, anionic starches from waste paper or deleted committee, lignin derivatives from sulfate pulp, wood pulp, TMP or CTMP substances, hemicelluloses and their degradation products from wood pulp, TMP or CTMP substances and lignin sulfonates from unbleached sulfite pulps.
- sodium silicate which comes from deinking and the peroxide bleaching of waste paper materials
- polyphosphates and polyacrylates from filler dispersions that are used in paper manufacture humic acids from raw water, carboxymethyl cellulose from waste paper or coated scrap, anionic starches from waste paper or deleted committee
- lignin derivatives from sulfate pulp, wood pulp, TMP or CTMP substances
- R1 and R2 can have the same or different meanings.
- they each represent H and / or C1- to C3-alkyl, preferably R1 and R2 each represent a hydrogen atom.
- the polymers which contain the units of the formulas I and II have K values of at least 130 (determined according to H. Fikentscher in 5% by weight saline solution at 25 ° C. and a polymer concentration of 0.1% by weight).
- the polymers are obtainable by homopolymerization or copolymerization of N-vinylamides of the formula
- the substituents R1 and R2 have the meaning given in the formulas I and II.
- Compounds of the formula III are, for example, N-vinylformamide, N-vinylacetamide, N-ethyl-N-vinylformamide, N-ethyl-N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide and N-vinylpropionamide.
- the homo- and copolymerization of the N-vinylamides of the formula III leads to homo- or copolymers which contain units of the formula I in copolymerized form.
- the homopolymers and copolymers of the vinylamides of the formula III are subjected to hydrolysis in the presence of acids or bases at temperatures up to 170 ° C., for example in the Range from 20 to 170 ° C, preferably 50 to 120 ° C.
- the degree of hydrolysis of the polymerized units of the formula I is essentially dependent on the concentration of the amounts of acid or base used and the temperature.
- Mineral acids such as hydrogen halide, sulfuric acid, nitric acid and phosphoric acid, and organic acids, for example, are suitable for the hydrolysis of the copolymers.
- Acetic acid, propionic acid, benzenesulfonic acid and alkylsulfonic acids such as dodecylsulfonic acid.
- bases can also be used for the hydrolysis, for example metal hydroxides of metals of the 1st and 2nd main group of the Periodic Table of the Elements, for example lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide.
- Ammonia and derivatives of ammonia for example triethylamine, monomethanolamine, diethanolamine, triethanolamine and morpholine, can also be used as bases.
- the hydrolysis of the homo- and copolymers of the N-vinylamides of the formula III is carried out to such an extent that less than 10, preferably 1 to 9 mol% of the units of the formula I contained in the polymers are converted into units of the formula II.
- copolymers are also suitable which contain up to 50% by weight, preferably up to 30% Wt .-%, at least one other ethylenically unsaturated monomer copolymerized.
- Suitable comonomers for the N-vinylamides of the formula III are, for example, vinyl acetate, vinyl propionate, C1- to C4-alkyl vinyl ether, N-vinylpyrrolidone, and also esters, nitriles and amides of ethylenically unsaturated C3- to C8-carboxylic acids, in particular esters, nitriles and amides of acrylic acid or methacrylic acid. Processes for the preparation of the hydrolyzed homopolymers and copolymers of compounds of the formula III are known.
- the hydrolyzed polymers can be present as an aqueous solution, as a water-in-oil polymer emulsion, as a powder or as a bead polymer.
- Bead polymers are prepared, for example, by the known reverse suspension polymerization process.
- the above-described homopolymers and copolymers containing less than 10 mol% of vinylamine units of the formula II are, according to the invention, a pulp containing impurities as drainage, retention and flocculants in amounts of 0.002 to 0.1, preferably 0.005 to 0.05,% by weight. -%, based on dry paper stock added.
- the Polymers to be used according to the invention are added to the paper stock in a very dilute aqueous solution, as is customary when using other high molecular weight water-soluble polymers.
- concentration in the aqueous solution is generally between 0.01 and 0.1% by weight.
- the main advantages of the process according to the invention are the low sensitivity of the polymers containing less than 10 mol% of units of formula II to the presence of interfering substances and the fact that that no additional fixative for the high molecular weight polymer, as described in EP-A-0 249 891, has to be used.
- the parts given in the examples are parts by weight. The percentages relate to the weight of the fabrics.
- 1 l of the pulp suspension to be tested is dewatered in a Schopper-Riegler test device.
- the time that is determined for different outlet volumes is evaluated as a criterion for the drainage rate of the substance suspension examined in each case.
- the drainage times were determined after a run of 500 or 600 ml of water.
- the charge density of the hydrolyzed polymers based on poly-N-vinylformamide was determined using an enzymatic formic acid determination method (company publication “Methods of Enzymatic Food Analysis” by Boehringer Mannheim GmbH, 1984).
- Polymer 4 homopolymer of N-vinylformamide with a K value of 218.
- Polymer 5 Hydrolyzed poly-N-vinylformamide, which contained 89.9 mol% of N-vinylformamide units and 10.1 mol% of vinylamine units and had a K value of 218.
- a pulp with a consistency of 4 g / l was produced from 100% mixed waste paper.
- the pH in the stock suspension was 8.1.
- 4% water glass, based on dry paper stock was added to the paper stock.
- Samples of this paper stock were each dewatered in the presence of the polymers shown in Table 1.
- the polymers were used in an amount of 0.04%, based on dry paper stock.
- the drainage times for 600 ml of filtrate in the Schopper-Riegler test device and the optical transmittance of the filtrate obtained in this way are given in Table 1.
- the paper stock described above was dewatered without any further addition.
- a pulp with a consistency of 4 g / l was produced from 80 parts of TMP fabric, 20 parts of bleached sulfate pulp and 30 parts of kaolin as filler.
- the pH was adjusted to 6.0 by adding alum.
- 50 ml of an aqueous TMP extract from an industrial-scale TMP production were added per liter.
- the polymers given in Table 2 were added to samples of this paper stock in an amount of 0.02% polymer, based on dry paper stock, and the dewatering time for 500 ml of filtrate in the Schopper-Riegler test device and the optical transmission were determined. The following results were obtained:
- a pulp was made from 100% unbleached sulfate pulp with a consistency of 5 g / l.
- the pH was 7.9.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Making Paper Articles (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)
Abstract
Description
Aus der US-A- 4 421 602 sind hydrolysierte Homopolymerisate von N-Vinylformamid bekannt, die 90 bis 10 mol.-% Vinylamin-Einheiten und 10 bis 90 mol.-% N-Vinylformamid-Einheiten enthalten. Die hydrolysierten Polyvinylformamide werden als Retentions- und Entwässerungsmittel bei der Herstellung von Papier verwendet. Aufgrund der Vinylamin-Einheiten besitzen die Polymerisate in wäßriger Lösung eine positive Ladung. Sie werden daher von den negativ geladenen Oberflächen der festen Partikeln im Papierstoff adsorbiert und erleichtern so die Bindung der ursprünglich negativ geladenen Teilchen aneinander. Als Folge davon beobachtet man eine erhöhte Entwässerungsgeschwindigkeit und eine verbesserte Retention. Die Wirksamkeit der kationischen Produkte wird bekanntlich durch die Anwesenheit von Störstoffen im Papierstoff deutlich negativ beeinflußt. Unter Störstoffen werden oligomere oder polymere Substanzen mit anionischem Ladungscharakter verstanden, die bei der Herstellung von Papier die Entwässerungsgeschwindigkeit und die Retention verschlechtern. Derartige Störstoffe reichern sich in den Wasserkreisläufen von Papiermaschinen zunehmend an, weil das gebrauchte Wasser in verstärktem Maße wieder zurückgeführt wird.US Pat. No. 4,421,602 discloses hydrolyzed homopolymers of N-vinylformamide which contain 90 to 10 mol% of vinylamine units and 10 to 90 mol% of N-vinylformamide units. The hydrolyzed polyvinylformamides are used as retention and drainage agents in the manufacture of paper. Because of the vinylamine units, the polymers have a positive charge in aqueous solution. They are therefore adsorbed by the negatively charged surfaces of the solid particles in the paper stock and thus facilitate the binding of the originally negatively charged particles to one another. As a result, an increased drainage rate and improved retention are observed. The effectiveness of the cationic products is known to be significantly adversely affected by the presence of contaminants in the paper stock. Interfering substances are understood to mean oligomeric or polymeric substances with an anionic charge character, which worsen the drainage rate and the retention in the manufacture of paper. Such contaminants accumulate increasingly in the water cycles of paper machines because the used water is recycled to an increasing extent.
Aus der EP-A- 0 249 891 ist ein Verfahren zur Herstellung von Papier, Pappe und Karton bekannt, bei dem man Störstoffe enthaltende Papierstoffe in Gegenwart von nichtionischen Polymeren, wie Homopolymerisaten des N-Vinylformamids oder des N-Vinylpyrrolidons, entwässert. Die genannten Polymerisate wirken dabei als Retentionsmittel und Entwässerungshilfsmittel. Ihre Wirksamkeit wird beträchtlich erhöht, wenn bei der Entwässerung noch zusätzlich nichtionische Kondensationsprodukte, z.B. Kondensationsprodukte aus Phenol und Formaldeyhd vom Resol- und Novolak-Typ anwesend sind.EP-A-0 249 891 discloses a process for the production of paper, cardboard and cardboard, in which paper materials containing impurities are dewatered in the presence of nonionic polymers, such as homopolymers of N-vinylformamide or of N-vinylpyrrolidone. The polymers mentioned act as retention aids and drainage aids. Their effectiveness is considerably increased if non-ionic condensation products, e.g. Condensation products of phenol and formaldehyde of the resol and novolak type are present.
Die EP-A-0071050 beschreibt ein Verfahren gemäß dem Oberbegriff von Anspruch 1.EP-A-0071050 describes a method according to the preamble of claim 1.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Entwässerungs-, Retentions- und Flockungsmittel für den Papierherstellungsprozeß zur Verfügung zu stellen, die in störstoffhaltigen Papierstoffen eine bessere Wirksamkeit als die oben beschriebenen Polymeren aufweisen.The present invention has for its object to provide dewatering, retention and flocculants for the papermaking process, which have a better effectiveness in paper containing impurities than the polymers described above.
Die Aufgabe wird erfindungsgemäß gelöst mit einem Verfahren zur Herstellung von Papier, Pappe und Karton aus Störstoffe enthaltenden Papierstoffen durch Entwässern in Gegenwart von Polymerisaten, die als charakteristische Bestandteile Einheiten der Formeln
in denen R¹, R² = H und/oder C₁- bis C₃-Alkyl bedeuten, einpolymerisiert enthalten und die K-Werte von mindestens 130 (bestimmt nach H. Fikentscher in 5 gew.%iger wäßriger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 0,1 Gew.%) aufweisen, wenn solche Polymerisate eingesetzt werden, in denen der Gehalt an Einheiten der Formel II weniger als 10 mol-% beträgt.The object is achieved according to the invention with a process for the production of paper, cardboard and cardboard from paper materials containing impurities by dewatering in the presence of polymers which, as characteristic constituents, form units of the formulas
in which R¹, R² = H and / or C₁- to C₃-alkyl, copolymerized and contain the K values of at least 130 (determined according to H. Fikentscher in 5% by weight aqueous saline solution at 25 ° C. and a polymer concentration of 0.1% by weight) if polymers are used in which the content of units of the formula II is less than 10 mol%.
Bei dem erfindungsgemäßen Verfahren wird ein störstoffhaltiger Papierstoff entwässert, für dessen Herstellung sämtliche Faserqualitäten entweder allein oder in Mischung untereinander in Betracht kommen. Den Faserstoffen können in üblichen Mengen anorganische Füllstoffe, wie beispielsweise Clay, Kreide, Gips oder Titandioxid sowie Mischungen dieser Füllstoffe zugefügt werden. Für die Herstellung des Papierstoffs wird in der Praxis Wasser verwendet, das zumindest teilweise oder vollständig von der Papiermaschine zurückgeführt wird. Es handelt sich hierbei um geklärtes oder ungeklärtes Siebwasser sowie um Mischungen solcher Wasserqualitäten. Das zurückgeführte Wasser enthält mehr oder weniger große Mengen an sogenannten Störstoffen, die - wie erwähnt - die Wirksamkeit der bisher gebräuchlichen kationischen Retentions- und Entwässerungshilfsmittel stark beeinträchtigen. Derartige Effekte sind beispielsweise in der technischen Literatur beschrieben, vgl. Tappi-Journal, Band 70, Heft 10, 79 (1987). Der Gehalt des Papierstoffs an solchen Störstoffen kann beispielsweise mit dem Summenparameter "Chemischer Sauerstoffbedarf" (CSB-Wert) charakterisiert werden. Mit diesem Summenparameter werden jedoch auch nichtionische oder niedrigmolekulare Substanzen erfaßt, die die Entwässerung oder Retention nicht unmittelbar stören, die aber beispielsweise als Abbauprodukte von Holzinhaltsstoffen immer als Begleitsubstanzen von Störstoffen auftreten. Die CSB-Werte der erfindungsgemäß zu entwässernden störstoffhaltigen Papierstoffe betragen 300 bis 30 000, vorzugsweise 1 000 bis 20 000 mg Sauerstoff/kg der wäßrigen Phase des störstoffhaltigen Papierstoffs.In the method according to the invention, a paper stock containing interfering substances is dewatered, for the production of which all fiber qualities are considered either alone or in a mixture with one another. Inorganic fillers such as clay, chalk, gypsum or titanium dioxide and mixtures of these fillers can be added to the fibrous materials in customary amounts. In practice, water is used for the production of the paper stock, which is at least partially or completely returned from the paper machine. These are clarified or untreated white water as well as mixtures of such water qualities. The returned water contains more or less large amounts of so-called contaminants, which - as mentioned - severely impair the effectiveness of the previously used cationic retention and drainage aids. Such effects are described for example in the technical literature, cf. Tappi-Journal, Volume 70, Issue 10, 79 (1987). The content of such contaminants in the paper stock can be characterized, for example, with the sum parameter "Chemical oxygen demand" (COD value). However, this sum parameter also includes nonionic or low molecular weight substances that do not directly interfere with dewatering or retention, but which, for example, as degradation products of wood constituents, always occur as accompanying substances for contaminants. The COD values of the pulp-containing paper stock to be dewatered according to the invention are 300 to 30,000, preferably 1,000 to 20,000 mg oxygen / kg of the aqueous phase of the pulp-containing paper.
Faserstoffe zur Herstellung der Pulpen, die Störstoffe enthalten, sind beispielsweise Holzstoffe, ungebleichte Zellstoffe, Altpapierstoffe sowie Papierstoffe aus allen Einjahrespflanzen. Zu Holzstoffen gehören beispielsweise Holzschliff, thermomechanischer Stoff (TMP), chemo-thermomechanischer Stoff (CTMP), Druckschliff, Halbzellstoff, Hochausbeutezellstoff und Refiner Mechanical Pulp (RMP). Bei ungebleichten Zellstoffen kommt vor allem der ungebleichte Kraftzellstoff, aber auch ungebleichter Sulfitzellstoff in Betracht. Bezüglich Altpapier sind sämtliche Qualitäten geeignet, sowohl sortiert als auch unsortiert. Besonders geeignet sind deinkte Altpapierstoffe. Verwendbare Einjahrespflanzen zur Herstellung von Papierstoffen sind beispielsweise Reis, Weizen, Zuckerrohr und Kenaf.Fibers for the production of pulps that contain contaminants are, for example, wood pulp, unbleached pulp, waste paper pulp and paper pulp from all annual plants. For example, wood pulps include wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure grinding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP). In the case of unbleached pulp, the unbleached kraft pulp is particularly suitable, but also the unbleached sulfite pulp. With regard to waste paper, all qualities are suitable, both sorted and unsorted. Are particularly suitable deinked waste paper. Usable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf.
In der technischen Literatur sind Störstoffe, die die Retention und Entwässerung bei der Papierherstellung beeinträchtigen, beispielhaft angegeben, z.B. in der bereits oben zitierten Literaturstelle, Tappi-Journal, Band 70, Heft 10, 79 (1987) und Wochenblatt für Papierfabrikation, Heft 13, 493 (1979). Danach sind folgende Verbindungen als Störstoffe anzusehen: Natriumsilikat, das aus dem Deinking und der Peroxidbleiche von Altpapierstoffen stammt, Polyphosphate und Polyacrylate aus Füllstoffdispersionen, die bei der Papierherstellung eingesetzt werden, Huminsäuren aus Rohwässern, Carboxymethylcellulose aus Altpapier oder gestrichenem Ausschuß, anionische Stärken aus Altpapier oder gestrichenem Ausschuß, Ligninderivate aus Sulfatzellstoff, Holzschliff, TMP- oder CTMP-Stoffen, Hemizellulosen und deren Abbauprodukte aus Holzschliff, TMP- oder CTMP-Stoffen und Ligninsulfonate aus ungebleichten Sulfitzellstoffen.In the technical literature, impurities that impair retention and dewatering in papermaking are given as examples, e.g. in the literature cited above, Tappi-Journal, Volume 70, Issue 10, 79 (1987) and Wochenblatt für Papierfabrikation, Issue 13, 493 (1979). According to this, the following compounds are to be regarded as interfering substances: sodium silicate, which comes from deinking and the peroxide bleaching of waste paper materials, polyphosphates and polyacrylates from filler dispersions that are used in paper manufacture, humic acids from raw water, carboxymethyl cellulose from waste paper or coated scrap, anionic starches from waste paper or deleted committee, lignin derivatives from sulfate pulp, wood pulp, TMP or CTMP substances, hemicelluloses and their degradation products from wood pulp, TMP or CTMP substances and lignin sulfonates from unbleached sulfite pulps.
Die Herstellung von Papier, Pappe und Karton aus den Störstoffe enthaltenden Papierstoffen durch Entwässern auf einem Papiermaschinensieb erfolgt in Gegenwart von Polymerisaten, die als charakteristische Bestandteile Einheiten der Formeln
enthalten. Die Substituenten R¹ und R² können gleiche oder verschiedene Bedeutung haben. Sie stehen in den Formeln I und II jeweils für H und/oder C₁- bis C₃-Alkyl, vorzugsweise bedeuten R¹ und R² jeweils ein Wasserstoffatom.The production of paper, cardboard and cardboard from the paper materials containing impurities by dewatering on a paper machine screen takes place in the presence of polymers, which are characteristic components of units of the formulas
contain. The substituents R¹ and R² can have the same or different meanings. In the formulas I and II, they each represent H and / or C₁- to C₃-alkyl, preferably R¹ and R² each represent a hydrogen atom.
Die Polymerisate, die die Einheiten der Formeln I und II enthalten, haben K-Werte von mindestens 130 (bestimmt nach H. Fikentscher in 5 gew.%iger Kochsalzlösung bei 25°C und einer Polymerkonzentration von 0,1 Gew.%). Die Polymerisate sind erhältlich durch Homopolymerisation oder Copolymerisation von N-Vinylamiden der Formel
Die Substituenten R¹ und R² haben die in den Formeln I und II angegebene Bedeutung. Verbindungen der Formel III sind beispielsweise N-Vinylformamid, N-Vinylacetamid, N-Ethyl-N-vinylformamid, N-Ethyl-N-vinylacetamid, N-Methyl-N-vinylformamid, N-Methyl-N-vinylacetamid und N-Vinylpropionamid.The substituents R¹ and R² have the meaning given in the formulas I and II. Compounds of the formula III are, for example, N-vinylformamide, N-vinylacetamide, N-ethyl-N-vinylformamide, N-ethyl-N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide and N-vinylpropionamide.
Die Homo- und Copolymerisation der N-Vinylamide der Formel III führt zu Homo- oder Copolymerisaten, die Einheiten der Formel I einpolymerisiert enthalten. Um daraus die erfindungsgemäß zu verwendenden Polymerisate zu erhalten, die Einheiten der Formel I und II aufweisen, unterwirft man die Homo- und Copolymerisate der Vinylamide der Formel III einer Hydrolyse in Gegenwart von Säuren oder Basen bei Temperaturen bis zu 170°C, beispielsweise in dem Bereich von 20 bis 170°C, vorzugsweise 50 bis 120°C. Der Hydrolysegrad der polymerisierten Einheiten der Formel I ist im wesentlichen von der Konzentration der dabei eingesetzten Mengen an Säure oder Base und der Temperatur abhängig. Für die Hydrolyse der Copolymerisate eignen sich Mineralsäuren, wie Halogenwasserstoffe, Schwefelsäure, Salpetersäure und Phosphorsäure, sowie organische Säuren, z.B. Essigsäure, Propionsäure, Benzolsulfonsäure und Alkylsulfonsäuren, wie Dodecylsulfonsäure.The homo- and copolymerization of the N-vinylamides of the formula III leads to homo- or copolymers which contain units of the formula I in copolymerized form. In order to obtain therefrom the polymers to be used according to the invention which have units of the formula I and II, the homopolymers and copolymers of the vinylamides of the formula III are subjected to hydrolysis in the presence of acids or bases at temperatures up to 170 ° C., for example in the Range from 20 to 170 ° C, preferably 50 to 120 ° C. The degree of hydrolysis of the polymerized units of the formula I is essentially dependent on the concentration of the amounts of acid or base used and the temperature. Mineral acids, such as hydrogen halide, sulfuric acid, nitric acid and phosphoric acid, and organic acids, for example, are suitable for the hydrolysis of the copolymers. Acetic acid, propionic acid, benzenesulfonic acid and alkylsulfonic acids such as dodecylsulfonic acid.
Zur Hydrolyse kann man jedoch auch Basen verwenden, z.B. Metallhydroxide von Metallen der 1. und 2. Hauptgruppe des Periodensystems der Elemente, z.B. Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid, Calciumhydroxid und Magnesiumhydroxid. Ebenso können als Basen auch Ammoniak und Derivate des Ammoniaks eingesetzt werden, beispielsweise Triethylamin, Monomethanolamin, Diethanolamin, Triethanolamin und Morpholin. Die Hydrolyse der Homo- und Copolymerisate der N-Vinylamide der Formel III wird soweit geführt, daß weniger als 10, vorzugsweise 1 bis 9 mol-% der in den Polymerisaten enthaltenen Einheiten der Formel I in Einheiten der Formel II überführt sind. Vorzugsweise verwendet man bei dem erfindungsgemäßen Verfahren zu weniger als 10 mol-% hydrolysiertes Poly-N-vinylformamid mit einem K-Wert von 160 bis 250. Daneben kommen auch Copolymerisate in Betracht, die bis zu 50 Gew.-%, vorzugsweise bis zu 30 Gew.-%, mindestens eines anderen ethylenisch ungesättigten Monomeren einpolymerisiert enthalten. Als Comonomere für die N-Vinylamide der Formel III eignen sich beispielsweise Vinylacetat, Vinylpropionat, C₁- bis C₄-Alkylvinylether, N-Vinylpyrrolidon, sowie Ester, Nitrile und Amide von ethylenisch ungesättigten C₃- bis C₈-Carbonsäuren, insbesondere Ester, Nitrile und Amide von Acrylsäure oder Methacrylsäure. Verfahren zur Herstellung der hydrolysierten Homo- und Copolymerisate von Verbindungen der Formel III sind bekannt. Die hydrolysierten Polymerisate können als wäßrige Lösung, als Wasser-in-Öl-Polymeremulsion, als Pulver oder als Perlpolymerisat vorliegen. Perlpolymerisate werden beispielsweise nach dem bekannten Verfahren der umgekehrten Suspensionspolymerisation hergestellt. Die oben beschriebenen, weniger als 10 mol-% Vinylamineinheiten der Formel II enthaltenden Homo- und Copolymerisate werden erfindungsgemäß einem Störstoffe enthaltenden Papierstoff als Entwässerungs-, Retentions- und Flockungsmittel in Mengen von 0,002 bis 0,1, vorzugsweise 0,005 bis 0,05 Gew.-%, bezogen auf trockenen Papierstoff, zugesetzt. Die erfindungsgemäß einzusetzenden Polymerisate werden - ebenso wie bei Anwendung anderer hochmolekularer wasserlöslicher Polymerisate üblich - in sehr verdünnter wäßriger Lösung zum Papierstoff gegeben. Die Konzentration in der wäßrigen Lösung liegt im allgemeinen zwischen 0,01 und 0,1 Gew.-%. Gegenüber den bekannten Verfahren zur Herstellung von Papier, Pappe und Karton aus störstoffhaltigen Papierstoffen liegen die wesentlichen Vorteile des erfindungsgemäßen Verfahrens in der geringen Empfindlichkeit der zu weniger als 10 mol-% Einheiten der Formel II enthaltenden Polymerisate gegen die Anwesenheit von Störstoffen sowie in der Tatsache, daß kein zusätzliches Fixiermittel für das hochmolekulare Polymere, wie in der EP-A-0 249 891 beschrieben, verwendet werden muß.However, bases can also be used for the hydrolysis, for example metal hydroxides of metals of the 1st and 2nd main group of the Periodic Table of the Elements, for example lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. Ammonia and derivatives of ammonia, for example triethylamine, monomethanolamine, diethanolamine, triethanolamine and morpholine, can also be used as bases. The hydrolysis of the homo- and copolymers of the N-vinylamides of the formula III is carried out to such an extent that less than 10, preferably 1 to 9 mol% of the units of the formula I contained in the polymers are converted into units of the formula II. Preferably less than 10 mol% of hydrolyzed poly-N-vinylformamide with a K value of 160 to 250 is used in the process according to the invention. In addition, copolymers are also suitable which contain up to 50% by weight, preferably up to 30% Wt .-%, at least one other ethylenically unsaturated monomer copolymerized. Suitable comonomers for the N-vinylamides of the formula III are, for example, vinyl acetate, vinyl propionate, C₁- to C₄-alkyl vinyl ether, N-vinylpyrrolidone, and also esters, nitriles and amides of ethylenically unsaturated C₃- to C₈-carboxylic acids, in particular esters, nitriles and amides of acrylic acid or methacrylic acid. Processes for the preparation of the hydrolyzed homopolymers and copolymers of compounds of the formula III are known. The hydrolyzed polymers can be present as an aqueous solution, as a water-in-oil polymer emulsion, as a powder or as a bead polymer. Bead polymers are prepared, for example, by the known reverse suspension polymerization process. The above-described homopolymers and copolymers containing less than 10 mol% of vinylamine units of the formula II are, according to the invention, a pulp containing impurities as drainage, retention and flocculants in amounts of 0.002 to 0.1, preferably 0.005 to 0.05,% by weight. -%, based on dry paper stock added. The Polymers to be used according to the invention are added to the paper stock in a very dilute aqueous solution, as is customary when using other high molecular weight water-soluble polymers. The concentration in the aqueous solution is generally between 0.01 and 0.1% by weight. Compared to the known processes for the production of paper, cardboard and cardboard from paper materials containing interfering substances, the main advantages of the process according to the invention are the low sensitivity of the polymers containing less than 10 mol% of units of formula II to the presence of interfering substances and the fact that that no additional fixative for the high molecular weight polymer, as described in EP-A-0 249 891, has to be used.
Die in den Beispielen angegebenen Teile sind Gewichtsteile. Die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe. Der K-Wert der Polymerisate wurde nach H. Fikentscher, Cellulosechemie, Band 13, 58 bis 64 und 71 bis 74 (1932) bestimmt; dabei bedeutet K=k.10³. Die K-Werte der Polymerisate wurden bei einer Polymerisatkonzentration von 0,1 Gew.-% in 5 gew.-%iger wäßriger Kochsalzlösung bei 25°C bestimmt.The parts given in the examples are parts by weight. The percentages relate to the weight of the fabrics. The K value of the polymers was determined according to H. Fikentscher, Cellulosechemie, Volume 13, 58 to 64 and 71 to 74 (1932); where K = k.10³. The K values of the polymers were determined at a polymer concentration of 0.1% by weight in 5% by weight aqueous sodium chloride solution at 25 ° C.
1 l der zu prüfenden Papierstoffsuspension wird jeweils in einem Schopper-Riegler-Testgerät entwässert. Die Zeit, die für verschiedene Auslaufvolumina ermittelt wird, wird als Kriterium für die Entwässerungsgeschwindigkeit der jeweils untersuchten Stoffsuspension gewertet. Die Entwässerungszeiten wurden nach einem Durchlauf von 500 bzw. 600 ml Wasser ermittelt.1 l of the pulp suspension to be tested is dewatered in a Schopper-Riegler test device. The time that is determined for different outlet volumes is evaluated as a criterion for the drainage rate of the substance suspension examined in each case. The drainage times were determined after a run of 500 or 600 ml of water.
Sie wird mit Hilfe eines Photometers bestimmt und ist ein Maß für die Retention von Fein- und Füllstoffen. Sie wird in Prozent angegeben. Je höher der Wert für die optische Durchlässigkeit ist, desto besser ist die Retention.It is determined using a photometer and is a measure of the retention of fine and fillers. It is given in percent. The higher the value for the optical permeability, the better the retention.
Die Ladungsdichte der hydrolysierten Polymerisate auf Basis von Poly-N-vinylformamid wurde mit Hilfe einer enzymatischen Ameisensäurebestimmungsmethode ermittelt (Firmenschrift "Methoden der enzymatischen Lebensmittelanalytik" von Boehringer Mannheim GmbH, 1984).The charge density of the hydrolyzed polymers based on poly-N-vinylformamide was determined using an enzymatic formic acid determination method (company publication "Methods of Enzymatic Food Analysis" by Boehringer Mannheim GmbH, 1984).
Folgende Polymerisate wurden als Entwässerungs- und Retentionsmittel getestet:The following polymers were tested as drainage and retention aids:
Polymer 1: Hydrolysiertes Poly-N-vinylformamid, das 94,5 mol-% Vinylformamid-Einheiten (Formel I mit R¹, R² = H) und 5,5 mol-% Vinylamin-Einheiten (vgl. Formel II mit R¹ = H) enthielt und einen K-Wert von 218 hatte.Polymer 1: hydrolyzed poly-N-vinylformamide which contains 94.5 mol% of vinylformamide units (formula I with R 1, R 2 = H) and 5.5 mol% of vinylamine units (cf. formula II with R 1 = H) contained and had a K value of 218.
Polymer 2: Partiell hydrolysiertes Poly-N-vinylformamid, das 96,5 mol-% N-Vinylformamid-Einheiten (vgl. Formel I mit R¹, R² = H) und 3,5 mol-% Vinylamin-Einheiten (Formel II mit R¹ = H) enthielt und einen K-Wert von 218 hatte.Polymer 2: Partially hydrolyzed poly-N-vinylformamide, the 96.5 mol% N-vinylformamide units (see. Formula I with R¹, R² = H) and 3.5 mol% vinylamine units (formula II with R¹ = H) and had a K value of 218.
Polymer 3: Partiell hydrolysiertes Poly-N-vinylformamid, das 93,3 mol-% N-Vinylformamid-Einheiten (Formel I mit R¹, R² = H) und 6,7 mol-% Vinylamin-Einheiten (vgl. Formel II mit R¹ = H) enthielt und einen K-Wert von 218 hatte.Polymer 3: Partially hydrolyzed poly-N-vinylformamide which contains 93.3 mol% of N-vinylformamide units (formula I with R 1, R 2 = H) and 6.7 mol% of vinylamine units (cf. formula II with R 1 = H) and had a K value of 218.
Zum Vergleich wurden folgende Polymerisate getestet:The following polymers were tested for comparison:
Polymer 4: Homopolymerisat aus N-Vinylformamid mit einem K-Wert von 218.Polymer 4: homopolymer of N-vinylformamide with a K value of 218.
Polymer 5: Hydrolysiertes Poly-N-vinylformamid, das 89,9 mol-% N-Vinylformamid-Einheiten und 10,1 mol-% Vinylamin-Einheiten enthielt und einen K-Wert von 218 hatte.Polymer 5: Hydrolyzed poly-N-vinylformamide, which contained 89.9 mol% of N-vinylformamide units and 10.1 mol% of vinylamine units and had a K value of 218.
Aus 100 % gemischtem Altpapier wurde eine Pulpe mit einer Stoffdichte von 4 g/l hergestellt. Der pH-Wert in der Stoffsuspension betrug 8,1. Zur Simulation eines deinking-Altpapierstoffes wurden dem Papierstoff 4 % Wasserglas, bezogen auf trockenen Papierstoff, zugesetzt. Proben dieses Papierstoffs wurden jeweils in Gegenwart der in Tabelle 1 angegebenen Polymerisate entwässert. Die Polymerisate wurden in einer Menge von jeweils 0,04 %, bezogen auf trockenen Papierstoff, eingesetzt. Die Entwässerungszeiten für 600 ml Filtrat im Schopper-Riegler-Testgerät und die optische Durchlässigkeit des dabei erhaltenen Filtrats sind in Tabelle 1 angegeben. Im Vergleichsbeispiel 3 wurde der oben beschriebene Papierstoff ohne jeden weiteren Zusatz entwässert.
Aus 80 Teilen TMP-Stoff, 20 Teilen gebleichtem Sulfatzellstoff und 30 Teilen Kaolin als Füllstoff wurde eine Pulpe mit der Stoffdichte 4 g/l hergestellt. Der pH-Wert wurde durch Zugabe von Alaun auf 6,0 eingestellt. Zur Simulation eines störstoffhaltigen Papierstoffs wurden pro Liter 50 ml eines wäßrigen TMP-Extrakts aus einer großtechnischen TMP-Produktion zugefügt. Zu Proben dieses Papierstoffs wurden die in Tabelle 2 angegebenen Polymerisate in einer Menge von 0,02 % Polymer, bezogen auf trockenen Papierstoff, zugesetzt sowie die Entwässerungszeit für 500 ml Filtrat im Schopper-Riegler-Testgerät sowie die optische Durchlässigkeit bestimmt. Dabei wurden folgende Ergebnisse erhalten:
Man stellte eine Pulpe aus 100 % ungebleichtem Sulfatzellstoff mit einer Stoffdichte von 5 g/l her. Der pH-Wert betrug 7,9. Eine Probe dieses Papierstoffs sowie Proben dieses Stoffs, die die in Tabelle 3 angegebenen Zusätze in einer Menge von 0,02 % Polymer, bezogen auf trockene Fasern enthielten, wurden in einem Schopper-Riegler-Testgerät entwässert. Die Entwässerungszeit wurde für 500 ml Filtrat im Testgerät bestimmt. Die dabei erhaltenen Ergebnisse sind in Tabelle 3 angegeben.
Claims (3)
- A process for the production of paper, board and cardboard from paper stocks containing interfering substances by drainage in the presence of polymers which contain, as characteristic polymerized components, units of the formulae
- A process as claimed in claim 1, wherein polymers which contain the units of the formula II in amounts of from 1 to 9 mol % are used.
- A process as claimed in claim 1 or 2, wherein R¹ and R² in the formulae I and II are each hydrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4002065 | 1990-01-25 | ||
| DE4002065A DE4002065A1 (en) | 1990-01-25 | 1990-01-25 | METHOD FOR PRODUCING PAPER, CARDBOARD AND CARDBOARD FROM PAPER CONTAINING SUBSTANCES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0438755A1 EP0438755A1 (en) | 1991-07-31 |
| EP0438755B1 true EP0438755B1 (en) | 1994-03-16 |
Family
ID=6398705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90125089A Expired - Lifetime EP0438755B1 (en) | 1990-01-25 | 1990-12-21 | Paper and board-paper making process from paper materials containing perturbating compounds |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5098521A (en) |
| EP (1) | EP0438755B1 (en) |
| JP (1) | JP2921609B2 (en) |
| AT (1) | ATE103023T1 (en) |
| CA (1) | CA2034869C (en) |
| DE (2) | DE4002065A1 (en) |
| DK (1) | DK0438755T3 (en) |
| ES (1) | ES2050350T3 (en) |
| FI (1) | FI102688B1 (en) |
| NO (1) | NO176526C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005090678A1 (en) * | 2004-03-16 | 2005-09-29 | Basf Aktiengesellschaft | Method for producing paper, paperboard and cardboard |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232553A (en) * | 1992-01-24 | 1993-08-03 | Air Products And Chemicals, Inc. | Fines retention in papermaking with amine functional polymers |
| US5401588A (en) * | 1992-12-23 | 1995-03-28 | Georgia-Pacific Resins Inc. | Gypsum microfiber sheet material |
| US5380403A (en) * | 1993-03-22 | 1995-01-10 | Air Products And Chemicals, Inc. | Amine functional poly(vinyl alcohol) for improving properties of recycled paper |
| BR9406395A (en) * | 1993-05-10 | 1996-02-13 | Grace W R & Co | Paper production process |
| US5700893A (en) * | 1993-11-12 | 1997-12-23 | Betzdearborn Inc. | Water-soluble cationic copolymers and their use as flocculants and drainage aids |
| US5529699A (en) * | 1993-11-12 | 1996-06-25 | W. R. Grace & Co.-Conn. | Water-soluble cationic copolymers and their use as flocculants |
| US5516852A (en) * | 1993-11-12 | 1996-05-14 | W. R. Grace & Co.-Conn. | Method of producing water-soluble cationic copolymers |
| US5720888A (en) * | 1993-11-12 | 1998-02-24 | Betzdearborn Inc. | Water-soluble cationic copolymers and their use as flocculants |
| US5473033A (en) * | 1993-11-12 | 1995-12-05 | W. R. Grace & Co.-Conn. | Water-soluble cationic copolymers and their use as drainage retention aids in papermaking processes |
| US6273998B1 (en) | 1994-08-16 | 2001-08-14 | Betzdearborn Inc. | Production of paper and paperboard |
| US20030192664A1 (en) * | 1995-01-30 | 2003-10-16 | Kulick Russell J. | Use of vinylamine polymers with ionic, organic, cross-linked polymeric microbeads in paper-making |
| DE19716821A1 (en) * | 1997-04-22 | 1998-10-29 | Basf Ag | Process for the production of paper, cardboard and cardboard |
| CN1906359A (en) * | 2004-03-30 | 2007-01-31 | 日油瑞新株式会社 | Pitch controlling agent |
| US8916026B2 (en) | 2010-11-16 | 2014-12-23 | Basf Se | Manufacture of cellulosic pulp sheets |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3128478A1 (en) * | 1981-07-18 | 1983-02-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING LINEAR, BASIC POLYMERISATS |
| FI70230C (en) * | 1981-07-18 | 1986-09-15 | Basf Ag | RAKKEDJIGA BASISKA POLYMERISAT FOERFARANDE FOER DERAS FRAMSTAELLNING OCH DERAS ANVAENDNING |
| DE3620065A1 (en) * | 1986-06-14 | 1987-12-17 | Basf Ag | METHOD FOR PRODUCING PAPER, CARDBOARD AND CARDBOARD |
-
1990
- 1990-01-25 DE DE4002065A patent/DE4002065A1/en not_active Withdrawn
- 1990-12-21 DE DE90125089T patent/DE59005019D1/en not_active Expired - Lifetime
- 1990-12-21 EP EP90125089A patent/EP0438755B1/en not_active Expired - Lifetime
- 1990-12-21 AT AT90125089T patent/ATE103023T1/en not_active IP Right Cessation
- 1990-12-21 DK DK90125089.4T patent/DK0438755T3/en active
- 1990-12-21 ES ES90125089T patent/ES2050350T3/en not_active Expired - Lifetime
-
1991
- 1991-01-09 US US07/639,097 patent/US5098521A/en not_active Expired - Lifetime
- 1991-01-22 FI FI910328A patent/FI102688B1/en active IP Right Grant
- 1991-01-23 JP JP3006194A patent/JP2921609B2/en not_active Expired - Lifetime
- 1991-01-24 CA CA002034869A patent/CA2034869C/en not_active Expired - Lifetime
- 1991-01-24 NO NO910283A patent/NO176526C/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005090678A1 (en) * | 2004-03-16 | 2005-09-29 | Basf Aktiengesellschaft | Method for producing paper, paperboard and cardboard |
| CN1934315B (en) * | 2004-03-16 | 2010-08-18 | 巴斯福股份公司 | Method for producing paper, paperboard and cardboard |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2921609B2 (en) | 1999-07-19 |
| CA2034869A1 (en) | 1991-07-26 |
| EP0438755A1 (en) | 1991-07-31 |
| CA2034869C (en) | 2001-08-14 |
| FI910328A0 (en) | 1991-01-22 |
| US5098521A (en) | 1992-03-24 |
| ATE103023T1 (en) | 1994-04-15 |
| FI910328A (en) | 1991-07-26 |
| NO176526B (en) | 1995-01-09 |
| DE59005019D1 (en) | 1994-04-21 |
| NO176526C (en) | 1995-04-19 |
| DK0438755T3 (en) | 1994-04-05 |
| JPH04333698A (en) | 1992-11-20 |
| FI102688B (en) | 1999-01-29 |
| NO910283L (en) | 1991-07-26 |
| NO910283D0 (en) | 1991-01-24 |
| DE4002065A1 (en) | 1991-08-01 |
| ES2050350T3 (en) | 1994-05-16 |
| FI102688B1 (en) | 1999-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0249891B1 (en) | Process for producing paper and cardboard | |
| EP0438755B1 (en) | Paper and board-paper making process from paper materials containing perturbating compounds | |
| EP0438707B1 (en) | Process for making paper and board | |
| DE3721426C2 (en) | N-vinylformamide copolymers and process for their preparation | |
| EP1792010B1 (en) | Method for the production of paper, paperboard and cardboard | |
| EP0672212B1 (en) | Use of hydrolysed copolymers of n-vinyl carboxylic acid amides and monoethylenically unsaturated carboxylic acids in the manufacture of paper | |
| DE102004056551A1 (en) | Process for the production of paper, cardboard and cardboard with high dry strength | |
| DE10315363A1 (en) | Aqueous slurries of finely divided fillers, process for their preparation and their use for the production of filler-containing papers | |
| EP0193111A2 (en) | Process for producing paper with a high dry strength | |
| WO2006066769A2 (en) | Papers with a high filler material content and high dry strength | |
| EP1727938B1 (en) | Method for producing paper, paperboard and cardboard | |
| EP0663031B1 (en) | Methods of dyeing paper | |
| DE4436317A1 (en) | Prodn. of paper with improved screen draining and retention | |
| DE2335330A1 (en) | POLYMERISATES CONTAINING N- (ALKYLAMINO) - AND / OR N- (ALKYLAMMONIUM) -ACRYLAMIDES AS RETENTION AIDS AND DEWATERING AIDS IN PAPER PRODUCTION | |
| EP0553135B1 (en) | Paper, paperboard and cardboard internal sizing process | |
| DE1264942C2 (en) | METHOD OF MANUFACTURING PAPER | |
| EP0384268B1 (en) | Process for the fixation of impurities in paper making | |
| DE3124011A1 (en) | WATER-SOLUBLE POLYMERISATE FROM DI-C (DOWN ARROW) - 1 (DOWN ARROW) - TO C (DOWN ARROW) 3 (DOWN ARROW) -ALKYL-AMINONEOPENTYL (METH) ACRYLATES AND THEIR USE AS DETERMINATION-DETERGENT DETERGENT DETERGENT | |
| DE60112739T2 (en) | DRAINAGE AID FOR PAPER PRODUCTION | |
| DE1617204C (en) | Resin glue masses and processes for their production | |
| DE102004061605A1 (en) | Manufacture of paper products in presence of aqueous elutriate containing fine, coated filler materials, adds specified additional cationic and amphoteric polymers | |
| DE3530477C2 (en) | ||
| DE102005029010A1 (en) | Production of paper, paperboard and cardboard comprises adding of polymer containing vinylamine units and an anionic polymer compound to a paper material, draining the paper material and drying the paper products | |
| CH496079A (en) | Olefin terpolymers having pendant amide and carboxylic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19901221 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT CH DE DK ES FR GB IT LI SE |
|
| 17Q | First examination report despatched |
Effective date: 19930510 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT CH DE DK ES FR GB IT LI SE |
|
| REF | Corresponds to: |
Ref document number: 103023 Country of ref document: AT Date of ref document: 19940415 Kind code of ref document: T |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| REF | Corresponds to: |
Ref document number: 59005019 Country of ref document: DE Date of ref document: 19940421 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19940328 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2050350 Country of ref document: ES Kind code of ref document: T3 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| EAL | Se: european patent in force in sweden |
Ref document number: 90125089.4 |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20071215 Year of fee payment: 18 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090105 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20091211 Year of fee payment: 20 Ref country code: CH Payment date: 20091215 Year of fee payment: 20 Ref country code: SE Payment date: 20091207 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20091218 Year of fee payment: 20 Ref country code: GB Payment date: 20091216 Year of fee payment: 20 Ref country code: FR Payment date: 20091221 Year of fee payment: 20 Ref country code: ES Payment date: 20100113 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20091217 Year of fee payment: 20 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20101220 |
|
| EUG | Se: european patent has lapsed | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20101220 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20110610 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20101222 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20101221 |