EP0013969A1 - Process for producing a paper having a high dry-strength and a low wet-strength - Google Patents

Process for producing a paper having a high dry-strength and a low wet-strength Download PDF

Info

Publication number
EP0013969A1
EP0013969A1 EP80100302A EP80100302A EP0013969A1 EP 0013969 A1 EP0013969 A1 EP 0013969A1 EP 80100302 A EP80100302 A EP 80100302A EP 80100302 A EP80100302 A EP 80100302A EP 0013969 A1 EP0013969 A1 EP 0013969A1
Authority
EP
European Patent Office
Prior art keywords
paper
strength
acrylic acid
weight
methacrylic acid
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
EP80100302A
Other languages
German (de)
French (fr)
Other versions
EP0013969B1 (en
Inventor
Juergen Dr. Hartmann
Joachim Dr. Stedefeder
Walter Denzinger
Sigberg Dr. Pfohl
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
Priority to AT80100302T priority Critical patent/ATE1591T1/en
Publication of EP0013969A1 publication Critical patent/EP0013969A1/en
Application granted granted Critical
Publication of EP0013969B1 publication Critical patent/EP0013969B1/en
Expired legal-status Critical Current

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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • the viscosity of the polymer salts in 2% strength aqueous solution at a temperature of 20 ° C. is 5 to 100 mPas (Brookfield viscometer, 20 revolutions / minute).
  • the homopolymers and copolymers are prepared by known processes by polymerizing the monomers, cf. US Pat. No. 2,819,189 and US Pat. No. 2,999,038.
  • the monomers or mixtures thereof are polymerized continuously or batchwise with the aid of radical polymerization initiators, preferably in water. If the alkali metal or alkaline earth metal salts of acrylic acid or methacrylic acid are already used in the polymerization of the monomers, the copolymer salt solutions to be used according to the invention are obtained directly.
  • Acrylic acid and / or methacrylic acid can be polymerized with the corresponding amides or nitriles in water in the manner of a precipitation polymerization.
  • the resulting copolymers can be neutralized directly with alkali or alkaline earth metal hydroxides.
  • the homopolymers or copolymers obtained in the precipitation polymerization in water can be isolated, dried and mixed with one or more dry, powdered alkali metal hydroxides or alkaline earth metal hydroxides or oxides. These powdery mixtures can then be easily dissolved in water to give a clear solution.
  • the homopolymers or copolymers are neutralized after the polymerization with alkali metal hydroxides or alkaline earth metal hydroxides or alkaline earth metal oxides.
  • the sodium and potassium as well as the calcium and magnesium salts of the copolymers mentioned above are of particular importance.
  • the alkali salts according to the invention do not include the ammonium salts of the copolymers.
  • the polymers contain 91 to 100, preferably 95 to 100% by weight of acrylic acid and / or methacrylic acid and 0 to 9, preferably up to 5% by weight of acrylonitrile, methacrylonitrile, acrylamide or methacrylamide, vinyl acetate, maleic anhydride, diisobutene and optionally acrylic ester or methacrylic acid ester.
  • the esters are preferably derived from monohydric, primary alcohols having 1 to 4 carbon atoms.
  • the calcium and magnesium salts of homopolymers of acrylic acid and methacrylic acid are of particular importance for the process according to the invention.
  • Calcium and magnesium salts and mixtures of alkaline earth and alkali salts of homopolymers of acrylic acid or methacrylic acid and copolymers of acrylic acid and acrylamide, acrylic acid and acrylonitrile, acrylic acid, methacrylic acid and acrylamide, and copolymers of acrylic acid, acrylamide and methacrylamide are preferably used.
  • the carboxyl groups of the polymers are at least at least 30% neutralized with alkaline earth ions.
  • the degree of neutralization is generally 70 to 100%.
  • the mixing ratio of the alkaline earth to alkali salts is preferably 30 to 50 to 70 to 50.
  • a 2% aqueous solution of the alkali or alkaline earth metal salts to be used according to the invention has a viscosity (Brookfield 20 / min) of 5 to 100, preferably 10 to 30 mPas at a temperature of 20 ° C.
  • the pH of the copolymer salt solution is in the range between 4.0 and 10.0.
  • the water-soluble alkali and alkaline earth salts of the polymers in question are applied to the paper in the form of a 1 to 10% strength aqueous solution.
  • the paper can be impregnated with the alkali or alkaline earth salt solution of the copolymers, e.g. in a size press, or spray a solution of the copolymer salt onto the paper.
  • the absorption of preparation solution depends on the absorbency of the paper used. In relation to the solids, to achieve a good increase in the dry strength of the paper, it is sufficient to impregnate the paper with 1 to 4% by weight of the alkali metal or alkaline earth metal salts of the polymers described.
  • the increase in the strength of the paper is immediately after drying the paper under usual conditions, e.g. Temperatures of 80 to 110 ° C, obtained. It is not necessary to age the impregnated paper.
  • the alkali metal and alkaline earth metal salts of the polymers to be used according to the invention also use together with the starch solutions and copolymer solutions which are frequently used in practice and which contain 2 to 10% by weight, preferably 2 to 6% by weight, of starch and 1 to 3% by weight of the alkali and alkaline earth metal salts of polymers to be used according to the invention.
  • the papers can be made from a variety of fiber materials such as sulfite or sulfate pulp (bleached or unbleached), wood pulp or waste paper.
  • the use of the alkaline earth metal salts of polymers of acrylic acid and / or methacrylic acid and the comonomers mentioned under b) as surface application agents for paper leads to an unexpected increase in the dry strength of the paper without the wet strength of the paper being appreciably increased.
  • the dry strength properties of the paper which are noticeably improved, are e.g. the tear length, burst pressure, pick resistance, tear resistance and the GMT value.
  • the invention is illustrated by the following examples.
  • the parts given in the examples are parts by weight, the percentages relate to the weight.
  • the indicated viscosities were measured at a temperature of 20 ° C in a Brookfield viscometer at 20 revolutions / minute.
  • the dry tear length was determined in accordance with DIN 53 112, sheet 1 and the wet tear length in accordance with DIN 53 112, sheet 2.
  • the pick resistance of the paper was determined according to the Dennison wax test.
  • a homopolymer of acrylic acid which was obtained by polymerizing acrylic acid in aqueous solution using potassium peroxide disulfate as a catalyst, is neutralized with magnesium hydroxide.
  • a 2% aqueous solution of the magnesium salt of the homopolymer is prepared, which has a pH of 5.0.
  • a wood-free, unsized offset paper produced on a paper machine with a freeness of 25 ° SR, 14% ash (kaolin) and 2% alum and a weight of 80 g / m 2 is mixed with a 2% aqueous solution of the above-mentioned magnesium salt Impregnated homopolymer of acrylic acid and then dried at a temperature of 100 ° C.
  • Table 1 shows the viscosity of the preparation solution, the amount of pure polymer salt applied to the paper, based on the weight of the paper, and some properties of the paper obtained.
  • Example 1 The homopolymer of acrylic acid described in Example 1 is neutralized with ammonia instead of magnesium oxide and used as a 2% solution at a pH of 5.0 as an impregnating agent for the offset paper specified in Example 1 (Table 1).
  • Example 1 The homopolymer of acrylic acid described in Example 1 is used in non-neutralized form as a 2% aqueous solution at a pH of 2.5 as an impregnating agent for the offset paper specified in Example 1.
  • Table 1 shows the properties of the paper obtained, together with those properties of the paper which were measured after treating the paper with water and drying (comparative example 1c).
  • a 2% solution this copolymer is applied to a wood-free, unsized offset paper with 1% alum, a freeness of 25 ° SR, 10% ash (kaolin) and a weight of 80 g / m 2 .
  • the impregnated paper is dried at a temperature of 100 ° C. Further information on the preparation solution and the properties of the impregnated paper can be found in Table 2.
  • the copolymer of 95% acrylic acid and 5% acrylamide described in Example 2 is neutralized with ammonia instead of calcium hydroxide and used as a 2% aqueous solution at a pH of 6.0 as an impregnating agent for the offset paper specified in Example 2 (Table 2).
  • the copolymer of 95% acrylic acid and 5% acrylamide given in Example 2 is used without neutralization in the form of a 2% aqueous solution, which has a pH of 2.5, for impregnating paper, which is described in Example 2 .
  • the paper was dried at the same temperature as in Example 2.
  • the results are shown in Table 2.
  • Table 2 gives the values which are obtained when the paper described in Example 2 is impregnated with water and dried at 100.degree.
  • the examples and comparative examples show that the polymer salts to be used according to the invention compared to the corresponding ammonium salts or the polyacids lead to a further increase in the dry strength of the paper without undesirably increasing the wet strength of the paper.

Abstract

A process for the manufacture of paper having a high dry strength and a low wet strength, by treating the surface of the paper with an aqueous solution of an alkali metal and/or alkaline earth metal salt of a polymer of (a) from 91 to 100% by weight of acrylic acid and/or methacrylic acid and (b) from 0 to 9% by weight of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, maleic anhydride, diisobutylene, an ester of acrylic acid and/or an ester of methacrylic acid, which has a viscosity of from 5 to 100 mPas in 2% strength aqueous solution at 20 DEG C., and drying the impregnated paper. The polymer is generally employed in an amount of from 1 to 4% by weight, based on dry paper, and increases the dry strength of the paper without substantially increasing the wet strength.

Description

In der DE-PS 27 41 753 wird ein Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Naßfestigkeit durch Behandeln der Oberfläche des Papiers mit wasserlöslichen Salzen von Polymerisaten auf Basis äthylenisch ungesättigter Carbonsäuren vorgeschlagen, das dadurch gekennzeichnet ist, daß als Salze von Polymerisaten wasserlösliche Alkali- und/oder Erdalkalisalze von Copolymerisaten aus

  • a) 90 bis 30 Gew.% Acrylsäure und/oder Methacrylsäure,
  • b) 10 bis 70 Gew.% Acrylnitril, Methacrylnitril, Acrylamid und/oder Methacrylamid sowie ggf.
  • c) bis zu 30 Gew.% eines Acrylsäure- oder Methacrylsäureesters,

die in 2 %-iger wäßriger Lösung bei einer Temperatur von 20°C eine Viskosität von 5 bis 100 mPas (Brookfield-Viskosimeter, 20 Umdrehungen/Minute) haben, verwendet werden.In DE-PS 27 41 753 a process for the production of paper with high dry strength and low wet strength by treating the surface of the paper with water-soluble salts of polymers based on ethylenically unsaturated carboxylic acids is proposed, which is characterized in that water-soluble salts of polymers Alkali and / or alkaline earth metal salts from copolymers
  • a) 90 to 30% by weight of acrylic acid and / or methacrylic acid,
  • b) 10 to 70% by weight of acrylonitrile, methacrylonitrile, acrylamide and / or methacrylamide and, if appropriate
  • c) up to 30% by weight of an acrylic or methacrylic ester,

which have a viscosity of 5 to 100 mPas (Brookfield viscometer, 20 revolutions / minute) in 2% aqueous solution at a temperature of 20 ° C.

Es wurde gefunden, daß man ebenfalls Papier mit hoher Trockenfestigkeit und niedriger Naßfestigkeit durch Behandeln der Oberfläche des Papiers mit wäßrigen Lösungen von Polymerisaten erhält, wenn wasserlösliche Alkali- und/ oder Erdalkalisalze von Polymerisaten aus

  • a) 91 bis 100 Gew.% Acrylsäure und/oder Methacrylsäure und
  • b) 0 bis 9 Gew.% Acrylnitril, Methacrylnitril, Acrylamid, Methacrylamid, Vinylacetat, Maleinsäureanhydrid, Diisobuten, Acrylsäure- und/oder Methacrylsäureester verwendet werden.
It has been found that paper with high dry strength and low wet strength can also be obtained by treating the surface of the paper with aqueous solutions of polymers when water-soluble alkali and / or alkaline earth metal salts are made from polymers
  • a) 91 to 100 wt.% Acrylic acid and / or methacrylic acid and
  • b) 0 to 9% by weight of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, maleic anhydride, diisobutene, acrylic acid and / or methacrylic acid esters can be used.

Die Viskosität der Polymerisatsalze beträgt in 2 %-iger ' wäßriger Lösung bei einer Temperatur von 20°C 5 bis 100 mPas (Brookfield-Viskosimeter, 20 Umdrehungen/Minute).The viscosity of the polymer salts in 2% strength aqueous solution at a temperature of 20 ° C. is 5 to 100 mPas (Brookfield viscometer, 20 revolutions / minute).

Die Homo- und Copolymerisate werden nach bekannten Verfahren durch Polymerisieren der Monomeren hergestellt, vgl. US-PS 2 819 189 und US-PS 2 999 038. Die Monomeren bzw. deren Mischungen werden dabei kontinuierlich oder diskontinuierlich mit Hilfe von radikalischen Polymerisationsinitiatoren, vorzugsweise in Wasser, polymerisiert. Wenn man bei der Polymerisation der Monomeren bereits die Alkali- bzw. Erdalkalisalze der Acrylsäure oder Methacrylsäure einsetzt, erhält man direkt die gemäß Erfindung zu verwendenden Copolymerisatsalz-Lösungen.' Acrylsäure und/oder Methacrylsäure können mit den entsprechenden Amiden oder Nitrilen in Wasser nach Art einer Fällungspolymerisation polymerisiert werden. Die dabei anfallenden Copolymerisate können direkt mit Alkali- bzw. Erdalkalihydroxiden neutralisiert werden.The homopolymers and copolymers are prepared by known processes by polymerizing the monomers, cf. US Pat. No. 2,819,189 and US Pat. No. 2,999,038. The monomers or mixtures thereof are polymerized continuously or batchwise with the aid of radical polymerization initiators, preferably in water. If the alkali metal or alkaline earth metal salts of acrylic acid or methacrylic acid are already used in the polymerization of the monomers, the copolymer salt solutions to be used according to the invention are obtained directly. Acrylic acid and / or methacrylic acid can be polymerized with the corresponding amides or nitriles in water in the manner of a precipitation polymerization. The resulting copolymers can be neutralized directly with alkali or alkaline earth metal hydroxides.

Es ist jedoch auch möglich, bei der Polymerisation zu 10 bis 40 % mit Ammonium-, Alkali- oder Erdalkaliionen neutralisierte Acrylsäure bzw. Methacrylsäure in wäßriger Lösung zu polymerisieren und die erhaltene wäßrige Polymerisatlösung anschließend mit Alkali- bzw. Erdalkalisalzen vollständig zu neutralisieren. Ein Herstellverfahren für die Copolymerisate, bei dem teilweise mit Ammoniumionen neutralisierte Acrylsäure oder Methacrylsäure eingesetzt wird, ist aus der DE-AS 20 04 676 bekannt. Die Polymerisate können auch nach dem Verfahren der umgekehrten Suspensionspolymerisation, das aus der DE-PS 1 081 228 bekannt ist sowie nach dem inversen Emulsionspolymerisationsverfahren gemäß der DE-PS 1 089 173 hergestellt werden.However, it is also possible to polymerize in the polymerization to 10 to 40% neutralized with ammonium, alkali or alkaline earth ions acrylic acid or methacrylic acid in aqueous solution and then to completely neutralize the aqueous polymer solution obtained with alkali or alkaline earth metal salts. A production process for the copolymers, in which acrylic acid or methacrylic acid partially neutralized with ammonium ions is used, is known from DE-AS 20 04 676. The polymers can also be prepared by the reverse suspension polymerization process known from DE-PS 1 081 228 and by the inverse emulsion polymerization process according to DE-PS 1 089 173.

Man kann jedoch auch die bei der Fällungspolymerisation in Wasser erhaltenen Homo- oder Copolymerisate isolieren, trocknen und mit einem oder mehreren trockenen, pulverförmigen Alkalihydroxiden bzw. Erdalkalihydroxiden oder -oxiden mischen. Diese pulvrigen Mischungen können dann ohne Schwierigkeiten in Wasser gelöst werden, wobei man eine klare Lösung erhält.However, the homopolymers or copolymers obtained in the precipitation polymerization in water can be isolated, dried and mixed with one or more dry, powdered alkali metal hydroxides or alkaline earth metal hydroxides or oxides. These powdery mixtures can then be easily dissolved in water to give a clear solution.

Sofern bei der Polymerisation nicht schon die Alkali- bzw. Erdalkalisalze der Acrylsäure oder Methacrylsäure eingesetzt werden, neutralisiert man die Homo- oder Copolymerisate im Anschluß an die Polymerisation mit Alkalihydroxiden bzw. Erdalkalihydroxiden oder Erdalkalioxiden. Besondere Bedeutung haben die Natrium- und Kalium- sowie die Calcium- und Magnesiumsalze der oben genannten Copolymerisate. Die Alkalisalze gemäß der Erfindung umfassen jedoch nicht die Ammoniumsalze der Copolymerisate. Die Polymerisate enthalten 91 bis 100, vorzugsweise 95 bis 100 Gew.% Acrylsäure und/oder Methacrylsäure sowie 0 bis 9, vorzugsweise bis zu 5 Gew.% Acrylnitril, Methacrylnitril, Acrylamid oder Methacrylamid, Vinylacetat, Maleinsäureanhydrid, Diisobuten sowie gegebenenfalls Acrylester oder Methacrylsäureester. Die Ester leiten sich vorzugsweise von einwertigen, primären Alkoholen mit 1 bis 4 Kohlenstoffatomen ab. Besondere Bedeutung für das erfindungsgemäße Verfahren haben die Calcium- und Magnesiumsalze von Homopolymerisaten der Acrylsäure und Methacrylsäure.If the alkali metal or alkaline earth metal salts of acrylic acid or methacrylic acid are not already used in the polymerization, the homopolymers or copolymers are neutralized after the polymerization with alkali metal hydroxides or alkaline earth metal hydroxides or alkaline earth metal oxides. The sodium and potassium as well as the calcium and magnesium salts of the copolymers mentioned above are of particular importance. However, the alkali salts according to the invention do not include the ammonium salts of the copolymers. The polymers contain 91 to 100, preferably 95 to 100% by weight of acrylic acid and / or methacrylic acid and 0 to 9, preferably up to 5% by weight of acrylonitrile, methacrylonitrile, acrylamide or methacrylamide, vinyl acetate, maleic anhydride, diisobutene and optionally acrylic ester or methacrylic acid ester. The esters are preferably derived from monohydric, primary alcohols having 1 to 4 carbon atoms. The calcium and magnesium salts of homopolymers of acrylic acid and methacrylic acid are of particular importance for the process according to the invention.

Vorzugsweise verwendet man Calcium- und Magnesiumsalze sowie Mischungen von Erdalkali- und Alkalisalzen von Hompolymerisaten der Acrylsäure oder Methacrylsäure sowie Copolymerisate aus Acrylsäure und Acrylamid, Acrylsäure und Acrylnitril, Acrylsäure, Methacrylsäure und Acrylamid, und Copolymerisate aus Acrylsäure, Acrylamid und Methacrylamid. Die Carboxylgruppen der Polymerisate sind zu mindestens 30 % mit Erdalkaliionen neutralisiert. Der Neutralisationsgrad beträgt im allgemeinen 70 bis 100 %. Das Mischungsverhältnis der Erdalkali- zu Alkalisalzen beträgt vorzugsweise 30 bis 50 zu 70 bis 50.Calcium and magnesium salts and mixtures of alkaline earth and alkali salts of homopolymers of acrylic acid or methacrylic acid and copolymers of acrylic acid and acrylamide, acrylic acid and acrylonitrile, acrylic acid, methacrylic acid and acrylamide, and copolymers of acrylic acid, acrylamide and methacrylamide are preferably used. The carboxyl groups of the polymers are at least at least 30% neutralized with alkaline earth ions. The degree of neutralization is generally 70 to 100%. The mixing ratio of the alkaline earth to alkali salts is preferably 30 to 50 to 70 to 50.

Eine 2 %-ige wäßrige Lösung der erfindungsgemäß zu verwendenden Alkali- bzw. Erdalkalisalze hat bei einer Temperatur von 20°C eine Viskosität (Brookfield 20/min) von 5 bis 100, vorzugsweise 10 bis 30 mPas. Der pH-Wert der Copolymerisatsalz-Lösung liegt in dem Bereich zwischen 4,0 und 10,0.A 2% aqueous solution of the alkali or alkaline earth metal salts to be used according to the invention has a viscosity (Brookfield 20 / min) of 5 to 100, preferably 10 to 30 mPas at a temperature of 20 ° C. The pH of the copolymer salt solution is in the range between 4.0 and 10.0.

Die wasserlöslichen Alkali- und Erdalkalisalze der in Betracht kommenden Polymerisate werden in Form einer 1 bis 10 %-igen wäßrigen Lösung auf das Papier aufgebracht. Man kann das Papier mit der Alkali- bzw. Erdalkalisalzlösung der Copolymerisate imprägnieren, z.B. in einer Leimpresse, oder eine Lösung des Copolymerisatsalzes auf das Papier aufsprühen. Die Aufnahme an Präparationslösung ist von der Saugfähigkeit des eingesetzten Papiers abhängig. Bezogen auf die Feststoffe reicht es zur Erzielung einer guten Trockenfestigkeitssteigerung des Papiers aus, das Papier mit 1 bis 4 Gew.% der beschriebenen Alkali- bzw. Erdalkalisalze der Polymerisate zu imprägnieren.The water-soluble alkali and alkaline earth salts of the polymers in question are applied to the paper in the form of a 1 to 10% strength aqueous solution. The paper can be impregnated with the alkali or alkaline earth salt solution of the copolymers, e.g. in a size press, or spray a solution of the copolymer salt onto the paper. The absorption of preparation solution depends on the absorbency of the paper used. In relation to the solids, to achieve a good increase in the dry strength of the paper, it is sufficient to impregnate the paper with 1 to 4% by weight of the alkali metal or alkaline earth metal salts of the polymers described.

Die Erhöhung der Festigkeit des Papiers wird direkt nach der Trocknung des Papiers unter üblichen Bedingungen, z.B. Temperaturen von 80 bis 110°C, erhalten. Eine Alterung des imprägnierten Papiers ist nicht erforderlich. Von besonderem Vorteil ist auch die Tatsache, daß die erfindungsgemäß zu verwendenden Alkali- und Erdalkalisalze der Polymerisate auch zusammen mit den häufig in der Praxis eingesetzten Stärkelösungen und Copolymerisatlösungen verwenden, die 2 bis 10 Gew.%, vorzugsweise 2 bis 6 Gew.% Stärke und 1 bis 3 Gew.% der gemäß Erfindung einzusetzenden Alkali- und Erdalkalisalze von Polymerisaten enthalten.The increase in the strength of the paper is immediately after drying the paper under usual conditions, e.g. Temperatures of 80 to 110 ° C, obtained. It is not necessary to age the impregnated paper. Also of particular advantage is the fact that the alkali metal and alkaline earth metal salts of the polymers to be used according to the invention also use together with the starch solutions and copolymer solutions which are frequently used in practice and which contain 2 to 10% by weight, preferably 2 to 6% by weight, of starch and 1 to 3% by weight of the alkali and alkaline earth metal salts of polymers to be used according to the invention.

Es können alle bekannten Papierqualitäten z.B. Schreib-, Druck- und Verpackungspapiere mit den erfindungsgemäß zu verwendenen Produkten imprägniert werden. Die Papiere können dabei aus einer Vielzahl von Fasermaterialien, wie Sulfit- oder Sulfat-Zellstoff (gebleicht oder ungebleicht), Holzschliff oder Altpapier hergestellt sein. Die Verwendung der Erdalkalisalze von Polymerisaten aus Acrylsäure und/ oder Methacrylsäure und den unter b) genannten Comonomeren als Oberflächenauftragsmittel für Papier führt zu einer unerwarteten Erhöhung der Trockenfestigkeit des Papiers, ohne daß dabei die Naßfestigkeit des Papiers nennenswert erhöht wird. Bei den Trockenfestigkeitseigenschaften des Papiers, die merklich verbessert werden, handelt es sich z.B. um die Reißlänge, den Berstdruck, die Rupffestigkeit, Weiterreißfestigkeit und den GMT-Wert.All known paper qualities e.g. Writing, printing and packaging papers are impregnated with the products to be used according to the invention. The papers can be made from a variety of fiber materials such as sulfite or sulfate pulp (bleached or unbleached), wood pulp or waste paper. The use of the alkaline earth metal salts of polymers of acrylic acid and / or methacrylic acid and the comonomers mentioned under b) as surface application agents for paper leads to an unexpected increase in the dry strength of the paper without the wet strength of the paper being appreciably increased. The dry strength properties of the paper, which are noticeably improved, are e.g. the tear length, burst pressure, pick resistance, tear resistance and the GMT value.

Die Erfindung wird anhand der folgenden Beispiele näher erläutert. Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Prozentangaben beziehen sich auf das Gewicht. Die angegebenen Viskositäten wurden bei einer Temperatur von 20°C in einem Brookfield-Viskosimeter bei 20 Umdrehungen/Minute gemessen. Die Trockenreißlänge wurde gemäß DIN 53 112, Blatt 1 und die Naßreißlänge gemäß DIN 53 112, Blatt 2, bestimmt. Die Rupffestigkeit des Papiers wurde nach dem Dennison-Wachs-Test ermittelt.The invention is illustrated by the following examples. The parts given in the examples are parts by weight, the percentages relate to the weight. The indicated viscosities were measured at a temperature of 20 ° C in a Brookfield viscometer at 20 revolutions / minute. The dry tear length was determined in accordance with DIN 53 112, sheet 1 and the wet tear length in accordance with DIN 53 112, sheet 2. The pick resistance of the paper was determined according to the Dennison wax test.

Beispiel 1example 1

Ein Homopolymerisat der Acrylsäure, das durch Polymerisieren von Acrylsäure in wäßriger Lösung mit Hilfe von Kaliumperoxiddisulfat als Katalysator erhalten wurde, wird mit Magnesiumhydroxid neutralisiert. Es wird eine 2 %-ige wäßrige Lösung des Magnesiumsalzes des Homopolymerisates hergestellt, die einen pH-Wert von 5,0 aufweist.A homopolymer of acrylic acid, which was obtained by polymerizing acrylic acid in aqueous solution using potassium peroxide disulfate as a catalyst, is neutralized with magnesium hydroxide. A 2% aqueous solution of the magnesium salt of the homopolymer is prepared, which has a pH of 5.0.

Ein auf einer Papiermaschine hergestelltes holzfreies, ungeleimtes Offsetpapier mit einem Mahlgrad von 25°SR, 14 % Asche (Kaolin) und 2 % Alaun und einem Gewicht von 80 g/m2 wird mit einer 2 %-igen wäßrigen Lösung des oben genannten Magnesiumsalzes des Homopolymerisates der Acrylsäure imprägniert und anschließend bei einer Temperatur von 100°C getrocknet. In der Tabelle 1 sind die Viskosität der Präparationslösung, die auf das Papier aufgetragene Menge des reinen Polymerisatsalzes, bezogen auf das Gewicht des Papiers, sowie einige Eigenschaften des erhaltenen Papiers zusammengestellt.A wood-free, unsized offset paper produced on a paper machine with a freeness of 25 ° SR, 14% ash (kaolin) and 2% alum and a weight of 80 g / m 2 is mixed with a 2% aqueous solution of the above-mentioned magnesium salt Impregnated homopolymer of acrylic acid and then dried at a temperature of 100 ° C. Table 1 shows the viscosity of the preparation solution, the amount of pure polymer salt applied to the paper, based on the weight of the paper, and some properties of the paper obtained.

Vergleichsbeispiel laComparative example la

Das im Beispiel 1 beschriebene Homopolymerisat der Acrylsäure wird anstelle von Magnesiumoxid mit Ammoniak neutralisiert und als 2 %-ige Lösung bei einem pH-Wert von 5,0 als Imprägnierungsmittel für das im Beispiel 1 angegebene Offsetpapier verwendet (Tabelle 1).The homopolymer of acrylic acid described in Example 1 is neutralized with ammonia instead of magnesium oxide and used as a 2% solution at a pH of 5.0 as an impregnating agent for the offset paper specified in Example 1 (Table 1).

Vergleichsbeispiel 1bComparative Example 1b

Das im Beispiel 1 beschriebene Homopolymerisat der Acrylsäure wird in nicht neutralisierter Form als 2 %-ige wäßrige Lösung bei einem pH-Wert von 2,5 als Imprägnierungsmittel für das im Beispiel 1 angegebene Offsetpapier verwendet. In der Tabelle 1 sind die Eigenschaften des erhaltenen Papiers zusammen mit denjenigen Eigenschaften des Papiers zusammengestellt, die nach Behandeln des Papiers mit Wasser und Trocknen gemessen wurden (Vergleichsbeispiel 1c).

Figure imgb0001
The homopolymer of acrylic acid described in Example 1 is used in non-neutralized form as a 2% aqueous solution at a pH of 2.5 as an impregnating agent for the offset paper specified in Example 1. Table 1 shows the properties of the paper obtained, together with those properties of the paper which were measured after treating the paper with water and drying (comparative example 1c).
Figure imgb0001

Beispiel 2Example 2

Ein Copolymerisat aus 95 % Acrylsäure und 5 % Acrylamid (hergestellt durch Polymerisieren von Acrylsäure und Acrylamid in wäßriger Lösung mit Kaliumperoxidisulfat als Katalysator wird durch Umsetzung mit Caiciumhydroxid in das Calciumsalz (pH-Wert = 6,0) umgewandelt. Eine 2 %-ige Lösung dieses Copolymerisates wird auf ein holzfreies, ungeleimtes Offsetpapier mit 1 % Alaun, einem Mahlgrad von 25°SR, 10 % Asche (Kaolin) und einem Gewicht von 80 g/m2 aufgebracht.A copolymer of 95% acrylic acid and 5% acrylamide (produced by polymerizing acrylic acid and acrylamide in aqueous solution with potassium peroxydisulfate as a catalyst is converted into the calcium salt (pH = 6.0) by reaction with calcium hydroxide. A 2% solution this copolymer is applied to a wood-free, unsized offset paper with 1% alum, a freeness of 25 ° SR, 10% ash (kaolin) and a weight of 80 g / m 2 .

Das imprägnierte Papier wird bei einer Temperatur von 100°C getrocknet. Weitere Angaben über die Präparationslösung sowie die Eigenschaften des imprägnierten Papiers können der Tabelle 2 entnommen werden.The impregnated paper is dried at a temperature of 100 ° C. Further information on the preparation solution and the properties of the impregnated paper can be found in Table 2.

Vergleichsbeispiel 2aComparative Example 2a

Das im Beispiel 2 beschriebene Copolymerisat aus 95 % Acrylsäure und 5 % Acrylamid wird anstelle von Calciumhydroxid mit Ammoniak neutralisiert und als 2 %-ige wäßrige Lösung bei einem pH-Wert von 6,0 als Imprägnierungsmittel für das im Beispiel 2 angegebene Offsetpapier verwendet (Tabelle 2).The copolymer of 95% acrylic acid and 5% acrylamide described in Example 2 is neutralized with ammonia instead of calcium hydroxide and used as a 2% aqueous solution at a pH of 6.0 as an impregnating agent for the offset paper specified in Example 2 (Table 2).

Vergleichsbeispiel 2bComparative Example 2b

Das im Beispiel 2 angegebene Copolymerisat aus 95 % Acrylsäure und 5 % Acrylamid wird ohne Neutralisation in Form einer 2 %-igen wäßrigen Lösung, die einen pH-Wert von 2,5 hat, zum Imprägnieren von Papier verwendet, das im Beispiel 2 beschrieben ist. Das Papier wurde bei der selben Temperatur getrocknet, wie im Beispiel 2. Die Ergebnisse sind in Tabelle 2 angegeben. Zum Vergleich sind außerdem in Tabelle 2 die Werte angegeben, die man erhält, wenn man das im Beispiel 2 beschriebene Papier mit Waser imprägniert und bei 100°C trocknet.

Figure imgb0002
Die Beispiele und Vergleichsbeispiele zeigen, daß die erfindungsgemäß zu verwendenden Polymerisatsalze gegenüber den entsprechenden Ammoniumsalzen bzw. den Polysäuren zu einer weiteren Trockenfestigkeitssteigerung des Papiers führen ohne dabei die Naßfestigkeit des Papiers unerwünscht zu erhöhen.The copolymer of 95% acrylic acid and 5% acrylamide given in Example 2 is used without neutralization in the form of a 2% aqueous solution, which has a pH of 2.5, for impregnating paper, which is described in Example 2 . The paper was dried at the same temperature as in Example 2. The results are shown in Table 2. For comparison are also in Table 2 gives the values which are obtained when the paper described in Example 2 is impregnated with water and dried at 100.degree.
Figure imgb0002
 The examples and comparative examples show that the polymer salts to be used according to the invention compared to the corresponding ammonium salts or the polyacids lead to a further increase in the dry strength of the paper without undesirably increasing the wet strength of the paper.

Claims (4)

1. Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Naßfestigkeit durch Behandeln der Oberfläche des Papiers mit wäßrigen Lösungen von Polymerisaten, dadurch gekennzeichnet, daß wasserlösliche Alkali- und/oder Erdalkalisalze von Polymerisaten aus a) 91 bis 100 Gew.% Acrylsäure und/oder Methacrylsäure und b) 0 bis 9 Gew.% Acrylnitril, Methacrylnitril, Acrylamid, Methacrylamid, Vinylacetat, Maleinsäureanhydrid, Diisobuten, Acrylsäure- und/oder Methacrylsäureester
verwendet werden.1. A process for the production of paper with high dry strength and low wet strength by treating the surface of the paper with aqueous solutions of polymers, characterized in that water-soluble alkali and / or alkaline earth metal salts from polymers a) 91 to 100 wt.% Acrylic acid and / or methacrylic acid and b) 0 to 9% by weight of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, maleic anhydride, diisobutene, acrylic acid and / or methacrylic acid ester
be used. 2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß wasserlösliche Calcium- und/oder Magnesiumsalze von Polymerisaten aus a) 91 bis 100 Gew.% Acrylsäure und/oder Methacrylsäure, b) 0 bis 9 Gew.% Acrylnitril, Methacrylnitril, Acrylamid, Methacrylamid, Vinylacetat, Maleinsäureanhydrid, Diisobuten, Acrylsäure- und/oder Methacrylsäureester,
die in 2 %-iger wäßriger Lösung bei einer Temperatur von 20°C eine Viskosität von 5 bis 100 mPas (Brookfield-Viskosität, 20 Umdrehungen/Minute) haben, verwendet werden.2. The method according to claim 1, characterized in that water-soluble calcium and / or magnesium salts of polymers a) 91 to 100% by weight of acrylic acid and / or methacrylic acid, b) 0 to 9% by weight of acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, maleic anhydride, diisobutene, acrylic acid and / or methacrylic acid ester,
which have a viscosity of 5 to 100 mPas (Brookfield viscosity, 20 revolutions / minute) in a 2% strength aqueous solution at a temperature of 20 ° C. 3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß Mischungen aus Alkali- und Erdalkalisalzen der Polymerisate verwendet werden.3. The method according to claim 1, characterized in that mixtures of alkali and alkaline earth metal salts of the polymers are used. 4. Verfahren gemäß den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Polymerisatsalze in einer Menge von 1 bis 4 Gew.%, bezogen auf trockenes Papier, verwendet werden.4. Process according to claims 1 to 3, characterized in that the polymer salts are used in an amount of 1 to 4% by weight, based on dry paper.
EP80100302A 1979-01-27 1980-01-22 Process for producing a paper having a high dry-strength and a low wet-strength Expired EP0013969B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80100302T ATE1591T1 (en) 1979-01-27 1980-01-22 PROCESS FOR MAKING PAPER WITH HIGH DRY STRENGTH AND LOW WET STRENGTH.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2903218 1979-01-27
DE19792903218 DE2903218A1 (en) 1979-01-27 1979-01-27 METHOD FOR PRODUCING PAPER WITH HIGH DRY RESISTANCE AND LOW WET STRENGTH

Publications (2)

Publication Number Publication Date
EP0013969A1 true EP0013969A1 (en) 1980-08-06
EP0013969B1 EP0013969B1 (en) 1982-09-22

Family

ID=6061575

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80100302A Expired EP0013969B1 (en) 1979-01-27 1980-01-22 Process for producing a paper having a high dry-strength and a low wet-strength

Country Status (10)

Country Link
US (1) US4294873A (en)
EP (1) EP0013969B1 (en)
JP (1) JPS55103393A (en)
AT (1) ATE1591T1 (en)
AU (1) AU553980B2 (en)
CA (1) CA1140819A (en)
DE (2) DE2903218A1 (en)
ES (1) ES8105058A2 (en)
FI (1) FI64964C (en)
NO (1) NO157186C (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193111A2 (en) * 1985-02-27 1986-09-03 BASF Aktiengesellschaft Process for producing paper with a high dry strength
EP0372388A3 (en) * 1988-11-30 1991-12-18 Kao Corporation Water-disintegrable cleaning sheet
US5281306A (en) * 1988-11-30 1994-01-25 Kao Corporation Water-disintegrable cleaning sheet
US6159340A (en) * 1996-02-29 2000-12-12 Basf Aktiengesellschaft Hydrolyzed polymers of N-vinylcarboxamides as paper, paperboard and cardboard dry strength enhancers

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2584508B2 (en) * 1989-02-28 1997-02-26 花王株式会社 Water disintegration paper for cleaning supplies
FR2670516B1 (en) * 1990-12-13 1993-04-09 Hoechst France PROCESS FOR COATING PAPERS AND ITS APPLICATION TO FLEXOGRAPHY.
US5266162A (en) * 1990-12-13 1993-11-30 Societe Francaise Hoechst Process for coating papers and its use in flexographic printing
JP3030976B2 (en) * 1991-09-09 2000-04-10 荒川化学工業株式会社 Rosin emulsion size for papermaking
US5741572A (en) * 1995-02-17 1998-04-21 Lexmark International, Inc. Heat fixing paper or sheet
DE19758479C2 (en) 1997-07-02 2002-07-11 Koehler Decor Gmbh & Co Kg impregnating
EP1656335A1 (en) 2003-08-14 2006-05-17 Basf Aktiengesellschaft Method for the production of (meth)acrolein and/or (meth)acrylic acid
US7390846B2 (en) * 2004-11-30 2008-06-24 Crompton Corporation Wood sizing agents for PVC composites
DE102007010422A1 (en) 2007-03-01 2008-09-04 Basf Se Preparation of a catalyst, useful in the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid, comprises attaching one of the active mass to the surface of the carrier body with the help of a binding agent
DE102009047291A1 (en) 2009-11-30 2010-09-23 Basf Se Producing (meth)acrolein, by heterogeneous catalyzed gas phase-partial oxidation, comprises guiding reaction gas mixture through a fresh fixed catalyst bed present in a reactor at increased temperature
DE102010048405A1 (en) 2010-10-15 2011-05-19 Basf Se Long term operation of heterogeneously catalyzed partial gas phase oxidation of propene to acrolein, comprises conducting reaction gas input mixture containing propene, molecular oxygen and inert gas, through solid catalyst bed
DE102011076931A1 (en) 2011-06-03 2012-12-06 Basf Se Aqueous solution containing acrylic acid and its conjugate base

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR931044A (en) * 1945-02-09 1948-02-11 Ici Ltd Paper treatment process
FR1579215A (en) * 1967-08-30 1969-08-22

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52132A (en) * 1975-06-23 1977-01-05 Nec Corp Memory
JPS5218803A (en) * 1975-08-05 1977-02-12 Nippon Zatsuka Shinkou Sentaa Method of molding wood product
DE2741753B1 (en) 1977-09-16 1979-03-22 Basf Ag Process for making paper with high dry strength and low wet strength

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR931044A (en) * 1945-02-09 1948-02-11 Ici Ltd Paper treatment process
FR1579215A (en) * 1967-08-30 1969-08-22

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0193111A2 (en) * 1985-02-27 1986-09-03 BASF Aktiengesellschaft Process for producing paper with a high dry strength
EP0193111A3 (en) * 1985-02-27 1987-05-20 Basf Aktiengesellschaft Process for producing paper with a high dry strength
EP0372388A3 (en) * 1988-11-30 1991-12-18 Kao Corporation Water-disintegrable cleaning sheet
US5281306A (en) * 1988-11-30 1994-01-25 Kao Corporation Water-disintegrable cleaning sheet
US6159340A (en) * 1996-02-29 2000-12-12 Basf Aktiengesellschaft Hydrolyzed polymers of N-vinylcarboxamides as paper, paperboard and cardboard dry strength enhancers

Also Published As

Publication number Publication date
DE2903218A1 (en) 1980-08-07
AU553980B2 (en) 1986-07-31
FI64964B (en) 1983-10-31
ES488034A0 (en) 1981-04-01
EP0013969B1 (en) 1982-09-22
ES8105058A2 (en) 1981-04-01
JPS55103393A (en) 1980-08-07
NO157186B (en) 1987-10-26
NO800183L (en) 1980-07-28
DE3060860D1 (en) 1982-11-04
ATE1591T1 (en) 1982-10-15
NO157186C (en) 1988-02-03
FI64964C (en) 1984-02-10
AU5489880A (en) 1980-07-31
US4294873A (en) 1981-10-13
CA1140819A (en) 1983-02-08
FI800072A (en) 1980-07-28

Similar Documents

Publication Publication Date Title
EP0013969B1 (en) Process for producing a paper having a high dry-strength and a low wet-strength
EP1819877B1 (en) Method for producing high dry strength paper, paperboard or cardboard
DE1546369C3 (en) Process for making paper, paperboard and the like with improved wet strength. Eliminated from: 1177824
EP1999314B1 (en) Method for producing paper, paperboard and cardboard having high dry strength
EP0216387A2 (en) Process for preparing vinyl amine-containing water soluble copolymers and their use as wet and dry strength agents for paper
EP0193111B1 (en) Process for producing paper with a high dry strength
DE2357165B2 (en) Surface size and coating slip for paper
EP0672212B1 (en) Use of hydrolysed copolymers of n-vinyl carboxylic acid amides and monoethylenically unsaturated carboxylic acids in the manufacture of paper
DE1669231A1 (en) Copolymer pigment binder
DE2425265C2 (en) Preparations for the surface sizing of paper
DE1546468A1 (en) Process for the production of polymer-modified cellulose fibers
DE69725779T2 (en) Sizing paper with latex dispersions from copolymers of hydrophobic monomers and low molecular weight styrene / maleic anhydride polymers
DE2741753B1 (en) Process for making paper with high dry strength and low wet strength
DE2741753C3 (en)
DE2339990C2 (en) Coating compositions for paper and their use
DE1696221C3 (en) Binder for paper coating slips on polyvinyl alcohol-B3 747t
EP0146000B1 (en) Process for preparing paper or card-board having a high dry and wet strength and alcali resistance
DE1771367B2 (en) USE OF ELECTRICALLY CONDUCTIVE PAPER FOR ELECTROGRAPHIC PRINTING
DE1696168C3 (en) Method for gluing paper
DE2040692C3 (en) Process for paper sizing
DE2117682C3 (en) Process for surface sizing of paper
EP0542125B1 (en) Process for separating a binder agent dissolved in water
DE3413447A1 (en) Process for producing paper with high dry strength and low wet strength
CH496079A (en) Olefin terpolymers having pendant amide and carboxylic
DE1617204C (en) Resin glue masses and processes for their production

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

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT NL SE

17P Request for examination filed

Effective date: 19801206

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT NL SE

REF Corresponds to:

Ref document number: 1591

Country of ref document: AT

Date of ref document: 19821015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3060860

Country of ref document: DE

Date of ref document: 19821104

ET Fr: translation filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911218

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19911219

Year of fee payment: 13

Ref country code: CH

Payment date: 19911219

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19920102

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920116

Year of fee payment: 13

Ref country code: DE

Payment date: 19920116

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920124

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920131

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930122

Ref country code: AT

Effective date: 19930122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19930131

Ref country code: BE

Effective date: 19930131

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19930131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930801

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930122

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 80100302.1

Effective date: 19930810

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