EP0039794B1 - Anionic dispersions, process for their preparation and their use as surface sizing agents for paper - Google Patents

Anionic dispersions, process for their preparation and their use as surface sizing agents for paper Download PDF

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Publication number
EP0039794B1
EP0039794B1 EP81102874A EP81102874A EP0039794B1 EP 0039794 B1 EP0039794 B1 EP 0039794B1 EP 81102874 A EP81102874 A EP 81102874A EP 81102874 A EP81102874 A EP 81102874A EP 0039794 B1 EP0039794 B1 EP 0039794B1
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Prior art keywords
polymerization
weight
water
solution
ethylenically unsaturated
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German (de)
French (fr)
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EP0039794A1 (en
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Konrad Dr. Richter
Lothar Dr. Hoehr
Fritz Dr. Reichel
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—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

Definitions

  • DE-A-2 548 393 sizing agents for the mass and surface sizing of paper based on anionic polymers in dispersion form are known, which are obtained by 10 to 60 parts by weight of a solution copolymer from 30 to 90 weight percent of a nonionic ethylenically unsaturated monomers and 70 to 10 percent by weight of an ethylenically unsaturated C 3 to C 5 carboxylic acid and / or maleic anhydride and, to a lesser extent, also monomers containing sulfonic acid groups, 90 to 40 parts by weight of a mixture of ethylenically unsaturated copolymerizable monomers which, on their own, polymerize hydrophobic Form copolymers with a glass transition temperature between + 60 and - 40 ° C, grafted on.
  • dispersions with high solids contents are obtained which result in a relatively low viscosity and alkali-stable sizing, but are sufficiently shear-stable only in the alkaline medium for use in the size press.
  • DE-A-2163 850 discloses a process for the surface sizing of paper and cardboard, in which aqueous dispersions of copolymers of 15 to 60 percent by weight of a nitrile of a, ⁇ -olefinically unsaturated carboxylic acid and other olefinically unsaturated monomers are used as sizing agents.
  • these copolymer dispersions also have sufficient shear stability only in the alkaline medium in order to be able to withstand the mechanical stress in the size press nip without coagulation.
  • this severely limits the applicability of these dispersions because, for example, it is not possible to combine them with acid-reacting substances, such as liquid acid dyes.
  • the object of the invention is to provide an anionic dispersion which, for. B. can be used as a surface sizing agent for paper and its sizing effect and processability is largely independent of the pH of the preparation solution.
  • the anionic dispersions according to the invention are low-foaming and are suitable as surface sizing agents for paper, while maintaining their sizing effect and stability regardless of the pH of the preparation solution. You can also use products containing formaldehyde, e.g. B. urea-formaldehyde or melamine-formaldehyde resins can be combined.
  • the sizes produced with the anionic dispersions according to the invention are resistant to alkalis. It is also possible to glue paper with a wide variety of fiber and filler compositions and with different alum or acid content. In particular, neutral sizing is alum-free, e.g. B. calcium carbonate-containing papers possible.
  • the polymerization takes place in a water-miscible solvent.
  • solvents are monohydric alcohols with 1 to 4 carbon atoms, ethanol, n-propanoi, isopropanol, Ethylene glycol monomethyl ether or dimethylformamide.
  • n-propanol and iso-propanol are used as solvents.
  • the solvents can contain up to 30 weight percent water.
  • nonionic ethylenically unsaturated monomers of group a) are alkenes with 2 to 10 carbon atoms, preferably those with a terminal double bond, such as ethylene or diolefins, in particular butadiene and isoprene, and vinylaromatic monomers, for.
  • Suitable monomers in this group are also carboxylic acid esters of ethylenically unsaturated C 3 - to C s -mono- and dicarboxylic acids and monohydric alcohols with 1 to 18, preferably 4 to 12 carbon atoms, the nitriles of the carboxylic acids mentioned, and vinyl esters of 1 to 12 carbon atoms containing aliphatic Carboxylic acids. From this group of monomers, preference is given to using styrene, n-butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, lauryl acrylate, acrylonitrile, methylacrylonitrile, vinyl acetate and vinyl propionate.
  • amides or substituted amides of a, ⁇ -ethylenically unsaturated mono- or dicarboxylic acids for.
  • B acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diethylaminomethylacrylate, diethylaminoethyl acrylate, dimethylaminopropylacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
  • the compound of formula 11 is preferably used as the monomers of group b) or
  • Some of the monomers containing sulfonic acid groups can be replaced by ethylenically unsaturated mono- and / or dicarboxylic acids or half-esters of dicarboxylic acids. If carboxylic acids are used in the polymerization, they are only present in minor amounts, in this case the monomer mixture of components a) and b) contains up to 4% by weight of copolymerizable ethylenically unsaturated carboxylic acids.
  • the solution polymerization of the monomers a) and b) takes place at temperatures from 20 to 160, preferably 60 to 140 ° C.
  • the water-miscible solvent used in solution polymerization can contain up to 30 percent by weight of water. In general, the content of water in solvent is between 6 and 15 percent by weight.
  • a limitation for the water content of the water-miscible solvent results from the monomer composition and from the fact that a homogeneous solution of a copolymer is produced in the first polymerization stage.
  • the concentration of the polymer in this homogeneous solution can vary within a wide range, e.g. B. between 70 and 20 weight percent.
  • the homogeneous polymer solution is then diluted with water in a weight ratio of 1: 3 to 1:50. Due to the content of sulfonic acid groups in the polymer, it is clearly soluble in the mixture of the water-miscible solvent in which the polymerization was carried out and the added water.
  • the concentration of the solution polymer in the solution diluted with water is in the range from 2 to 25 percent by weight.
  • the aqueous polymer solution, from which the water-miscible organic solvent can optionally be distilled off, serves as a template for the second polymerization stage, in which nonionic ethylenically unsaturated monomers are polymerized in the manner of an emulsion polymerization. Based on 1 part by weight of the solution polymer, 1 to 4 parts by weight of a nonionic ethylenically unsaturated monomer or a mixture of the monomers is used.
  • Suitable nonionic ethylenically unsaturated monomers are all those monomers which are used as monomers of group a) for the preparation of the solution copolymer.
  • Styrene, C 4 -C 8 -alkyl acrylates and methacrylates, such as butyl esters of acrylic acid and methacrylic acid, hexyl acrylate and 2-ethyl-hexyl acrylate, acrylonitrile or vinyl acetate are preferably used.
  • the emulsion polymerization takes place in the temperature range from 40 to 150 ° C., preferably 60 to 100 ° C., using customary amounts of water-soluble polymerization initiators.
  • the upper limit for the polymerization initiators is 4 percent by weight, based on the monomers to be polymerized.
  • Suitable polymerization initiators for emulsion polymerization are, for example, peroxides, hydroperoxides, hydrogen peroxide and inorganic peroxides, e.g. B. hydrogen peroxide, potassium peroxodisulfate but also redox systems, such as. B. potassium peroxodisulfate / addition products of bisulfites to aldehydes and tert-butyl hydroperoxide / ascorbic acid.
  • the emulsion polymerization is preferably carried out in the absence of emulsifiers, but emulsifiers can additionally be used in an amount of up to 3 percent by weight, based on the polymer.
  • emulsifiers are, for example, nonionic emulsifiers which are obtained by ethoxylating phenol or phenol derivatives, e.g. B. octylphenol or nonylphenol can be obtained.
  • Such emulsifiers contain 4 to 30 moles of ethylene oxide per mole of phenol.
  • anionic emulsifiers are suitable, for example, alkyl sulfonates, such as sodium dodecyl sulfonate, sodium lauryl sulfonate, alkyl sulfates, alkylbenzenesulfonic acids or their salts or alkylarylsufonates.
  • alkyl sulfonates such as sodium dodecyl sulfonate, sodium lauryl sulfonate, alkyl sulfates, alkylbenzenesulfonic acids or their salts or alkylarylsufonates.
  • the mixtures of nonionic and anionic emulsifiers can also be added to the dispersion after the emulsion polymer has been prepared. Based on the dispersed polymer, 0.05 to 3 percent by weight of an emulsifier or mixture of emulsifiers is used. Stable anionic dispersions are obtained which are used for the surface sizing of paper.
  • the sizing agent according to the invention is adjusted with water to the concentration that is just required for paper sizing, for example to a polymer content of 0.05 to 1.0 percent by weight, based on the preparation solution.
  • the amount of copolymer. that is applied to the paper for sizing is usually between 0.02 and 3, preferably between 0.3 and 0.8 percent by weight, based on dry paper stock.
  • the anionic dispersions the solids content of which can be up to 50 percent by weight, are diluted with water.
  • the preparation solutions can also contain other auxiliary substances. e.g. B. starch, dyes, wax emulsions and resin glue.
  • the anionic dispersions according to the invention are effective as sizing agents in the entire pH range and do not need to be adjusted to a specific pH. However, it is possible to partially or completely neutralize the dispersions with sodium hydroxide solution, potassium hydroxide solution or ammonia or amines and to use them in this form as sizing agents.
  • the dispersions according to the invention are used as surface sizing agents in the customary manner, ie. H. usually in combination with starch or synthetic dry strength agents, whereby the preparation solution is usually applied to the paper using a size press. It is of course also possible to spray the preparation solution by spraying or dipping or z. B. with the help of the water scraper on the paper webs. The paper treated with the preparation solution is then dried. The glue is already fully developed after drying.
  • the dispersion in 0.01% strength aqueous solution is measured in a cuvette with an edge length of 2.5 cm using light of the wavelength 546 nm.
  • the particle diameter can be calculated (cf. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prague 1976, Edice Marco, Rada D-DATA, SVAZEK D -1).
  • the resulting anionic dispersion had a solids content of 32% and an LD value of 99.
  • the preparation was carried out as for dispersion 4, except that 23 parts of styrene, 8.9 parts of methacrylamido-propanesulfonic acid and 2.35 parts of azoisobutyronitrile, dissolved in 33 parts of dimethylformamide, were heated to 85 ° C. for the prepolymer. After 30 minutes, a further 0.6 parts of the initiator were added. After a further 90 minutes, the prepolymer was dissolved in 205 parts of water and, as in Example 4, the following emulsion polymerization was carried out.
  • the anionic dispersion 5 had an LD value of 96 at a solids content of 33.1%.
  • the prepolymer was prepared under the conditions given in Example 1 from 40 parts lauryl acrylate, 16 parts 2-acrylamido-2-methyl-propanesulfonic acid, 40 parts isopropanol, 4.8 parts Water and 4.0 parts of azoisobutyronitrile.
  • 67 parts of styrene and 37 parts of ethylhexyl acrylate, and 1.3 parts of potassium persulfate were used.
  • the anionic dispersion had an LD value of 94 at a solids content of 28.7%.
  • the prepolymer was prepared from 13 parts of 2-acrylamido-2-methyl-propanesulfonic acid, 25.8 parts of styrene, 32.4 parts of isopropanol, 3.9 parts of water and 3.3 parts of azoisobutyronitrile.
  • 72 parts of styrene and 40 parts of isobutyl acrylate were added.
  • the result was an anionic dispersion with a solids content of 29% and an LD value of 98.
  • comparative dispersion 1 was prepared by polymerizing 67 parts of butyl acrylate, 30 parts of acrylonitrile, 3 parts of methacrylic acid and 3 parts of sodium dodecyl sulfonate as an emulsifier in water to give an anionic dispersion with a solids content of 30% by weight.
  • the LD value was 99.
  • a dispersion was prepared by polymerizing a monomer mixture of 67 parts of butyl acrylate, 30 parts of acrylonitrile, 4.5 parts of vinylsulfonic acid and 3 parts of sodium dodecylsulfonate as emulsifier.
  • An anionic dispersion with a solids content of 40% by weight was obtained.
  • the LD value was 92.
  • a dispersion was prepared by preparing a solution polymer from 130 parts of styrene, 50 parts of acrylic acid and 20 parts of maleic anhydride at 85 ° C., adjusting it ammoniacally and, in addition, a mixture of 300 parts of isobutyl acrylate and 300 Parts of acrylonitrile polymerized at 85 ° C.
  • the dispersions described above were checked for their sizing effect.
  • a non-glued, wood-free offset paper containing 14% ash and 1% alum served as the test paper.
  • the weight per unit area was 70 g / m 2
  • the degree of grinding was 25 ° SR (degree of grinding measured according to Schopper-Riegler, see Ullmanns Encyklopadie der Technische Chemie, 3rd edition, Urban & Schwarzenberg, Kunststoff-Berlin 1962, volume 13, pages 123 and 124 ).
  • the preparation solutions each contained 6 g / l of polymer, based on the solids content of the dispersions and 60 g / l of an oxidatively degraded potato starch. The liquor absorption was 90% in all cases, based on dry paper.
  • the dispersions 1 to 7 according to the invention are compared in the table below with the comparative dispersions 1 to 4. (Dispersion 1 was used in Example 1, dispersion 2 in Example 2, etc.).
  • the sizing preparations described above were also tested for stability on an experimental paper machine.
  • anionic dispersion 1 the preparation solution was heated to a temperature of 60 ° C. and used to glue paper. After a running time of 40 minutes, no deposit formation was found on the size roller application rollers.
  • comparative dispersion 1 the preparation solution was heated to a temperature of 30 ° C. and used as a sizing agent. Deposits appeared on the size press roller after only 15 minutes. The experiment was repeated, but the preparation solution was adjusted to a pH of 9. At a temperature of 30 ° C this preparation solution could be applied to the paper without being deposited on the rollers, but at a temperature of 60 ° C the rollers of the size press were already occupied after 10 minutes.
  • the preparation solution which contained the comparison dispersion 2 as a sizing agent, also showed deposits on the rollers of the size press as soon as the preparation solution was heated to a temperature of 60.degree.
  • the preparation solution which contained the comparative dispersion 3 as a sizing agent, also proved to be stable in the stability test at 60 ° with weakly acidic papers. However, if strongly acidic papers were impregnated, a size press coating gradually formed after 30 minutes because the pH of the preparation solution dropped.
  • Comparative dispersions 1-2 according to DE-A-21 63850 and comparative dispersion 3 according to DE-A-2548393 are therefore clearly inferior to the anionic dispersion according to the invention in terms of sizing effect and / or stability.
  • a non-sized, wood-free offset paper that contained 14% ash and 1% alum and had a basis weight of 70 g / m 2 (freeness 25 ° SR) was sized with a preparation solution containing 4.5 g / 1 polymer, based on the solids content of the anionic dispersion 1 and 60 g / l of an oxidatively degraded potato starch.
  • a preparation solution containing 4.5 g / 1 polymer based on the solids content of the anionic dispersion 1 and 60 g / l of an oxidatively degraded potato starch.
  • the Cobb values were tested with water and with sodium hydroxide solution of various concentrations. The following results were obtained:
  • the sizing of the dispersion according to the invention is therefore resistant to alkalis.
  • the anionic sizing agent 1 can be combined with a melamine-formaldehyde resin in such a way that neither the sizing nor the wet strength effect of the melamine-formaldehyde resin is impaired.
  • Samples of the paper specified in the example with the preparation solutions a) and b) were sized on the surface. The results found are summarized in the table.

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Abstract

1. An anionic dispersion produced by a two-stage polymerization reaction, a mixture of nonionic ethylenically unsaturated monomers containing sulphonic acid groups being copolymerized in the first polymerization stage in the manner of a solution copolymerization in a water-miscible solvent in the presence of a polymerization initiator, which is soluble in the monomer mixture, to give a homogeneous solution, and, after dilution with water, polymerization being carried out in the second polymerization stage in the manner of an emulsion polymerization in the presence of a usual amount of a water-soluble polymerization initiator, characterized in that in the first polymerization stage a mixture of a) 85 to 55% by weight of nonionic ethylenically unsaturated monomers, and b) 15 to 45% by weight of ethylenically unsaturated monomers containing sulphonic acid groups is copolymerized in the presence of 0.015 to 0.15 mole of a polymerization initiator, which is soluble in the monomer mixture, per mole of monomer mixture, the homogeneous polymer solution is diluted with water in a weight ratio of 1 : 3 to 1 : 50, and 1 to 4 parts by weight of at least one nonionic ethylenically unsaturated monomer per part by weight of the solution polymer are polymerized in this polymer solution in the second polymerization stage.

Description

Aus der DE-A-2 548 393 sind Leimungsmittel für die Masse- und Oberflächenleimung von Papier auf der Basis anionischer Polymerisate in Dispersionsform bekannt, die dadurch erhalten werden, daß man auf 10 bis 60 Gewichtsteile eines Lösungscopolymerisates aus 30 bis 90 Gewichtsprozent eines nichtionischen ethylenisch ungesättigten Monomeren und 70 bis 10 Gewichtsprozent einer ethylenisch ungesättigten C3- bis C5-Carbonsäure und/oder Maleinsäureanhydrid und in untergeordnetem Maße auch Sulfonsäuregruppen enthaltende Monomere, 90 bis 40 Gewichsteile eines Gemisches von ethylenisch ungesättigten miteinander copolymerisierbaren Monomeren, die für sich alleine polymerisiert hydrophobe Copolymerisate mit einer Glastemperatur zwischen + 60 und - 40 °C bilden, aufpfropft.DE-A-2 548 393 sizing agents for the mass and surface sizing of paper based on anionic polymers in dispersion form are known, which are obtained by 10 to 60 parts by weight of a solution copolymer from 30 to 90 weight percent of a nonionic ethylenically unsaturated monomers and 70 to 10 percent by weight of an ethylenically unsaturated C 3 to C 5 carboxylic acid and / or maleic anhydride and, to a lesser extent, also monomers containing sulfonic acid groups, 90 to 40 parts by weight of a mixture of ethylenically unsaturated copolymerizable monomers which, on their own, polymerize hydrophobic Form copolymers with a glass transition temperature between + 60 and - 40 ° C, grafted on.

Man erhält auf diese Weise zwar Dispersionen mit hohen Feststoffgehalten, die eine relativ geringe Viskosität und alkalistabile Leimungen ergeben, jedoch nur im alkalischen Medium genügend scherstabil für die Anwendung in der Leimpresse sind.In this way, dispersions with high solids contents are obtained which result in a relatively low viscosity and alkali-stable sizing, but are sufficiently shear-stable only in the alkaline medium for use in the size press.

Aus der DE-A-2163 850 ist ein Verfahren zur Oberflächenleimung von Papier und Karton bekannt, bei dem man als Leimungsmittel wäßrige Dispersionen von Copolymerisaten aus 15 bis 60 Gewichtsprozent eines Nitrils einer a,ß-olefinisch ungesättigten Carbonsäure und anderen olefinisch ungesättigten Monomeren verwendet. Diese Copolymerisatdispersionen besitzen jedoch ebenfalls nur im alkalischen Medium eine ausreichende Scherstabilität, um die mechanische Beanspruchung im Leimpressenspalt ohne Koagulation überstehen zu können. Dadurch ist aber die Anwendbarkeit dieser Dispersionen stark eingeschränkt, weil es beispielsweise nicht möglich ist, sie zusammen mit sauer reagierenden Stoffen, wie etwa flüssigen sauren Farbstoffen, zu kombinieren.DE-A-2163 850 discloses a process for the surface sizing of paper and cardboard, in which aqueous dispersions of copolymers of 15 to 60 percent by weight of a nitrile of a, β-olefinically unsaturated carboxylic acid and other olefinically unsaturated monomers are used as sizing agents. However, these copolymer dispersions also have sufficient shear stability only in the alkaline medium in order to be able to withstand the mechanical stress in the size press nip without coagulation. However, this severely limits the applicability of these dispersions because, for example, it is not possible to combine them with acid-reacting substances, such as liquid acid dyes.

Aufgabe der Erfindung ist es, eine anionische Dispersion zur Verfügung zu stellen, die z. B. als Oberflächenleimungsmittel für Papier verwendet werden kann und dessen Leimungswirkung und Verarbeitbarkeit vom pH-Wert der Präparationslösung weitgehend unabhängig ist.The object of the invention is to provide an anionic dispersion which, for. B. can be used as a surface sizing agent for paper and its sizing effect and processability is largely independent of the pH of the preparation solution.

Die Aufgabe wird erfindungsgemäß gelöst mit anionischen Dispersionen, die durch eine zweistufige Polymerisation hergestellt sind, wobei in der ersten Polymerisationsstufe eine Monomerenmischung aus nichtionischen ethylenisch ungesättigten Monomeren und ethylenisch ungesättigten Sulfonsäuregruppen enthaltenden Monomeren in einem mit Wasser mischbaren Lösungsmittel nach Art einer Lösungscopolymerisation in Gegenwart eines in dem Monomerengemisch löslichen Polymerisationsinitiators zu einer homogenen Lösung copolymerisiert und wobei nach dem Verdünnen mit Wasser in einer zweiten Polymerisationsstufe nach Art einer Emulsionspolymerisation in Gegenwart von üblichen Mengen wasserlöslicher Polymerisationsinitiatoren polymerisiert wird, wenn man in der ersten Polymerisationsstufe eine Monomerenmischung aus

  • a) 85 bis 55 Gewichtsprozent nichtionischen ethylenisch ungesättigten Monomeren und
  • b) 15 bis 45 Gewichtsprozent ethylenisch ungesättigten Sulfonsäuregruppen enthaltenden Monomeren in Gegenwart von 0,015 bis 0,15 Mol pro Mol der Monomerenmischung eines in dem Monomerengemisch löslichen Polymerisationsinitiators copolymerisiert, die homogene Polymerlösung mit Wasser im Gewichtsverhältnis 1: 3 bis 1: 50 verdünnt und in dieser Polymerlösung, bezogen auf 1 Gewichtsteil des Lösungspolymerisats, 1 bis 4 Gewichtsteile mindestens eines nichtionischen ethylenisch ungesättigten Monomeren in der zweiten Polymerisationsstufe polymerisiert.
The object is achieved according to the invention with anionic dispersions which are produced by a two-stage polymerization, in the first polymerization stage a monomer mixture comprising nonionic ethylenically unsaturated monomers and ethylenically unsaturated sulfonic acid groups in a water-miscible solvent in the manner of a solution copolymerization in the presence of a Copolymerized monomer mixture soluble polymerization initiator to a homogeneous solution and polymerized after dilution with water in a second polymerization stage in the manner of an emulsion polymerization in the presence of usual amounts of water-soluble polymerization initiators, if in the first polymerization stage from a monomer mixture
  • a) 85 to 55 percent by weight of nonionic ethylenically unsaturated monomers and
  • b) 15 to 45% by weight of monomers containing ethylenically unsaturated sulfonic acid groups are copolymerized in the presence of 0.015 to 0.15 mol per mol of the monomer mixture of a polymerization initiator which is soluble in the monomer mixture, the homogeneous polymer solution is diluted with water in a weight ratio of 1: 3 to 1:50 and in this Polymer solution, based on 1 part by weight of the solution polymer, polymerized 1 to 4 parts by weight of at least one nonionic ethylenically unsaturated monomer in the second polymerization stage.

Die erfindungsgemäßen anionischen Dispersionen sind schaumarm, als Oberflächenleimungsmittel für Papier geeignet, wobei sie ihre Leimungswirkung und Stabilität unabhängig vom pH-Wert der Präparationslösung behalten. Sie können außerdem mit formaldehydhaltigen Produkten, z. B. Harnstoff-Formaldehyd- oder Melamin-Formaldehyd-Harzen kombiniert werden. Die mit den erfindungsgemäßen anionischen Dispersionen hergestellten Leimungen sind gegen Alkalien beständig. Es ist außerdem möglich, Papier mit unterschiedlichster Faserstoff- und Füllstoffzusammensetzung und mit verschiedenem Alaungehalt bzw. Säuregehalt zu leimen. Insbesondere ist auch die Neutralleimung alaunfreier, z. B. kalziumcarbonathaltiger Papiere möglich. Diese Ergebnisse waren nicht zu erwarten weil man aufgrund der hohen Hydrophile der freien Sulfonsäuregruppen im Copolymerisat annehmen mußte, daß keine ausreichende Hydrophobierung und damit Leimung des Papiers erhalten wird.The anionic dispersions according to the invention are low-foaming and are suitable as surface sizing agents for paper, while maintaining their sizing effect and stability regardless of the pH of the preparation solution. You can also use products containing formaldehyde, e.g. B. urea-formaldehyde or melamine-formaldehyde resins can be combined. The sizes produced with the anionic dispersions according to the invention are resistant to alkalis. It is also possible to glue paper with a wide variety of fiber and filler compositions and with different alum or acid content. In particular, neutral sizing is alum-free, e.g. B. calcium carbonate-containing papers possible. These results were not to be expected because, owing to the high hydrophilicity of the free sulfonic acid groups in the copolymer, it had to be assumed that sufficient hydrophobization and therefore sizing of the paper would not be obtained.

Die erfindungsgemäßen anionischen Dispersionen für die Oberflächenleimung von Papier werden mit Hilfe von zwei unterschiedlichen Polymerisationsverfahren hergestellt. Zunächst wird in einer ersten Polymerisatlonsstufe eine Monomerenmischung aus

  • a) 85 bis 55 Gewichtsprozent nichtionischen ethylenisch ungesättigten Monomeren und
  • b) 15 bis 45 Gewichtsprozent ethylenisch ungesättigten Sulfonsäuregruppen enthaltenden Monomeren in einem mit Wasser mischbaren Lösungsmittel zu einer homogenen Lösung eines Copolymerisates copolymerisiert. Dafür verwendet man Polymerisationsinitiatoren, die in dem Monomerengemisch löslich sind. Im Gegensatz zur üblichen Lösungspolymerisation werden die Initiatoren in einer beträchtlich höheren Menge eingesetzt. Man verwendet 0,015 bis 0,15 Mol Initiator bzw. eines Initiatorgemisches pro Mol der Monomerenmischung. Die Zerfallskonstante der Polymerisationsinitiatoren liegt in dem Bereich von 10-4 bis 10-2 x sec-'. Als Polymerisationsinitiatoren verwendet man beispielsweise Azobisisobuttersäurenitril, Lauroylperoxid, Benzoylperoxid und/oder tert.-Butylperbenzoat.
The anionic dispersions according to the invention for the surface sizing of paper are produced with the aid of two different polymerization processes. First, a monomer mixture is formed in a first polymer stage
  • a) 85 to 55 percent by weight of nonionic ethylenically unsaturated monomers and
  • b) 15 to 45% by weight of monomers containing ethylenically unsaturated sulfonic acid groups are copolymerized in a water-miscible solvent to give a homogeneous solution of a copolymer. For this, polymerization initiators are used which are soluble in the monomer mixture. In contrast to conventional solution polymerization, the initiators are used in a considerably higher amount. 0.015 to 0.15 mol of initiator or of an initiator mixture is used per mol of the monomer mixture. The decay constant of the polymerization initiators is in the range of 10- 4 to 10- 2 x sec- '. Azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide and / or tert-butyl perbenzoate are used as polymerization initiators, for example.

Die Polymerisation erfolgt in einem mit Wasser mischbaren Lösungsmittel. Solche Lösungsmittel sind beispielsweise einwertige Alkohole mit 1 bis 4 Kohlenstoffatomen, Ethanol, n-Propanoi, lsopropanol, Ethylenglykolmonomethylether oder auch Dimethylformamid.The polymerization takes place in a water-miscible solvent. Examples of such solvents are monohydric alcohols with 1 to 4 carbon atoms, ethanol, n-propanoi, isopropanol, Ethylene glycol monomethyl ether or dimethylformamide.

Vorzugsweise verwendet man als Lösungsmittel n-Propanol und iso-Propanol. Die Lösungsmittel können bis zu 30 Gewichtsprozent Wasser enthalten.Preferably n-propanol and iso-propanol are used as solvents. The solvents can contain up to 30 weight percent water.

Als nichtionische ethylenisch ungesättigte Monomere der Gruppe a) kommen beispielsweise Alkene mit 2 bis 10 Kohlenstoffatomen, vorzugsweise solche mit endständiger Doppelbindung, wie Äthylen oder Diolefine, insbesondere Butadien und Isopren sowie vinylaromatische Monomere, z. B. Styrol und substituierte Styrole, z. B. a-Methylstyrol und Äthylstyrol in Betracht. Geeignete Monomere dieser Gruppe sind außerdem Carbonsäureester aus ethylenisch ungesättigten C3- bis Cs-Mono- und Dicarbonsäuren und einwertigen Alkoholen mit 1 bis 18, vorzugsweise 4 bis 12 Kohlenstoffatomen, die Nitrile der genannten Carbonsäuren, sowie Vinylester von 1 bis 12 Kohlenstoffatome enthaltenden aliphatischen Carbonsäuren. Vorzugsweise verwendet man aus dieser Monomerengruppe Styrol, n-Butylacrylat, Isobutylacrylat, Ethylhexylacrylat, Laurylacrylat, Acrylnitril, Methylacrylnitril, Vinylacetat und Vinylpropionat.Examples of nonionic ethylenically unsaturated monomers of group a) are alkenes with 2 to 10 carbon atoms, preferably those with a terminal double bond, such as ethylene or diolefins, in particular butadiene and isoprene, and vinylaromatic monomers, for. B. styrene and substituted styrenes, e.g. B. a-methyl styrene and ethyl styrene into consideration. Suitable monomers in this group are also carboxylic acid esters of ethylenically unsaturated C 3 - to C s -mono- and dicarboxylic acids and monohydric alcohols with 1 to 18, preferably 4 to 12 carbon atoms, the nitriles of the carboxylic acids mentioned, and vinyl esters of 1 to 12 carbon atoms containing aliphatic Carboxylic acids. From this group of monomers, preference is given to using styrene, n-butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, lauryl acrylate, acrylonitrile, methylacrylonitrile, vinyl acetate and vinyl propionate.

Es ist selbstverständlich möglich, auch Mischungen der genannten Monomeren zu verwenden, z. B. Mischungen aus Styrol und Ethylhexylacrylat, Styrol und Butylacrylat, Styrol, Isobutylacrylat und Acrylnitril oder Vinylisobutylefher. Diese Gruppe von Monomeren bildet, wenn sie für allein polymerisiert wird, hydrophobe Polymerisate, d. h. Polymerisate, die in Wasser nicht löslich sind. In untergeordnetem Maße, d. h. bis zu 5 Gewichtsprozent, bezogen auf die Mischung der Monomeren a) und b), können die Lösungspolymerisate wasserlösliche nichtionische Monomere enthalten, z. B. Amide oder substituierte Amide von a,ß-ethylenisch ungesättigten Mono- oder Dicarbonsäuren, z. B. Acrylamid, Methacrylamid, N-Methylolacrylamid, N-Methylolmethacrylamid, Diethylaminomethylacrylat, Diethylaminoethylacrylat, Dimethylaminopropylacrylat, Dimethylaminomethylmethacrylat, Dimethylaminoethylmethacrylat und Diethylaminoethylmethacrylat.It is of course possible to use mixtures of the monomers mentioned, for. B. mixtures of styrene and ethylhexyl acrylate, styrene and butyl acrylate, styrene, isobutyl acrylate and acrylonitrile or vinyl isobutyl ether. This group of monomers, when polymerized alone, forms hydrophobic polymers, i.e. H. Polymers that are not soluble in water. To a lesser extent, i. H. up to 5 percent by weight, based on the mixture of monomers a) and b), the solution polymers can contain water-soluble nonionic monomers, e.g. B. amides or substituted amides of a, β-ethylenically unsaturated mono- or dicarboxylic acids, for. B. acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, diethylaminomethylacrylate, diethylaminoethyl acrylate, dimethylaminopropylacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

Die Monomeren der Gruppe b) sind ethylenisch ungesättigte Sulfonsäuregruppen enthaltende Verbindungen. Es handelt sich hierbei in erster Linie um Sulfonsäuregruppen enthaltende Derivate von Acrylamiden, Methacrylamiden, Acrylsäureestern und Methacrylsäureestern. Diese Verbindungen können z. B. mit Hilfe der allgemeinen Formel I charakterisiert werden :

Figure imgb0001
in der

  • R = H, CH3
  • X = -NH-, -0- und
  • A = C1- bis Ca-Alkylen bedeuten.
The group b) monomers are compounds containing ethylenically unsaturated sulfonic acid groups. These are primarily derivatives of acrylamides, methacrylamides, acrylic acid esters and methacrylic acid esters containing sulfonic acid groups. These connections can e.g. B. can be characterized using the general formula I:
Figure imgb0001
 in the
  • R = H, CH 3
  • X = -NH-, -0- and
  • A = C 1 - to C a -alkylene.

Vorzugsweise verwendet man als Monomere der Gruppe b) die Verbindung der Formel 11

Figure imgb0002
Figure imgb0003
oder
Figure imgb0004
 The compound of formula 11 is preferably used as the monomers of group b)
Figure imgb0002
Figure imgb0003
 or
Figure imgb0004

Ein Teil der Sulfonsäuregruppen enthaltenden Monomeren kann durch ethylenisch ungesättigte Mono- und/oder Dicarbonsäuren bzw. Halbester von Dicarbonsäuren ersetzt werden. Falls Carbonsäuren bei der Polymerisation mitverwendet werden, sind sie nur in untergeordneter Menge anwesend, die Monomerenmischung aus den Komponenten a) und b) enthält in diesem Fall bis zu 4 Gewichtsprozent an copolymerisierbaren ethylenisch ungesättigten Carbonsäuren.Some of the monomers containing sulfonic acid groups can be replaced by ethylenically unsaturated mono- and / or dicarboxylic acids or half-esters of dicarboxylic acids. If carboxylic acids are used in the polymerization, they are only present in minor amounts, in this case the monomer mixture of components a) and b) contains up to 4% by weight of copolymerizable ethylenically unsaturated carboxylic acids.

Die Lösungspolymerisation der Monomeren a) und b) erfolgt bei Temperaturen von 20 bis 160, vorzugsweise 60 bis 140 °C. Das bei der Lösungspolymerisation eingesetzte mit Wasser mischbare Lösungsmittel kann bis zu 30 Gewichtsprozent Wasser enthalten. Im allgemeinen liegt der Gehalt von Wasser in Lösungsmittel zwischen 6 und 15 Gewichtsprozent. Eine Begrenzung für den Wassergehalt des mit Wasser mischbaren Lösungsmittels ergibt sich aufgrund der Monomerenzusammensetzung und daraus, daß in der ersten Polymerisationsstufe eine homogene Lösung eines Copolymerisates hergestellt wird. Die Konzentration des Polymerisates in dieser homogenen Lösung kann in einem weiten Bereich schwanken, z. B. zwischen 70 und 20 Gewichtsprozent.The solution polymerization of the monomers a) and b) takes place at temperatures from 20 to 160, preferably 60 to 140 ° C. The water-miscible solvent used in solution polymerization can contain up to 30 percent by weight of water. In general, the content of water in solvent is between 6 and 15 percent by weight. A limitation for the water content of the water-miscible solvent results from the monomer composition and from the fact that a homogeneous solution of a copolymer is produced in the first polymerization stage. The concentration of the polymer in this homogeneous solution can vary within a wide range, e.g. B. between 70 and 20 weight percent.

Die homogene Polymerlösung wird im Anschluß and die Polymerisation im Gewichtsverhältnis 1 : 3 bis 1 : 50 mit Wasser verdünnt. Aufgrund des Gehaltes an Sulfonsäuregruppen im Polymerisat ist es in der Mischung aus dem mit Wasser mischbaren Lösungsmittel, in dem die Polymerisation erfolgte, und dem zugesetzten Wasser klar löslich. Die Konzentration des Lösungspolymerisates in der mit Wasser verdünnten Lösung liegt in dem Bereich von 2 bis 25 Gewichtsprozent. Die wäßrige Polymerlösung, aus der das mit Wasser mischbare organische Lösungsmittel gegebenenfalls abdestilliert werden kann, dient als Vorlage für die zweite Polymerisationsstufe, in der nichtionische ethylenisch ungesättigte Monomere nach Art einer Emulsionspolymerisation polymerisiert werden. Bezogen auf 1 Gewichtsteil des Lösungspolymerisats verwendet man 1 bis 4 Gewichtsteile eines nichtionischen ethylenisch ungesättigten Monomeren oder eines Gemisches der Monomeren.The homogeneous polymer solution is then diluted with water in a weight ratio of 1: 3 to 1:50. Due to the content of sulfonic acid groups in the polymer, it is clearly soluble in the mixture of the water-miscible solvent in which the polymerization was carried out and the added water. The concentration of the solution polymer in the solution diluted with water is in the range from 2 to 25 percent by weight. The aqueous polymer solution, from which the water-miscible organic solvent can optionally be distilled off, serves as a template for the second polymerization stage, in which nonionic ethylenically unsaturated monomers are polymerized in the manner of an emulsion polymerization. Based on 1 part by weight of the solution polymer, 1 to 4 parts by weight of a nonionic ethylenically unsaturated monomer or a mixture of the monomers is used.

Geeignete nichtionische ethylenisch ungesättigte Monomere sind alle diejenigen Monomeren, die als Monomere der Gruppe a) für die Herstellung des Lösungscopolymerisates verwendet werden. Vorzugsweise verwendet man Styrol, C4- bis C8-Alkylacrylate und -methacrylate, wie Butylester der Acrylsäure und Methacrylsäure, Hexylacrylat und 2-Ethyl-hexylacrylat, Acrylnitril oder Vinylacetat.Suitable nonionic ethylenically unsaturated monomers are all those monomers which are used as monomers of group a) for the preparation of the solution copolymer. Styrene, C 4 -C 8 -alkyl acrylates and methacrylates, such as butyl esters of acrylic acid and methacrylic acid, hexyl acrylate and 2-ethyl-hexyl acrylate, acrylonitrile or vinyl acetate are preferably used.

Die Emulsionspolymerisation erfolgt in dem Temperaturbereich von 40 bis 150 °C, vorzugsweise 60 bis 100 °C unter Verwendung üblicher Mengen an wasserlöslichen Polymerisationsinitiatoren. Die obere Grenze für die Polymerisationsinitiatoren beträgt 4 Gewichtsprozent, bezogen auf die zu polymerisierenden Monomeren. Geeignete Polymerisationsinitiatoren für die Emulsionspolymerisation sind beispielsweise Peroxide, Hydroperoxide, Wasserstoffperoxid und anorganische Peroxide, z. B. Wasserstoffperoxid, Kaliumperoxodisulfat aber auch Redoxsysteme, wie z. B. Kaliumperoxodisulfat/Additionsprodukte von Bisulfiten an Aldehyde sowie tert.-Butylhydroperoxid/Ascorbinsäure.The emulsion polymerization takes place in the temperature range from 40 to 150 ° C., preferably 60 to 100 ° C., using customary amounts of water-soluble polymerization initiators. The upper limit for the polymerization initiators is 4 percent by weight, based on the monomers to be polymerized. Suitable polymerization initiators for emulsion polymerization are, for example, peroxides, hydroperoxides, hydrogen peroxide and inorganic peroxides, e.g. B. hydrogen peroxide, potassium peroxodisulfate but also redox systems, such as. B. potassium peroxodisulfate / addition products of bisulfites to aldehydes and tert-butyl hydroperoxide / ascorbic acid.

Die Emulsionspolymerisation wird vorzugsweise in Abwesenheit von Emulgatoren durchgeführt, jedoch können zusätzlich Emulgatoren in einer Menge bis zu 3 Gewichtsprozent, bezogen auf das Polymerisat, mitverwendet werden. Geeignete Emulgatoren sind beispielsweise nichtionische Emulgatoren, die durch Ethoxylierung von Phenol oder Phenolderivaten, z. B. Octylphenol oder Nonylphenol erhalten werden. Solche Emulgatoren enthalten 4 bis 30 Mol Ethylenoxid pro Mol Phenol. Außerdem eignen sich anionische Emulgatoren beispielsweise Alkylsulfonate, wie Natriumdodecylsulfonat, Natriumlaurylsulfonat, Alkylsulfate, Alkylbenzolsulfonsäuren oder ihre Salze oder Alkylarylsufonate.The emulsion polymerization is preferably carried out in the absence of emulsifiers, but emulsifiers can additionally be used in an amount of up to 3 percent by weight, based on the polymer. Suitable emulsifiers are, for example, nonionic emulsifiers which are obtained by ethoxylating phenol or phenol derivatives, e.g. B. octylphenol or nonylphenol can be obtained. Such emulsifiers contain 4 to 30 moles of ethylene oxide per mole of phenol. In addition, anionic emulsifiers are suitable, for example, alkyl sulfonates, such as sodium dodecyl sulfonate, sodium lauryl sulfonate, alkyl sulfates, alkylbenzenesulfonic acids or their salts or alkylarylsufonates.

Es ist selbstverständlich auch möglich, die Mischungen aus nichtionischen und anionischen Emulgatoren bei der Emulsionspolymerisation zu verwenden. Die Emulgatoren können jedoch auch nach der Herstellung des Emulsionspolymerisates zur Dispersion zugegeben werden. Bezogen auf das dispergierte Polymere verwendet man 0,05 bis 3 Gewichtsprozent eines Emulgators oder Emulgatorengemisches. Man erhält stabile anionische Dispersionen, die für die Oberflächenleimung von Papier eingesetzt werden.It is of course also possible to use the mixtures of nonionic and anionic emulsifiers in the emulsion polymerization. However, the emulsifiers can also be added to the dispersion after the emulsion polymer has been prepared. Based on the dispersed polymer, 0.05 to 3 percent by weight of an emulsifier or mixture of emulsifiers is used. Stable anionic dispersions are obtained which are used for the surface sizing of paper.

Bei der Oberflächenleimung wird das erfindungsgemäße Leimungsmittel mit Wasser auf die Konzentration eingestellt, die für die Papierleimung gerade erforderlich ist, beispielsweise auf einen Polymerisatgehalt von 0,05 bis 1,0 Gewichtsprozent, bezogen auf die Präparationslösung. Die Menge an Copolymerisat. die auf das Papier zur Leimung aufgetragen wird, liegt in der Regel zwischen 0,02 und 3, vorzugsweise zwischen 0,3 und 0,8 Gewichtsprozent, bezogen auf trockenen Papierstoff. Zur Herstellung der Präparationslösungen werden die anionischen Dispersionen, deren Feststoffgehalt bis zu 50 Gewichtsprozent betragen kann, mit Wasser verdünnt. Die Präparationslösungen können außerdem weitere Hilfsstoffe enthalten. z. B. Stärke, Farbstoffe, Wachsemulsionen und Harzleim. Die erfindungsgemäßen anionischen Dispersionen sind im gesamten pH-Bereich als Leimungsmittel wirksam und brauchen nicht auf einen bestimmten pH-Wert eingestellt zu werden. Es ist jedoch möglich, die Dispersionen mit Natronlauge, Kalilauge oder Ammoniak bzw. Aminen teilweise oder vollständig zu neutralisieren und in dieser Form als Leimungsmittel einzusetzen. Die Anwendung der erfindungsgemäßen Dispersionen als Oberflächenleimungsmittel erfolgt in der üblichen Weise, d. h. meist in Kombination mit Stärke oder synthetischen Trockenverfestigungsmitteln, wobei die Präparationslösung in der Regel mit Hilfe einer Leimpresse auf das Papier aufgebracht wird. Es ist selbstverständlich auch möglich, die Präparationslösung durch Sprühen oder Tauchen oder z. B. mit Hilfe des Wasserschabers auf die Papierbahnen aufzubringen. Das mit der Präparationslösung behandelte Papier wird anschließend getrocknet. Die Leimung ist nach dem trocknen bereits voll ausgebildet.In the case of surface sizing, the sizing agent according to the invention is adjusted with water to the concentration that is just required for paper sizing, for example to a polymer content of 0.05 to 1.0 percent by weight, based on the preparation solution. The amount of copolymer. that is applied to the paper for sizing is usually between 0.02 and 3, preferably between 0.3 and 0.8 percent by weight, based on dry paper stock. To prepare the preparation solutions, the anionic dispersions, the solids content of which can be up to 50 percent by weight, are diluted with water. The preparation solutions can also contain other auxiliary substances. e.g. B. starch, dyes, wax emulsions and resin glue. The anionic dispersions according to the invention are effective as sizing agents in the entire pH range and do not need to be adjusted to a specific pH. However, it is possible to partially or completely neutralize the dispersions with sodium hydroxide solution, potassium hydroxide solution or ammonia or amines and to use them in this form as sizing agents. The dispersions according to the invention are used as surface sizing agents in the customary manner, ie. H. usually in combination with starch or synthetic dry strength agents, whereby the preparation solution is usually applied to the paper using a size press. It is of course also possible to spray the preparation solution by spraying or dipping or z. B. with the help of the water scraper on the paper webs. The paper treated with the preparation solution is then dried. The glue is already fully developed after drying.

Die Erfindung wird mit Hilfe der folgenden Beispiele näher erläutert. Die in den Beispielen angegebenen Teile sind Gewichtsteile. Der Leimungsgrad der Papiere mit Hilfe des Cobb-Wertes nach DIN 53132 und der Tintenschwimmzeit bis zum 50 %igen Durchschlag mit einer Normtinte nach DIN 53 126 charakterisiert.The invention is explained in more detail with the aid of the following examples. The parts given in the examples are parts by weight. The degree of sizing of the papers with the help of the Cobb value DIN 53132 and the ink swimming time up to 50% breakthrough with a standard ink according to DIN 53 126.

Beispiele 1 bis 7Examples 1 to 7 Herstellung der Dispersion 1Preparation of the dispersion 1

In einem Polymerisationskessel, der mit Rührer, Rückflußkühler und Destillationseinrichtung ausgestattet ist, werden 60 Teile Styrol, 30 Teile 2-Acrylamido-2-methyl-propansuifosäure, 75 Teile Isopropanol, 17 Teile Wasser und 7,5 Teile Azobisisobuttersäurenitril bei einer Temperatur von 80 °C vermischt und unter Rühren und Rückflußsieden 2 Stunden bei dieser Temperatur polymerisiert. Danach fügt man 508 Teile Wasser zu. Man hält die Temperatur in dem Bereich von 80 bis etwa 85 °C und wartet so lange, bis sich das in der ersten Polymerisationsstufe hergestellte Lösungspolymerisat aufgelöst hat.In a polymerization kettle equipped with a stirrer, reflux condenser and distillation device, 60 parts of styrene, 30 parts of 2-acrylamido-2-methyl-propanesuifoic acid, 75 parts of isopropanol, 17 parts of water and 7.5 parts of azobisisobutyronitrile are added at a temperature of 80 ° C mixed and polymerized with stirring and refluxing for 2 hours at this temperature. Then add 508 parts of water. The temperature is kept in the range from 80 to about 85 ° C. and the process is continued until the solution polymer prepared in the first polymerization stage has dissolved.

In der zweiten Polymerisationsstufe fügt man zu der wäßrigen Lösung des Lösungspolymerisates zunächst 20% einer Lösung von 2,9 Teilen Kaliumperoxodisulfat in 100 Teilen Wasser zu und gibt innerhalb von 2 Stunden eine Monomerenmischung aus 125 Teilen Styrol und 75 Teilen Ethylhexylacrylat zu. Nach Zugabe der Monomerenmischung wird die restliche Initiatorlösung innerhalb eines Zeitraumes von 2 1/4 Stunden zum Reaktionsgemisch zugefügt. Man erhält auf diese Weise eine dünnflüssige anionische Dispersion mit einem Feststoffgehalt von 30 % und einem LD-Wert von 97 (Dispersion 1).In the second polymerization stage, 20% of a solution of 2.9 parts of potassium peroxodisulfate in 100 parts of water are first added to the aqueous solution of the solution polymer, and a monomer mixture of 125 parts of styrene and 75 parts of ethylhexyl acrylate is added over the course of 2 hours. After the monomer mixture has been added, the remaining initiator solution is added to the reaction mixture over a period of 2 1/4 hours. This gives a low-viscosity anionic dispersion with a solids content of 30% and an LD value of 97 (dispersion 1).

Zur Bestimmung des LD-Wertes (Lichtdurchlässigkeit) wird die Dispersion in 0,01 %iger, wäßriger Lösung in einer Küvette mit 2,5 cm Kantenlänge mit Licht der Wellenlänge 546 nm vermessen. Mit Hilfe der « Mie-Theorie » läßt sich daraus der Teilchendurchmesser berechnen (vgl. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prag 1976, Edice Marco, Rada D-DATA, SVAZEK D-1).To determine the LD value (light transmittance), the dispersion in 0.01% strength aqueous solution is measured in a cuvette with an edge length of 2.5 cm using light of the wavelength 546 nm. With the help of the "Mie theory" the particle diameter can be calculated (cf. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prague 1976, Edice Marco, Rada D-DATA, SVAZEK D -1).

Herstellung der Dispersion 2Preparation of the dispersion 2

Man verfährt wie im Beispiel beschrieben und stellt zunächst ein Lösungscopolymerisat aus 60 Teilen Styrol und 25 Teilen 2-Acrylamino-2-methylpropan-sulfosäure her und erhält durch anschließende Emulsionspolymerisation von 25 Teilen Styrol und 110 Teilen Ethylhexylacrylat die anionische Dispersion 2 (LD-Wert 98, Feststoffgehalt 30 %).The procedure is as described in the example, and a solution copolymer is first prepared from 60 parts of styrene and 25 parts of 2-acrylamino-2-methylpropane sulfonic acid, and anionic dispersion 2 (LD value 98) is obtained by subsequent emulsion polymerization of 25 parts of styrene and 110 parts of ethylhexyl acrylate , Solids content 30%).

Herstellung der Dispersion 3Preparation of the dispersion 3

In einem Rührkessel mit Rückflußkühler wurden 47 Teile 97 %iger Ethanol mit 4 Teilen Wasser, 32 Teilen Styrol und 16 Teilen 2-Acrylamido-propansulfonsäure gemischt und 2,3Teile Azobisisobuttersäurenitril zugesetzt. Die Mischung wurde auf 80 °C erhitzt und nach 30 Minuten weitere 0,8 Teile des Initiators zugefügt. Nach weiteren 90 Minuten löste man in 183 Teilen Wasser und fügte 20 % einer Lösung von 1,8 Teilen Kaliumpersulfat in 100 Teilen Wasser zu. Der Rest wurde gleichzeitig mit einer Mischung von 99 Teilen Styrol und 55 Teilen Ethylhexyl-acrylat innerhalb von 2 Stunden zugegeben. Es resultierte eine Dispersion mit einem Feststoffgehalt von 34 % und einem LD-Wert von 91.In a stirred kettle with a reflux condenser, 47 parts of 97% ethanol were mixed with 4 parts of water, 32 parts of styrene and 16 parts of 2-acrylamido-propanesulfonic acid, and 2.3 parts of azobisisobutyronitrile were added. The mixture was heated to 80 ° C. and a further 0.8 part of the initiator was added after 30 minutes. After a further 90 minutes, the mixture was dissolved in 183 parts of water and 20% of a solution of 1.8 parts of potassium persulfate in 100 parts of water were added. The rest was added simultaneously with a mixture of 99 parts of styrene and 55 parts of ethylhexyl acrylate within 2 hours. The result was a dispersion with a solids content of 34% and an LD value of 91.

Herstellung der Dispersion 4Preparation of the dispersion 4

In einem Rührbehälter mit Rückflußkühler wurden 50 Teile Methylglykol, 6,5 Teile Wasser, 32 Teile Styrol und 16 Teile 2-Acrylamino-2-methyl-propansulfosäure mit 3,2 Teilen Azobisisobuttersäurenitril auf 85 °C erhitzt. Nach 30 Minuten setzte man weitere 0,8 Teile des Initiators zu, rührte weitere 90 Minuten bei 95 °C, fügte erst 231 Teile Wasser und dann 20 Teile einer 1,3 %igen Kaliumsulfatlösung in Wasser zu. Danach wurden innerhalb von zwei Stunden gleichzeitig 80Teile der 1,3%igen Kaliumpersulfatlösung und eine Mischung aus 72 Teilen Styrol und 40 Teilen Ethylhexylacrylat zugegeben. Die resultierende anionische Dispersion hatte einen Feststoffgehalt von 32 % und einen LD-Wert von 99.50 parts of methyl glycol, 6.5 parts of water, 32 parts of styrene and 16 parts of 2-acrylamino-2-methyl-propanesulfonic acid were heated to 85 ° C. with 3.2 parts of azobisisobutyronitrile in a stirred tank with a reflux condenser. After 30 minutes, a further 0.8 parts of the initiator were added, the mixture was stirred at 95 ° C. for a further 90 minutes, first 231 parts of water and then 20 parts of a 1.3% strength potassium sulfate solution in water were added. Thereafter, 80 parts of the 1.3% potassium persulfate solution and a mixture of 72 parts of styrene and 40 parts of ethylhexyl acrylate were added simultaneously within two hours. The resulting anionic dispersion had a solids content of 32% and an LD value of 99.

Herstellung der Dispersion 5Preparation of the dispersion 5

Die Herstellung erfolgte wie bei der Dispersion 4, nur werden für das Vorpolymerisat 23 Teile Styrol, 8,9 Teile Methacrylamido-propansulfosäure und 2,35 Teile Azoisobuttersäurenitril, gelöst in 33 Teilen Dimethylformamid, auf 85 °C erhitzt. Nach 30 Minuten setzte man weitere 0,6 Teile des Initiators hinzu. Nach weiteren 90 Minuten wurde das Vorpolymerisat in 205 Teilen Wasser gelöst und wie im Beispiel 4 die folgende Emulsionspolymerisation ausgeführt. Die anionische Dispersion 5 hatte bei einem Feststoffgehalt von 33,1 % einen LD-Wert von 96.The preparation was carried out as for dispersion 4, except that 23 parts of styrene, 8.9 parts of methacrylamido-propanesulfonic acid and 2.35 parts of azoisobutyronitrile, dissolved in 33 parts of dimethylformamide, were heated to 85 ° C. for the prepolymer. After 30 minutes, a further 0.6 parts of the initiator were added. After a further 90 minutes, the prepolymer was dissolved in 205 parts of water and, as in Example 4, the following emulsion polymerization was carried out. The anionic dispersion 5 had an LD value of 96 at a solids content of 33.1%.

Herstellung der Dispersion 6Preparation of the dispersion 6

Das Vorpolymerisat wurde unter den in Beispiel 1 angegebenen Bedingungen aus 40 Teilen Laurylacrylat, 16 Teilen 2-Acrylamido-2-methyl-propansulfosäure, 40 Teilen Isopropanol, 4,8Teilen Wasser und 4,0 Teilen Azoisobuttersäurenitril hergestellt. Zur nachfolgenden Emulsionspolymerisation wurden - analog Beispiel 1 - 67 Teile Styrol und 37 Teile Ethylhexylacrylat, sowie 1,3 Teile Kaliumpersulfat verwendet.The prepolymer was prepared under the conditions given in Example 1 from 40 parts lauryl acrylate, 16 parts 2-acrylamido-2-methyl-propanesulfonic acid, 40 parts isopropanol, 4.8 parts Water and 4.0 parts of azoisobutyronitrile. For the subsequent emulsion polymerization, analogously to Example 1, 67 parts of styrene and 37 parts of ethylhexyl acrylate, and 1.3 parts of potassium persulfate were used.

Die anionische Dispersion hatte bei einem Feststoffgehalt von 28,7 % einen LD-Wert von 94.The anionic dispersion had an LD value of 94 at a solids content of 28.7%.

Herstellung der Dispersion 7Preparation of the dispersion 7

Analog zu Beispiel wurde aus 13 Teilen 2-Acrylamido-2-methyl-propansulfosäure, 25,8 Teilen Styrol, 32,4 Teilen Isopropanol, 3,9 Teilen Wasser und 3,3 Teilen Azoisobuttersäurenitril das Vorpolymerisat hergestellt. Bei der anschließenden Emulsionspolymerisation (Bedingungen wie in Beispiel 1 angegeben) wurden 72 Teile Styrol und 40 Teile iso-Butylacrylat hinzugefügt. Es resultierte eine anionische Dispersion mit einem Feststoffgehalt von 29 % und einem LD-Wert von 98.Analogously to Example, the prepolymer was prepared from 13 parts of 2-acrylamido-2-methyl-propanesulfonic acid, 25.8 parts of styrene, 32.4 parts of isopropanol, 3.9 parts of water and 3.3 parts of azoisobutyronitrile. In the subsequent emulsion polymerization (conditions as given in Example 1), 72 parts of styrene and 40 parts of isobutyl acrylate were added. The result was an anionic dispersion with a solids content of 29% and an LD value of 98.

Vergleichsdispersion 1Comparative dispersion 1

Gemäß der Lehre der DE-A-21 63 850 wurde die Vergleichsdispersion 1 hergestellt, indem man 67 Teile Butylacrylat, 30 Teile Acrylnitril, 3 Teile Methacrylsäure und 3 Teile Natriumdodecylsulfonat als Emulgator in Wasser zu einer anionischen Dispersion mit einem Feststoffgehalt von 30 Gewichtsprozent polymerisierte. Der LD-Wert betrug 99.According to the teaching of DE-A-21 63 850, comparative dispersion 1 was prepared by polymerizing 67 parts of butyl acrylate, 30 parts of acrylonitrile, 3 parts of methacrylic acid and 3 parts of sodium dodecyl sulfonate as an emulsifier in water to give an anionic dispersion with a solids content of 30% by weight. The LD value was 99.

Vergleichsdispersion 2Comparative dispersion 2

Gemäß der Lehre der DE-A-21 63 850 wurde eine Dispersion hergestellt, indem man eine Monomerenmischung aus 67 Teilen Butylacrylat, 30 Teilen Acrylnitril, 4,5 Teilen Vinylsulfonsäure und 3 Teilen Natriumdodecylsulfonat als Emulgator polymerisierte. Man erhielt eine anionische Dispersionen mit einem Feststoffgehalt von 40 Gewichtsprozent. Der LD-Wert betrug 92.According to the teaching of DE-A-21 63 850, a dispersion was prepared by polymerizing a monomer mixture of 67 parts of butyl acrylate, 30 parts of acrylonitrile, 4.5 parts of vinylsulfonic acid and 3 parts of sodium dodecylsulfonate as emulsifier. An anionic dispersion with a solids content of 40% by weight was obtained. The LD value was 92.

Vergleichsdispersion 3Comparative dispersion 3

Gemäß der Lehre der DE-A-25 48 393 wurde eine Dispersion hergestellt, indem man ein Lösungspolymerisat aus 130 Teilen Styrol, 50 Teilen Acrylsäure und 20 Teilen Maleinsäureanhydrid bei 85°C herstellte, ammoniakalisch einstellte und dazu ein Gemisch aus 300 Teilen Isobutylacrylat und 300 Teilen Acrylnitril bei 85 °C polymerisierte.According to the teaching of DE-A-25 48 393, a dispersion was prepared by preparing a solution polymer from 130 parts of styrene, 50 parts of acrylic acid and 20 parts of maleic anhydride at 85 ° C., adjusting it ammoniacally and, in addition, a mixture of 300 parts of isobutyl acrylate and 300 Parts of acrylonitrile polymerized at 85 ° C.

Man erhielt eine anionische Dispersion mit einem Feststoffgehalt von 42 % und einem LD-Wert von 95.An anionic dispersion with a solids content of 42% and an LD value of 95 was obtained.

Vergleichsdispersion 4Comparative dispersion 4

Hier wird gezeigt, daß die Anwendung niederer Initiatormengen entgegen der erfindungsgemäßen Arbeitsweise bei der Darstellung des Vorpolymerisates der erfindungsgemäßen Dispersionen die Leimungswirkung der resultierenden Dispersion ungünstig beeinflußt.It is shown here that the use of low initiator quantities, contrary to the procedure according to the invention, in the preparation of the prepolymer of the dispersions according to the invention adversely affects the sizing effect of the resulting dispersion.

5,95 Teile Styrol in 7,5 Teilen Isopropanol und 0,9 Teilen Wasser wurden analog zu den vorgehenden Beispielen mit 3 Teilen 2-Acrylamldo-2-methyl-propansulfonsäure vermischt und die Mischung mit 0,27 Teilen Azoisobuttersäurenitril als Initiator 2 Stunden lang bei 75 bis 80°C polymerisiert. Die Emulsionspolymerisation erfolgt in üblicher Weise mit 13,2 Teilen Styrol und 7,4 Teilen Ethylenhexylacrylat bei 85 °C. Bei einem Feststoffgehalt von 29,5 % hatte die resultierende anionische Dispersion einen LD-Wert von 37.5.95 parts of styrene in 7.5 parts of isopropanol and 0.9 part of water were mixed analogously to the preceding examples with 3 parts of 2-acrylamldo-2-methyl-propanesulfonic acid and the mixture with 0.27 parts of azoisobutyronitrile as initiator for 2 hours polymerized at 75 to 80 ° C. The emulsion polymerization is carried out in a conventional manner with 13.2 parts of styrene and 7.4 parts of ethylene hexyl acrylate at 85 ° C. With a solids content of 29.5%, the resulting anionic dispersion had an LD value of 37.

Die oben beschriebenen Dispersionen wurden auf ihre Leimungswirkung überprüft. Als Prüfpapier diente ein in der Masse ungeleimtes, holzfreies Offsetpapier, das 14 % Asche und 1 % Alaun enthielt. Das Flächengewicht betrug 70 g/m2, der Mahlgrad 25 °SR (Mahlgrad gemessen nach Schopper-Riegler, vgl. Ullmanns Encyklopädie der technischen Chemie, 3. Auflage, Urban & Schwarzenberg, München-Berlin 1962, Band 13, Seiten 123 und 124). Die Präparationslösungen enthielten jeweils 6 g/I Polymerisat, bezogen auf den Feststoffgehalt der Dispersionen und 60 g/I einer oxidativ abgebauten Kartoffelstärke. Die Flottenaufnahme betrug in allen Fällen 90 %, bezogen auf trockenes Papier.The dispersions described above were checked for their sizing effect. A non-glued, wood-free offset paper containing 14% ash and 1% alum served as the test paper. The weight per unit area was 70 g / m 2 , the degree of grinding was 25 ° SR (degree of grinding measured according to Schopper-Riegler, see Ullmanns Encyklopadie der Technische Chemie, 3rd edition, Urban & Schwarzenberg, Munich-Berlin 1962, volume 13, pages 123 and 124 ). The preparation solutions each contained 6 g / l of polymer, based on the solids content of the dispersions and 60 g / l of an oxidatively degraded potato starch. The liquor absorption was 90% in all cases, based on dry paper.

Die erfindungsgemäßen Dispersionen 1 bis 7 sind in der nachfolgenden Tabelle den Vergleichsdispersionen 1 bis 4 gegenübergestellt. (Die Dispersion 1 wurde im Beispiel 1, die Dispersion 2 im Beispiel 2 usw. verwendet).The dispersions 1 to 7 according to the invention are compared in the table below with the comparative dispersions 1 to 4. (Dispersion 1 was used in Example 1, dispersion 2 in Example 2, etc.).

(Siehe Tabelle Seite 7 f.)(See table on page 7 f.)

Figure imgb0005
Figure imgb0005

Die oben beschriebenen Leimungsmittelpräparationen wurden außerdem auf einer Versuchspapiermaschine bezüglich der Stabilität getestet. Im Fall der anionischen Dispersion 1 wurde die Präparationslösung auf eine Temperatur von 60 °C erwärmt und zum Leimen von Papier verwendet. Nach einer Laufzeit von 40 Minuten konnte auf den Auftragswalzen der Leimpresse keinerlei Belagbildung festgestellt werden. Im Fall der Vergleichsdispersion 1 wurde die Präparationslösung auf eine Temperatur von 30 °C erwärmt und als Leimungsmittel verwendet. Bereits nach 15 Minuten traten Ablagerungen an der Leimpressenwalze auf. Der Versuch wurde wiederholt, jedoch die Präparationslösung auf einen pH-Wert von 9 eingestellt. Bei einer Temperatur von 30°C konnte diese Präparationslösung ohne Ablagerung an den Walzen auf das Papier aufgetragen werden, jedoch belegten sich bei einer Temperatur von 60 °C die Walzen der Leimpresse bereits nach 10 Minuten.The sizing preparations described above were also tested for stability on an experimental paper machine. In the case of anionic dispersion 1, the preparation solution was heated to a temperature of 60 ° C. and used to glue paper. After a running time of 40 minutes, no deposit formation was found on the size roller application rollers. In the case of comparative dispersion 1, the preparation solution was heated to a temperature of 30 ° C. and used as a sizing agent. Deposits appeared on the size press roller after only 15 minutes. The experiment was repeated, but the preparation solution was adjusted to a pH of 9. At a temperature of 30 ° C this preparation solution could be applied to the paper without being deposited on the rollers, but at a temperature of 60 ° C the rollers of the size press were already occupied after 10 minutes.

Auch die Präparationslösung, die die Vergleichsdispersion 2 als Leimungsmittel enthielt, ergab Ablagerungen auf den Walzen der Leimpresse, sobald die Präparationslösung auf eine Temperatur von 60 °C erwärmt wurde. Die Präparationslösung, die die Vergleichsdispersion 3 als Leimungsmittel enthielt, erwies sich bei dem Stabilitätstest auch bei 60° bei schwach sauren Papieren als stabil. Wurden jedoch stark saure Papiere imprägniert, bildete sich nach 30 Minuten allmählich ein Leimpressenbelag, da der pH-Wert der Präparationslösung abfiel.The preparation solution, which contained the comparison dispersion 2 as a sizing agent, also showed deposits on the rollers of the size press as soon as the preparation solution was heated to a temperature of 60.degree. The preparation solution, which contained the comparative dispersion 3 as a sizing agent, also proved to be stable in the stability test at 60 ° with weakly acidic papers. However, if strongly acidic papers were impregnated, a size press coating gradually formed after 30 minutes because the pH of the preparation solution dropped.

Die Vergleichsdispersionen 1-2 gemäß DE-A-21 63850 sowie die Vergleichsdispersion 3 gemäß DE-A-2548393 sind demnach der erfindungsgemäßen anionischen Dispersion in Leimungswirkung und/ oder Stabilität deutlich unterlegen.Comparative dispersions 1-2 according to DE-A-21 63850 and comparative dispersion 3 according to DE-A-2548393 are therefore clearly inferior to the anionic dispersion according to the invention in terms of sizing effect and / or stability.

Beispiel 8Example 8

Ein in der Masse ungeleimtes, holzfreies Offsetpapier, das 14 % Asche und 1 % Alaun enthielt und ein Flächengewicht von 70 g/m2 hatte (Mahlgrad 25° SR), wurde mit einer Präparationslösung geleimt, die 4,5 g/1 Polymerisat, bezogen auf den Feststoffgehaltder anionischen Dispersion 1 und 60 g/I einer oxidativ abgebauten Kartoffelstärke enthielt. Zur Prüfung der Alkalifestigkeit der Leimung wurden die Cobb-Werte mit Wasser und mit Natronlauge verschiedener Konzentrationen geprüft. Dabei wurden folgende Ergebnisse erhalten :

Figure imgb0006
A non-sized, wood-free offset paper that contained 14% ash and 1% alum and had a basis weight of 70 g / m 2 (freeness 25 ° SR) was sized with a preparation solution containing 4.5 g / 1 polymer, based on the solids content of the anionic dispersion 1 and 60 g / l of an oxidatively degraded potato starch. To check the alkali resistance of the sizing, the Cobb values were tested with water and with sodium hydroxide solution of various concentrations. The following results were obtained:
Figure imgb0006

Die Leimung der erfindungsgemäßen Dispersion ist demnach beständig gegen Alkalien.The sizing of the dispersion according to the invention is therefore resistant to alkalis.

Beispiel 9Example 9

In diesem Beispiel wird demonstriert, daß das anionische Leimungsmittel 1 mit einem Melamin-Formaldehyd-Harz in der Weise kombiniert werden kann, ohne daß weder die Leimung noch die Naßverfestigkeitswirkung des Melamin-Formaldehyd-Harzes beeinträchtigt werden. Es wurden Proben des im Beispiels angegebenen Papiers mit den Präparationslösungen a) und b) in der Oberfläche geleimt. Die dabei gefundenen Ergebnisse sind in der Tabelle zusammengestellt.

Figure imgb0007
In this example it is demonstrated that the anionic sizing agent 1 can be combined with a melamine-formaldehyde resin in such a way that neither the sizing nor the wet strength effect of the melamine-formaldehyde resin is impaired. Samples of the paper specified in the example with the preparation solutions a) and b) were sized on the surface. The results found are summarized in the table.
Figure imgb0007

Claims (7)

1. An anionic dispersion produced by a two-stage polymerization reaction, a mixture of nonionic ethylenically unsaturated monomers containing sulphonic acid groups being copolymerized in the first polymerization stage in the manner of a solution copolymerization in a water-miscible solvent in the presence of a polymerization initiator, which is soluble in the monomer mixture, to give a homogeneous solution, and, after dilution with water, polymerization being carried out in the second polymerization stage in the manner of an emulsion polymerization in the presence of a usual amount of a water-soluble polymerization initiator, characterized in that in the first polymerization stage a mixture of
a) 85 to 55 % by weight of nonionic ethylenically unsaturated monomers, and
b) 15 to 45 % by weight of ethylenically unsaturated monomers containing sulphonic acid groups is copolymerized in the presence of 0.015 to 0.15 mole of a polymerization initiator, which is soluble in the monomer mixture, per mole of monomer mixture, the homogeneous polymer solution is diluted with water in a weight ratio of 1 : 3 to 1 : 50, and 1 to 4 parts by weight of at least one nonionic ethylenically unsaturated monomer per part by weight of the solution polymer are polymerized in this polymer solution in the second polymerization stage.
2. An anionic dispersion as claimed in claim 1, characterized in that a mixture of
a) styrene, methyl methacrylate, ethylhexyl acrylate and/or lauryl acrylate, and
b) 2-acrylamino-2-methylpropane sulphonic acid is polymerized in the first polymerization stage.
3. A process for the production of an anionic dispersion as claimed in claims 1 and 2 by polymerization in two stages, a mixture of nonionic ethylenically unsaturated monomers and ethylenically. unsaturated monomers containing sulphonic acid groups being copolymerized in the first polymerization stage in the manner of a solution copolymerization in a water-miscible solvent in the presence of a polymerization initiator, which is soluble in the monomer mixture, to give a homogeneous solution, and, after dilution with water, polymerization being carried out in the second polymerization stage in the manner of an emulsion polymerization in the presence of a usual amount of a water-soluble polymerization initiator, wherein in the first polymerization stage a mixture of
a) 85 to 55 % by weight of nonionic ethylenically unsaturated monomers, and
b) 15 to 45 % by weight of ethylenically unsaturated monomers containing sulphonic acid groups is copolymerized in the presence of 0.015 to 0.15 mole of a polymerization initiator, which is soluble in the monomer mixture, per mole of monomer mixture, the homogeneous polymer solution is diluted with water in a weight ratio of 1 : 3 to 1 : 50, and 1 to 4 parts by weight of a least one nonionic ethylenically unsaturated monomer per part by weight of the solution polymer are polymerized in this polymer solution in the second polymerization stage.
4. The use of an anionic dispersion as claimed in claims 1 and 2 as a surface sizing agent for paper.
EP81102874A 1980-05-12 1981-04-15 Anionic dispersions, process for their preparation and their use as surface sizing agents for paper Expired EP0039794B1 (en)

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AT81102874T ATE4513T1 (en) 1980-05-12 1981-04-15 ANIONIC DISPERSIONS, PROCESS FOR THEIR PREPARATION AND THEIR USE AS SURFACE SIZES FOR PAPER.

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DE3018081 1980-05-12

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EP0039794B1 true EP0039794B1 (en) 1983-08-24

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NL127267C (en) * 1958-12-27
BE789727A (en) * 1971-10-06 1973-04-05 Calgon Corp WATER-SOLUBLE POLYMERS OF 2-ACYLAMIDO-2-METHYLPROPANE SULPHONIC ACID
DE2548393A1 (en) * 1975-10-29 1977-05-12 Basf Ag Sizing material for paper - with high solids, low viscosity and good alkali stability
US4065523A (en) * 1975-11-24 1977-12-27 Rohm And Haas Company Process for increasing molecular weight of a polymer

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