EP0392353A2 - Aqueous resin dispersions - Google Patents

Aqueous resin dispersions Download PDF

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Publication number
EP0392353A2
EP0392353A2 EP90106518A EP90106518A EP0392353A2 EP 0392353 A2 EP0392353 A2 EP 0392353A2 EP 90106518 A EP90106518 A EP 90106518A EP 90106518 A EP90106518 A EP 90106518A EP 0392353 A2 EP0392353 A2 EP 0392353A2
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polymer
aqueous
weight
synthetic resin
resin dispersions
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German (de)
French (fr)
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EP0392353B1 (en
EP0392353A3 (en
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Maximilian Dr. Angel
Andreas Dr. Einwiller
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof

Definitions

  • the present invention relates to aqueous synthetic resin dispersions which can be obtained by preparing an aqueous starting dispersion of a polymer A which has a glass transition temperature of -50 to + 60 ° C and from monoethylenically unsaturated monomers which, with the exception of carboxyl groups and their derivatives, no further polymerisable or with one another carry condensable groups and, if appropriate, butadiene is built up, and an aqueous solution of a polymer B which is essentially composed of N-hydroxycarboxymethylamides of acrylic and / or methacrylic acid and / or of water-soluble salts of these N-hydroxycarboxymethylamides, at the beginning, in the course and / or after completion of the preparation of the aqueous starting dispersion with the proviso that the solids content of polymer B, based on the total amount of polymer A and polymer B, is 0.5 to 10% by weight.
  • the invention also relates to the use of these synthetic resin dispersions as binders in the production of nonwovens from nonwoven fabrics.
  • Non-woven fabrics are textile fabrics that are made by solidifying loose accumulations of individual fibers (non-woven fabrics).
  • the consolidation of nonwoven fabrics by impregnation or coating with aqueous synthetic resin dispersions and subsequent evaporation of the water is generally known.
  • EP-A 19169 relates to aqueous dispersions of copolymers which contain repeating units of the general formula I, in which R1 is hydrogen or the methyl group, contain and at least 85% by weight of acrylic and / or methacrylic acid esters containing 1 to 8 carbon atoms, alkanols and / or vinyl esters of acetic or propionic acid and / or vinyl chloride, of which said Monomers up to 40% of their weight can be replaced by acrylonitrile, styrene or butadiene, and 0 to 5% of their weight from ⁇ , ⁇ -monoolefinic unsaturated mono- and / or dicarboxylic acids containing 3 to 5 carbon atoms and / or their amides.
  • dispersions are recommended as binders for the production of nonwoven fabrics from nonwoven fabrics in order to obtain nonwovens that are washable and cleanable on the one hand and that formaldehyde is not released when they are processed and used.
  • the performance properties of the dispersions disclosed by way of example leave something to be desired, since nonwovens consolidated with these dispersions result in nonwovens which are not heat-sealable.
  • the combination of heat sealability as well as resistance to washing and cleaning is particularly important when using nonwovens in the hygiene sector, where a combination of hygienic nonwovens with itself or with other substrates is often required without the use of additional adhesives.
  • the earlier application P 37 34 752.7 relates to aqueous dispersions of copolymers which contain 85 to 99.5% by weight of ⁇ , ⁇ -monoolefinically unsaturated carboxylic esters with 3 to 12 C atoms and 0.5 to 10% by weight of monomers of the general formula II, in which the variables R2 and R3 independently of one another and independently of R1 have the same meaning as R1, and 0 to 5% by weight of 3 to 5 carbon atoms containing ⁇ , ⁇ -monoethylenically unsaturated mono- and / or dicarboxylic acids and / or their amides are built up, with up to 35% by weight of the incorporated ⁇ , ⁇ -monoolefinic unsaturated carboxylic acid esters can be monocarboxylic acid vinyl esters.
  • dispersions are recommended as binders for the production of nonwovens from nonwovens in order to obtain washable and cleaning-resistant nonwovens, during the processing and use of which no formaldehyde is released and which at the same time have heat sealability.
  • a disadvantage of these dispersions is that they have to be prepared by a complex emulsion polymerization process with two stages of different monomer compositions.
  • Aqueous synthetic resin dispersions are known from EP-A 281 083, the films of which have increased blocking resistance and which are also known as Binders in nonwovens are suitable.
  • the associated copolymers essentially contain vinyl acetate, 1 to 20% by weight of ethylene, 0.5 to 15% by weight, based on vinyl acetate, acrylamidoglycolic acid or related compounds, and 0.1 to 5% by weight of an acrylamide.
  • the object of the present invention was to provide synthetic resin dispersions which can be obtained in a simple manner and are particularly suitable for consolidating nonwovens, with washable and cleaning-resistant nonwovens being obtained, no formaldehyde being released during their processing and which additionally having a satisfactory heat-sealability exhibit.
  • the building blocks of polymer A are preferably ethylene, ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids containing 3 to 5 carbon atoms and their unsubstituted amides, particularly preferably acrylic and methacrylic acid and also maleic and itaconic acid and those thereof Mono- or diamides derived from carboxylic acids, esters of ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids bearing 2 to 5 carbon atoms and alkanols containing 1 to 8 carbon atoms, in particular the esters of acrylic and methacrylic acid, of which the acrylic acid esters are preferred, Vinyl esters of aliphatic monocarboxylic acids carrying up to 6 carbon atoms, acrylonitrile and methacrylonitrile, vinyl aromatic monomers such as styrene, vinyl toluenes, chlorostyrenes or tert-butyl styrenes
  • acrylic acid esters are methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, while among the esters of methacrylic acid n-butyl methacrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate are preferred.
  • Preferred vinyl esters are vinyl acetate and vinyl propionate, while styrene is preferred by the vinyl aromatic monomers.
  • the aqueous starting dispersions containing the polymers A are expediently prepared by single-stage polymerization of the respective monomers in an aqueous medium under the known conditions of emulsion polymerization in the presence of water-soluble radical-forming initiators and emulsifiers and, if appropriate, in the presence of protective colloids and regulators and other auxiliaries.
  • Peroxides such as sodium peroxydisulfate, hydrogen peroxide or combined systems which contain an organic reducing agent, a peroxide and a small amount of a metal compound soluble in the polymerization medium, the metallic component of which can occur in several valence stages, come primarily as water-soluble polymerization initiators, e.g. Ascorbic acid / iron (II) sulfate / hydrogen peroxide.
  • Particularly suitable emulsifiers are ethoxylated alkylphenols (EO grade: 3 to 30, alkyl radicals C8 to C10), the alkali metal salts of their sulfated derivatives, the alkali metal salts of alkylsulfonic acids such as sodium n-dodecylsulfonate or sodium n-tetradecylsulfonate as well as the alkali metal sulfates Sodium n-dodecylbenzenesulfonate or sodium n-tetradecylbenzenesulfonate has proven itself.
  • the emulsion polymerization temperature is usually 0 to 100, preferably 20 to 90 ° C.
  • the emulsion polymerization can be carried out as a batch process or in the form of a feed process.
  • the feed process is preferred, in which part of the polymerization batch is initially charged, heated to the polymerization temperature and then the rest is fed continuously in separate feeds, one of which contains the monomers in pure or in emulsified form.
  • the supply of the monomers as an aqueous emulsion is preferred.
  • the number average molecular weight M n of the dispersed polymer is generally 5 ⁇ 103 to 5 ⁇ 106, preferably 105 to 2 ⁇ 106.
  • the starting dispersions are advantageously produced with a solids content of 35 to 65% by weight.
  • the polymerization temperature is usually 45 to 95, preferably 60 to 85 ° C.
  • the polymerization can be carried out as a batch process or in the form of a feed process.
  • the feed process is preferred, with an aqueous solution containing the monomers and, as the first part of a combined initiator system, hydrogen peroxide being introduced in a particularly preferred manner, heated to the polymerization temperature and then maintaining the polymerization temperature within a few hours with the organic reducing agent and the aqueous part containing soluble metal compound continuously supplies the second part of the combined initiator system and then polymerizes for a further 1 to 2 h.
  • the weight average molecular weight M w is usually in the range of 105 to 106.
  • the synthetic resin dispersions according to the invention are particularly suitable as binders for the production of nonwovens from nonwoven fabrics, to which they impart heat-sealability and resistance to washing and cleaning, ie in particular high wet strength, and a soft feel.
  • synthetic resin dispersions according to the invention with a total solids content of 10 to 30% by weight are preferably used.
  • External auxiliaries, inert fillers, thickeners, dyes, agents for increasing the resistance to aging or flame retardants can also be used in the usual amounts as auxiliaries.
  • the synthetic resin dispersions according to the invention are suitable both for strengthening nonwovens made of natural fibers such as plant, animal or mineral fibers, and also nonwovens made of synthetic fibers, the nonwovens being needled, rolled, shrunk and / or reinforced with yarns. Examples are fibers made of cotton, wool, polyamides, polyesters, polyolefins, synthetic cellulose (viscose), rock wool or asbestos fibers.
  • the synthetic resin dispersions according to the invention are suitable for impregnating and coating woven and / or mesh-like flat textile structures, and also as binders for textile printing pastes, paper coating slips, coating compounds, leather protective layers, as coating agents for films and as finishing agents for textiles.
  • a solution of 150 g of acrylamidoglycolic acid, 1.5 g of a 40% by weight aqueous solution of a mixture of equal parts of Na-n-dodecylsulfonate and Na-n-tetradecylsulfonate and 1 g of a 30% by weight aqueous hydrogen peroxide solution in 1248 g of water was heated to the polymerization temperature of 80 ° C. and, while maintaining this temperature, a solution of 0.3 g of ascorbic acid and 0.001 g of iron (II) sulfate in 100 g of water was added continuously over the course of 2 h. The mixture was then polymerized at 80 ° C for 1 h.
  • solution B1 350 g of solution B1 were stirred into 2000 g of a 50% by weight aqueous starting dispersion of pure polyethyl acrylate prepared by single-stage emulsion polymerization. A stable synthetic resin dispersion with a solids content of 44% by weight was obtained.
  • a lengthwise (fiber orientation preferably in one direction, the longitudinal direction) non-woven fabric made of polyester fibers of length 40 mm and an average fiber fineness of 1.7 dtex (1 dtex corresponds to a fiber mass of 1 ⁇ 10 ⁇ 4 g with a fiber length of 1 m) was carried out in independent tests with the synthetic resin dispersions B2 and B3, which previously had a uniform solids content of 20% by weight. had been diluted, soaked, brought to separate the excess dispersion portion between two counter-rotating rollers and then exposed to a temperature of 150 ° C for 4 min.
  • the binder content of the nonwovens thus obtained was 33% by weight in all cases with a final weight of 50 g / m 2.
  • Table 1 also contains the result of a comparative test V, in which a 20% by weight synthetic resin dispersion was used instead of the synthetic resin dispersions according to the invention, which had been obtained by diluting a dispersion according to Preparation Example 4 from EP 19169.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)

Abstract

Aqueous dispersions of synthetic resins are obtainable by combining an aqueous starting dispersion of a polymer A which has a glass transition temperature of from -50 to +60 DEG C and is built up from monoethylenically unsaturated monomers which carry, apart from carboxyl groups and derivatives thereof, no further polymerisable or mutually condensable groups, and optionally butadiene, and an aqueous solution of a polymer B which is built up essentially from N-hydroxycarboxymethylamides of acrylic and/or methacrylic acid and/or from water-soluble salts of these N-hydroxycarboxymethylamides, at the beginning, during and/or after completion of the preparation of the aqueous starting dispersion, with the proviso that the solid content of the polymer B, based on the total amount of polymers A and B, is from 0.5 to 10% by weight.

Description

Die vorliegende Erfindung betrifft wäßrige Kunstharzdispersionen, dadurch erhältlich, daß man eine wäßrige Ausgangsdispersion eines Polymerisats A, das eine Glasübergangstemperatur von -50 bis +60°C aufweist und aus mono­ethylenisch ungesättigten Monomeren, die, Carboxylgruppen und deren Derivate ausgenommen, keine weiteren polymerisierbaren oder miteinander kondensierbare Gruppierungen tragen, und gegebenenfalls Butadien aufgebaut ist, und eine wäßrige Lösung eines Polymerisats B, das im wesentlichen aus N-Hydroxycarboxymethylamiden der Acryl- und/oder Methacrylsäure und/oder aus wasserlöslichen Salzen dieser N-Hydroxycarboxymethylamide aufgebaut ist, am Beginn, im Verlauf und/oder nach Fertigstellung der Herstellung der wäßrigen Ausgangsdispersion mit der Maßgabe zusammengibt, daß der Feststoffanteil des Polymerisats B, bezogen auf die Gesamtmenge aus Polymerisat A und Polymerisat B, 0,5 bis 10 Gew.% beträgt.The present invention relates to aqueous synthetic resin dispersions which can be obtained by preparing an aqueous starting dispersion of a polymer A which has a glass transition temperature of -50 to + 60 ° C and from monoethylenically unsaturated monomers which, with the exception of carboxyl groups and their derivatives, no further polymerisable or with one another carry condensable groups and, if appropriate, butadiene is built up, and an aqueous solution of a polymer B which is essentially composed of N-hydroxycarboxymethylamides of acrylic and / or methacrylic acid and / or of water-soluble salts of these N-hydroxycarboxymethylamides, at the beginning, in the course and / or after completion of the preparation of the aqueous starting dispersion with the proviso that the solids content of polymer B, based on the total amount of polymer A and polymer B, is 0.5 to 10% by weight.

Außerdem betrifft die Erfindung die Verwendung dieser Kunstharz­dispersionen als Bindemittel bei der Herstellung von Vliesstoffen aus Faservliesen.The invention also relates to the use of these synthetic resin dispersions as binders in the production of nonwovens from nonwoven fabrics.

Als Vliesstoffe werden textile Flächengebilde zusammengefaßt, die durch Verfestigen lockerer Anhäufungen von Einzelfasern (Faservliesen) hergestellt werden. Die Verfestigung von Faservliesen durch Imprägnieren oder Beschichten mit wäßrigen Kunstharzdispersionen und anschließendes Abdampfen des Wassers ist allgemein bekannt. Die EP-A 19169 betrifft wäßrige Dispersionen von Copolymerisaten, die wiederkehrende Einheiten der allgemeinen Formel I,

Figure imgb0001
in der R¹ Wasserstoff oder die Methylgruppe bedeutet, enthalten und zu mindestens 85 % ihres Gewichtes aus Acryl- und/oder Methacrylsäureestern 1 bis 8 C-Atome enthaltender Alkanole und/oder Vinylestern der Essig- oder Propionsäure und/oder Vinylchlorid, wobei von den genannten Monomeren bis zu 40 % ihres Gewichtes durch Acrylnitril, Styrol oder Butadien ersetzt sein können, sowie zu 0 bis 5 % ihres Gewichtes aus α,β-monoolefinisch ungesättigten 3 bis 5 C-Atome aufweisenden Mono- und/oder Dicarbonsäuren und/oder deren Amiden aufgebaut sind. Diese Dispersionen werden als Binde­mittel für die Herstellung von Vliesstofen aus Faservliesen empfohlen, um Vliesstoffe zu erhalten, die einerseits wasch- und reinigungsbeständig sind und bei deren Verarbeitung und Gebrauch andererseits kein Formaldehyd freigesetzt wird. Die anwendungstechnischen Eigenschaften der beispielhaft offenbarten Dispersionen lassen jedoch zu wünschen übrig, da mit diesen Dispersionen verfestigte Faservliese Vliesstoffe ergeben, die nicht heiß­siegelfähig sind. Die Kombination von Heißsiegelfähigkeit sowie Wasch- und Reinigungsbeständigkeit ist jedoch insbesondere bei der Verwendung von Vliesstoffen im Hygienebereich von Bedeutung, wo vielfach ohne Mit­verwendung zusätzlicher Klebstoffe ein Verbund von Hygienevliesstoffen mit sich oder mit anderen Substraten gefordert wird.Non-woven fabrics are textile fabrics that are made by solidifying loose accumulations of individual fibers (non-woven fabrics). The consolidation of nonwoven fabrics by impregnation or coating with aqueous synthetic resin dispersions and subsequent evaporation of the water is generally known. EP-A 19169 relates to aqueous dispersions of copolymers which contain repeating units of the general formula I,
Figure imgb0001
 in which R¹ is hydrogen or the methyl group, contain and at least 85% by weight of acrylic and / or methacrylic acid esters containing 1 to 8 carbon atoms, alkanols and / or vinyl esters of acetic or propionic acid and / or vinyl chloride, of which said Monomers up to 40% of their weight can be replaced by acrylonitrile, styrene or butadiene, and 0 to 5% of their weight from α, β-monoolefinic unsaturated mono- and / or dicarboxylic acids containing 3 to 5 carbon atoms and / or their amides. These dispersions are recommended as binders for the production of nonwoven fabrics from nonwoven fabrics in order to obtain nonwovens that are washable and cleanable on the one hand and that formaldehyde is not released when they are processed and used. However, the performance properties of the dispersions disclosed by way of example leave something to be desired, since nonwovens consolidated with these dispersions result in nonwovens which are not heat-sealable. The combination of heat sealability as well as resistance to washing and cleaning is particularly important when using nonwovens in the hygiene sector, where a combination of hygienic nonwovens with itself or with other substrates is often required without the use of additional adhesives.

Die ältere Anmeldung P 37 34 752.7 betrifft wäßrige Dispersionen von Copolymerisaten, die zu 85 bis 99,5 Gew.% aus α,β-monoolefinisch unge­sättigten Carbonsäureestern mit 3 bis 12 C-Atomen, zu 0,5 bis 10 Gew.% aus Monomeren der allgemeinen Formel II, in der die Variablen R² und R³ un­abhängig voneinander und unabhängig von R¹ die gleiche Bedeutung wie R¹ haben,

Figure imgb0002
und zu 0 bis 5 Gew.% aus 3 bis 5 C-Atome enthaltenden α,β-monoethylenisch ungesättigten Mono- und/oder Dicarbonsäuren und/oder deren Amiden aufgebaut sind, wobei bis zu 35 Gew.% der eingebauten α,β-monoolefinisch ungesättigten Carbonsäureester Monocarbonsäurevinylester sein können. Diese Dispersionen werden als Bindemittel für die Herstellung von Vlies­stoffen aus Faservliesen empfohlen, um wasch- und reinigungsbeständige Vliesstoffe zu erhalten, bei deren Verarbeitung und Gebrauch kein Formaldehyd freigesetzt wird und die gleichzeitig Heißsiegelfähigkeit aufweisen. Nachteilig an diesen Dispersionen ist jedoch, daß ihre Herstellung nach einem komplexen Emulsionspolymerisationsverfahren mit zwei Stufen unterschiedlicher Monomerenzusammensetzung erfolgen muß.The earlier application P 37 34 752.7 relates to aqueous dispersions of copolymers which contain 85 to 99.5% by weight of α, β-monoolefinically unsaturated carboxylic esters with 3 to 12 C atoms and 0.5 to 10% by weight of monomers of the general formula II, in which the variables R² and R³ independently of one another and independently of R¹ have the same meaning as R¹,
Figure imgb0002
 and 0 to 5% by weight of 3 to 5 carbon atoms containing α, β-monoethylenically unsaturated mono- and / or dicarboxylic acids and / or their amides are built up, with up to 35% by weight of the incorporated α, β-monoolefinic unsaturated carboxylic acid esters can be monocarboxylic acid vinyl esters. These dispersions are recommended as binders for the production of nonwovens from nonwovens in order to obtain washable and cleaning-resistant nonwovens, during the processing and use of which no formaldehyde is released and which at the same time have heat sealability. A disadvantage of these dispersions, however, is that they have to be prepared by a complex emulsion polymerization process with two stages of different monomer compositions.

Aus der EP-A 281 083 sind wäßrige Kunstharzdispersionen bekannt, deren Verfilmungen eine erhöhte Blockfestigkeit aufweisen und die ebenfalls als Bindemittel in Vliesstoffen geeignet sind. Die zugehörigen Copolymerisate enthalten im wesentlichen Vinylacetat, 1 bis 20 Gew.% Ethylen, 0,5 bis 15 Gew.%, bezogen auf Vinylacetat, Acrylamidoglycolsäure oder verwandte Verbindungen sowie 0,1 bis 5 Gew.% eines Acrylamids.Aqueous synthetic resin dispersions are known from EP-A 281 083, the films of which have increased blocking resistance and which are also known as Binders in nonwovens are suitable. The associated copolymers essentially contain vinyl acetate, 1 to 20% by weight of ethylene, 0.5 to 15% by weight, based on vinyl acetate, acrylamidoglycolic acid or related compounds, and 0.1 to 5% by weight of an acrylamide.

Der vorliegenden Erfindung lag die Bereitstellung von Kunstharzdisper­sionen als Aufgabe zugrunde, die auf einfache Art und Weise erhältlich und insbesondere zum Verfestigen von Faservliesen geeignet sind, wobei wasch- und reinigungsbeständige Vliesstoffe erhalten werden, bei deren Verarbeitung kein Formaldehyd freigesetzt wird und die zusätzlich eine zufriedenstellende Heißsiegelfähigkeit aufweisen.The object of the present invention was to provide synthetic resin dispersions which can be obtained in a simple manner and are particularly suitable for consolidating nonwovens, with washable and cleaning-resistant nonwovens being obtained, no formaldehyde being released during their processing and which additionally having a satisfactory heat-sealability exhibit.

Demgemäß wurden die eingangs definierten wäßrigen Kunstharzdispersionen gefunden.Accordingly, the aqueous synthetic resin dispersions defined at the outset have been found.

Als Bausteine des Polymerisats A kommen neben Butadien vorzugsweise Ethylen, 3 bis 5 C-Atome enthaltende α,β-monoethylenisch ungesättigte Mono- und Dicarbonsäuren sowie deren unsubstituierte Amide, besonders bevorzugt Acryl- und Methacrylsäure sowie ferner Male in- und Itaconsäure und die von diesen Carbonsäuren abgeleiteten Mono- oder Diamide, Ester aus 2 bis 5 C-Atome tragenden α,β-monoethylenisch ungesättigten Monocarbon­säuren und 1 bis 8 C-Atome tragenden Alkanolen, insbesondere die Ester der Acryl- und der Methacrylsäure, von denen die Acrylsäureester bevorzugt sind, Vinylester von bis zu 6 C-Atomen tragenden aliphatischen Monocarbon­säuren, Acryl- und Methacrylnitril, vinylaromatische Monomere wie Styrol, Vinyltoluole, Chlorstyrole oder tert.-Butylstyrole sowie Vinylhalogenide wie Vinyl- und Vinylidenchlorid in Betracht. Besonders bevorzugte Acryl­säureester sind Methylacrylat, Ethylacrylat, iso-Propylacrylat, n-Butyl­acrylat, iso-Butylacrylat sowie 2-Ethylhexylacrylat, während unter den Estern der Methacrylsäure n-Butylmethacrylat, iso-Butylmethacrylat sowie 2-Ethylhexylmethacrylat bevorzugt werden. Bevorzugte Vinylester sind das Vinylacetat und das Vinylpropionat, während von den vinylaromatischen Monomeren Styrol bevorzugt wird.In addition to butadiene, the building blocks of polymer A are preferably ethylene, α, β-monoethylenically unsaturated mono- and dicarboxylic acids containing 3 to 5 carbon atoms and their unsubstituted amides, particularly preferably acrylic and methacrylic acid and also maleic and itaconic acid and those thereof Mono- or diamides derived from carboxylic acids, esters of α, β-monoethylenically unsaturated monocarboxylic acids bearing 2 to 5 carbon atoms and alkanols containing 1 to 8 carbon atoms, in particular the esters of acrylic and methacrylic acid, of which the acrylic acid esters are preferred, Vinyl esters of aliphatic monocarboxylic acids carrying up to 6 carbon atoms, acrylonitrile and methacrylonitrile, vinyl aromatic monomers such as styrene, vinyl toluenes, chlorostyrenes or tert-butyl styrenes and vinyl halides such as vinyl and vinylidene chloride. Particularly preferred acrylic acid esters are methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, while among the esters of methacrylic acid n-butyl methacrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate are preferred. Preferred vinyl esters are vinyl acetate and vinyl propionate, while styrene is preferred by the vinyl aromatic monomers.

Insgesamt werden die Gewichtsanteile der am Aufbau des Polymerisats A beteiligten Monomeren mit Hilfe der Beziehung von Fox so gewählt, daß das Polymerisat A eine Glasübergangstemperatur von -50 bis +60, vorzugsweise von -50 bis -5°C aufweist. Nach Fox (T.G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956) gilt für die Glasübergangstemperatur von Mischpolymerisaten in guter Näherung:

Figure imgb0003
wobei X¹, X², .... , Xn die Massenbrüche der Monomeren 1, 2, .... , n und Tg¹, Tg², .... , Tgn die Glastemperaturen der jeweils nur aus einem der Monomeren 1,2 .... oder n aufgebauten Polymeren in Grad Kelvin bedeuten. Die Glastemperaturen dieser Homopolymerisate der oben aufgeführten Monomeren sind bekannt und z.B. in J. Brandrup, E.H. Immergut, Polymer Handbook 1st Ed. J. Wiley, New York 1966 und 2nd Ed. J. Wiley, New York 1975 aufgeführt.Overall, the proportions by weight of the monomers involved in the synthesis of polymer A are selected with the aid of Fox's relationship so that polymer A has a glass transition temperature of from -50 to +60, preferably from -50 to -5 ° C. According to Fox (TG Fox, Bull. Am. Phys. Soc. (Ser. II) 1 , 123 (1956), the following applies in good approximation to the glass transition temperature of copolymers:
Figure imgb0003
 where X¹, X², ...., X n are the mass fractions of the monomers 1, 2, ...., n and Tg¹, Tg², ...., Tg n are the glass transition temperatures of only one of the monomers 1,2 .... or n built polymers in degrees Kelvin. The glass transition temperatures of these homopolymers of the monomers listed above are known and are described, for example, in J. Brandrup, EH Immergut, Polymer Handbook 1 st Ed. J. Wiley, New York 1966, 2 nd Ed. J. Wiley, New York listed in 1975.

Die Herstellung der die Polymerisate A enthaltenden wäßrigen Ausgangs­dispersionen erfolgt zweckmäßigerweise durch einstufige Polymerisation der jeweiligen Monomeren in wäßrigem Medium unter den bekannten Bedingungen der Emulsionspolymerisation in Gegenwart von wasserlöslichen radikal­bildenden Initiatoren und Emulgatoren sowie gegebenenfalls in Gegenwart von Schutzkolloiden und Reglern sowie weiterer Hilfsmitel. Als wasserlös­liche Polymerisationsinitiatoren kommen vor allem Peroxide wie Natrium­peroxidisulfat, Wasserstoffperoxid oder kombinierte Systeme, die ein organisches Reduktionsmittel, ein Peroxid und eine geringe Menge einer im Polymerisationsmedium löslichen Metallverbindung, deren metallische Komponente in mehreren Wertigkeitsstufen auftreten kann, enthalten, z.B. Ascorbinsäure/Eisen(II)sulfat/Wasserstoffperoxid, in Betracht.The aqueous starting dispersions containing the polymers A are expediently prepared by single-stage polymerization of the respective monomers in an aqueous medium under the known conditions of emulsion polymerization in the presence of water-soluble radical-forming initiators and emulsifiers and, if appropriate, in the presence of protective colloids and regulators and other auxiliaries. Peroxides such as sodium peroxydisulfate, hydrogen peroxide or combined systems which contain an organic reducing agent, a peroxide and a small amount of a metal compound soluble in the polymerization medium, the metallic component of which can occur in several valence stages, come primarily as water-soluble polymerization initiators, e.g. Ascorbic acid / iron (II) sulfate / hydrogen peroxide.

Als Emulgatoren haben sich insbesondere ethoxylierte Alkylphenole (EO-Grad: 3 bis 30, Alkylrest C₈ bis C₁₀), die Alkalimetallsalze ihrer sulfatierten Derivate, die Alkalimetallsalze von Alkylsulfonsäuren wie Natrium-n-dodecylsulfonat oder Natrium-n-tetradecylsulfonat sowie die Alkalimetallsalze von Alkylarylsulfonsäuren wie Natrium-n-dodecyl­benzolsulfonat oder Natrium-n-tetradecylbenzolsulfonat bewährt. Die Emulsionspolymerisationstemperatur beträgt üblicherweise 0 bis 100, vorzugsweise 20 bis 90°C.Particularly suitable emulsifiers are ethoxylated alkylphenols (EO grade: 3 to 30, alkyl radicals C₈ to C₁₀), the alkali metal salts of their sulfated derivatives, the alkali metal salts of alkylsulfonic acids such as sodium n-dodecylsulfonate or sodium n-tetradecylsulfonate as well as the alkali metal sulfates Sodium n-dodecylbenzenesulfonate or sodium n-tetradecylbenzenesulfonate has proven itself. The emulsion polymerization temperature is usually 0 to 100, preferably 20 to 90 ° C.

Die Emulsionspolymerisation kann als Chargenprozeß oder in Form eines Zulaufverfahrens durchgeführt werden. Bevorzugt ist das Zulaufverfahren, bei dem man einen Teil des Polymerisationsansatzes vorlegt, auf die Polymerisationstemperatur erhitzt und anschließend den Rest in getrennten Zuläufen, von denen einer die Monomeren in reiner oder in emulgierter Form enthält, kontinuierlich zuführt. Die Zufuhr der Monomeren als wäßrige Emulsion wird bevorzugt. Das zahlenmittlere Molekulargewicht M n des dispergierten Polymerisates beträgt im allgemeinen 5 · 10³ bis 5 · 10⁶, bevorzugt 10⁵ bis 2 · 10⁶. Mit Vorteil werden die Ausgangsdispersionen mit einem Feststoffgehalt von 35 bis 65 Gew.% hergestellt.The emulsion polymerization can be carried out as a batch process or in the form of a feed process. The feed process is preferred, in which part of the polymerization batch is initially charged, heated to the polymerization temperature and then the rest is fed continuously in separate feeds, one of which contains the monomers in pure or in emulsified form. The supply of the monomers as an aqueous emulsion is preferred. The number average molecular weight M n of the dispersed polymer is generally 5 · 10³ to 5 · 10⁶, preferably 10⁵ to 2 · 10⁶. The starting dispersions are advantageously produced with a solids content of 35 to 65% by weight.

Die Herstellung der wäßrigen Lösungen der Polymerisate B erfolgt üblicherweise durch radikalische Polymerisation in wäßriger Lösung und wird u.a. in J. Polymer Sci., Polym. Lett. Ed. 17 (1979) S. 369 - 378 beschrieben. Als wasserlösliche Polymerisationsinitiatoren können in der Regel die gleichen Substanzen verwendet werden, die auch zur Herstellung der Ausgangsdispersion (A) geeignet sind. Üblicherweise werden sie, bezogen auf die Monomeren, in Mengen von 0,1 bis 3 Gew.% eingesetzt. Mit Vorteil wird in Gegenwart geringer Mengen an Emulgatoren polymerisiert (bis zu 10 Gew.%, bezogen auf die Monomeren), wobei vorzugsweise die gleichen Emulgatoren wie zur Herstellung der Ausgangsdispersion (A) verwendet werden. Die Polymerisationstemperatur beträgt üblicherweise 45 bis 95, vorzugsweise 60 bis 85°C. Die Polymerisation kann als Chargen­prozeß oder in Form eines Zulaufverfahrens durchgeführt werden. Bevorzugt ist das Zulaufverfahren, wobei man in besonders bevorzugter Weise eine die Monomeren und, als ersten Teil eines kombinierten Initiatorsystems, Wasserstoffperoxid enthaltende wäßrige Lösung vorlegt, auf die Polymeri­sationstemperatur erhitzt und anschließend unter Aufrechterhaltung der Polymerisationstemperatur innerhalb von wenigen Stunden mit einer das organische Reduktionsmittel und die lösliche Metallverbindung enthaltenden wäßrigen Lösung den zweiten Teil des kombinierten Initiatorsystems kontinuierlich zuführt und anschließend noch 1 bis 2 h nachpolymerisiert. Das gewichtsmittlere Molekulargewicht M w liegt üblicherweise im Bereich von 10⁵ bis 10⁶.The aqueous solutions of the polymers B are usually prepared by free-radical polymerization in aqueous solution and is described, inter alia, in J. Polymer Sci., Polym. Lett. Ed. 17 (1979) pp. 369-378. The same substances which are also suitable for the preparation of the starting dispersion (A) can generally be used as water-soluble polymerization initiators. They are usually used in amounts of 0.1 to 3% by weight, based on the monomers. It is advantageous to polymerize in the presence of small amounts of emulsifiers (up to 10% by weight, based on the monomers), preferably using the same emulsifiers as used to prepare the starting dispersion (A). The polymerization temperature is usually 45 to 95, preferably 60 to 85 ° C. The polymerization can be carried out as a batch process or in the form of a feed process. The feed process is preferred, with an aqueous solution containing the monomers and, as the first part of a combined initiator system, hydrogen peroxide being introduced in a particularly preferred manner, heated to the polymerization temperature and then maintaining the polymerization temperature within a few hours with the organic reducing agent and the aqueous part containing soluble metal compound continuously supplies the second part of the combined initiator system and then polymerizes for a further 1 to 2 h. The weight average molecular weight M w is usually in the range of 10⁵ to 10⁶.

Da die N-Hydroxycarboxymethylamide der Acryl- und/oder Methacrylsäure nur mäßig wasserlöslich sind, werden zur Herstellung von wäßrigen Lösungen der Polymerisate B bevorzugt ihre in Wasser besser löslichen Alkali­metall- oder Ammoniumsalze, insbesondere ihre Natrium- und Kaliumsalze, eingesetzt. Besonders bevorzugt erfolgt die Polymerisation in wäßrigen Lösungen, die Gemische aus freien Säuren und ihren korrespondierenden Alkalimetall- oder Ammoniumsalzen enthalten und vorzugsweise einen pH-Wert von 2 bis 7, besonders bevorzugt von 2 bis 4, aufweisen. Die Wirksamkeit der Polymeren B wird nicht wesentlich beeinträchtigt, wenn diese in Mengen von bis zu 20 % ihres Gewichtes zusätzlich wasserlösliche Monomere wie Acrylsäure, Methacrylsäure oder deren Amide einpolymerisiert enthalten.Since the N-hydroxycarboxymethylamides of acrylic and / or methacrylic acid are only moderately water-soluble, their more water-soluble alkali metal or ammonium salts, in particular their sodium and potassium salts, are preferably used to prepare aqueous solutions of the polymers B. The polymerization is particularly preferably carried out in aqueous solutions which contain mixtures of free acids and their corresponding alkali metal or ammonium salts and preferably have a pH of 2 to 7, particularly preferably 2 to 4. The effectiveness of the polymers B is not significantly impaired if, in amounts of up to 20% by weight, they additionally contain copolymerized water-soluble monomers such as acrylic acid, methacrylic acid or their amides.

Die erfindungsgemäßen wäßrigen Kunstharzdispersionen sind vorzugsweise erhältlich, indem man am Beginn, im Verlauf und/oder nach Fertigstellung der Herstellung einer Ausgangsdispersion (A) in diese eine wäßrige Lösung eines Polymerisats B einrührt, wobei bevorzugt in eine fertiggestellte Ausgangsdispersion eingerührt wird, und die einzusetzenden Mengen so bemißt, daß der Feststoffanteil des Polymerisats B, bezogen auf die Gesamtmenge aus Polymerisat A und Polymerisat B 0,5 bis 10, bevorzugt 2 bis 5 Gew.% beträgt. Von besonderem Vorteil ist, daß das zusammengeben einer Ausgangsdispersion A und einer wäßrigen Lösung eines Polymerisats B zur Herstellung einer bestimmten erfindungsgemäßen Kunstharzdispersion sowohl beim Hersteller, als auch erst beim Verbraucher erfolgen kann. Die erfindungsgemäßen Kunstharzdispersionen eignen sich insbesondere als Bindemittel für die Herstellung von Vliesstoffen aus Faservliesen, denen sie Heißsiegelfähigkeit sowie Wasch- und Reinigungsbeständigkeit, d.h. insbesondere eine hohe Naßfestigkeit, und weichen Griff verleihen. Bei ihrem Einsatz zum Binden von Faservliesen werden vorzugsweise erfindungs­gemäße Kunstharzdispersionen mit einem Gesamtfeststoffgehalt von 10 bis 30 Gew.% verwendet. Dabei können als Hilfsmittel u.a. äußere Weichmacher, inerte Füllstoffe, Verdickungsmittel, Farbstoffe, Mittel zur Erhöhung der Alterungsbeständigkeit oder Flammschutzmittel in den üblichen Mengen mitverwendet werden. Die erfindungsgemäßen Kunstharzdispersionen eignen sich sowohl zum Verfestigen von Faservliesen aus Naturfasern wie Pflanzen-, Tier- oder Mineralfasern, als auch von Faservliesen aus synthetischen Fasern, wobei die Faservliese genadelt, gewalzt, geschrumpft und/oder mit Garnen verstärkt sein können. Beispiele sind Fasern aus Baumwolle, Wolle, Polyamiden, Polyestern, Polyolefinen, synthetischer Cellulose (Viscose), Steinwolle oder Asbestfasern. Außerdem eignen sich die erfindungsgemäßen Kunstharzdispersionen zum Imprägnieren und Beschichten von gewobenen und/oder einen Maschenaufbau aufweisenden flächigen textilen Gebilden, sowie als Bindemittel für Textildruckpasten, Papierstreichmassen, Beschichtungsmassen, Lederschutzschichten, als Überzugsmittel für Folien sowie als Ausrüstungsmittel für Textilien.The aqueous synthetic resin dispersions according to the invention are preferably obtainable by stirring an aqueous solution of a polymer B into this at the beginning, in the course and / or after completion of the preparation of a starting dispersion (A), preferably stirring into a finished starting dispersion, and the amounts to be used so dimensioned that the solids content of the polymer B, based on the Total amount of polymer A and polymer B is 0.5 to 10, preferably 2 to 5% by weight. It is particularly advantageous that the combination of a starting dispersion A and an aqueous solution of a polymer B to produce a particular synthetic resin dispersion according to the invention can be carried out both by the manufacturer and only by the consumer. The synthetic resin dispersions according to the invention are particularly suitable as binders for the production of nonwovens from nonwoven fabrics, to which they impart heat-sealability and resistance to washing and cleaning, ie in particular high wet strength, and a soft feel. When used to bind nonwovens, synthetic resin dispersions according to the invention with a total solids content of 10 to 30% by weight are preferably used. External auxiliaries, inert fillers, thickeners, dyes, agents for increasing the resistance to aging or flame retardants can also be used in the usual amounts as auxiliaries. The synthetic resin dispersions according to the invention are suitable both for strengthening nonwovens made of natural fibers such as plant, animal or mineral fibers, and also nonwovens made of synthetic fibers, the nonwovens being needled, rolled, shrunk and / or reinforced with yarns. Examples are fibers made of cotton, wool, polyamides, polyesters, polyolefins, synthetic cellulose (viscose), rock wool or asbestos fibers. In addition, the synthetic resin dispersions according to the invention are suitable for impregnating and coating woven and / or mesh-like flat textile structures, and also as binders for textile printing pastes, paper coating slips, coating compounds, leather protective layers, as coating agents for films and as finishing agents for textiles.

Die erfindungsgemäßen Kunstharzdispersionen können bei ihrem Einsatz als Bindemittel für Faservliese in an sich bekannter Weise, z.B. durch Tränken, Sprühen, Streichen oder Bedrucken aufgebracht werden. Danach wird in der Regel das überschüssige Bindemittel abgetrennt, z.B. durch Abquetschen zwischen zwei gegenläufigen Walzen, das bindemittelhaltige Faservlies getrocknet und anschließend noch einige Minuten unter Hitze gehalten, wobei im allgemeinen Temperaturen von 110 bis 200, vorzugsweise von 120 bis 170°C angewandt werden. Der Bindemittelanteil im Vliesstoff beträgt üblicherweise 20 bis 60, bevorzugt 20 bis 35 Gew.% (wasserfrei gerechnet).When used as binders for nonwovens, the synthetic resin dispersions according to the invention can be applied in a manner known per se, for example by impregnation, spraying, brushing or printing. Thereafter, the excess binder is generally separated off, for example by squeezing between two counter-rotating rollers, the binder-containing nonwoven fabric is dried and then kept under heat for a few minutes, temperatures of from 110 to 200, preferably from 120 to 170 ° C. being generally used. The proportion of binder in the nonwoven is usually 20 to 60, preferably 20 to 35% by weight (calculated as anhydrous).

BeispieleExamples Beispiel 1example 1 Herstellung einer wäßrigen Polyacrylamidoglycolsäure-Lösung B1Preparation of an aqueous polyacrylamidoglycolic acid solution B1

Eine Lösung von 150 g Acrylamidoglycolsäure, 1,5 g einer 40 gew.%igen wäßrigen Lösung eines Gemisches aus gleichen Teilen Na-n-dodecylsulfonat und Na-n-tetradecylsulfonat sowie 1 g einer 30 gew.%igen wäßrigen Wasserstoffperoxidlösung in 1248 g wasser wurde auf die Polymerisations­temperatur von 80°C erhitzt und unter Aufrechterhaltung dieser Temperatur im Verlauf von 2 h kontinuierlich mit einer Lösung von 0,3 g Ascorbinsäure und 0,001 g Eisen(II)sulfat in 100 g Wasser versetzt. Anschließend wurde noch 1 h bei 80°C nachpolymerisiert.A solution of 150 g of acrylamidoglycolic acid, 1.5 g of a 40% by weight aqueous solution of a mixture of equal parts of Na-n-dodecylsulfonate and Na-n-tetradecylsulfonate and 1 g of a 30% by weight aqueous hydrogen peroxide solution in 1248 g of water was heated to the polymerization temperature of 80 ° C. and, while maintaining this temperature, a solution of 0.3 g of ascorbic acid and 0.001 g of iron (II) sulfate in 100 g of water was added continuously over the course of 2 h. The mixture was then polymerized at 80 ° C for 1 h.

Der Feststoffgehalt der erhaltenen niederviskosen wäßrigen Lösung betrug 10 Gew.%.The solids content of the low-viscosity aqueous solution obtained was 10% by weight.

Beispiel 2 und 3Examples 2 and 3 Herstellung der erfindungsgemäßen Kunstharzdispersionen B2 und B3Production of the synthetic resin dispersions B2 and B3 B2B2

In 2000 g einer 50 gew.%igen, durch einstufige Emulsionspolymerisation hergestellten, wäßrigen Ausgangsdispersion von reinem Polyethylacrylat wurden 350 g der Lösung B1 eingerührt. Es wurde eine stabile Kunstharz­dispersion eines Feststoffgehaltes von 44 Gew.% erhalten.350 g of solution B1 were stirred into 2000 g of a 50% by weight aqueous starting dispersion of pure polyethyl acrylate prepared by single-stage emulsion polymerization. A stable synthetic resin dispersion with a solids content of 44% by weight was obtained.

B3B3

In 2000 g einer 50 gew.%igen, durch einstufige Emulsionspolymerisation hergestellten, wäßrigen Ausgangsdispersion eines Copolymerisats aus 52,5 Gew.% Ethylacrylat, 31,5 Gew.% Methylacrylat, 10 Gew.% Styrol und 6 Gew.% n-Butylacrylat wurden 250 g der Lösung B1 eingerührt. Es wurde eine stabile Kunstharzdispersion eines Feststoffgehaltes von 45 Gew.% erhalten.In 2000 g of a 50% by weight aqueous starting dispersion of a copolymer prepared from 52.5% by weight of ethyl acrylate, 31.5% by weight of methyl acrylate, 10% by weight of styrene and 6% by weight of n-butyl acrylate, prepared by single-stage emulsion polymerization 250 g of solution B1 are stirred in. A stable synthetic resin dispersion with a solids content of 45% by weight was obtained.

Beispiel 4Example 4 Untersuchung verschieden gebundener FaservlieseInvestigation of differently bound nonwovens


A) Ein längsgelegtes (Faserorientierung bevorzugt in einer Richtung, der Längsrichtung) Faservlies aus Polyester-Fasern der Länge 40 mm und einer durchschnittlichen Faserfeinheit von 1,7 dtex (1 dtex entspricht einer Fasermasse von 1 · 10⁻⁴ g bei einer Faserlänge von 1 m) wurde in unabhängigen Versuchen mit den Kunstharzdispersionen B2 und B3, die zuvor auf einen einheitlichen Feststoffgehalt von 20 Gew.% verdünnt worden waren, getränkt, zur Abtrennung des überschüssigen Dispersions­anteils zwischen zwei gegenläufige Walzen gebracht und danach 4 min einer Temperatur von 150°C ausgesetzt. Der Bindemittelanteil der so erhaltenen Vliesstoffe betrug, bei einem Flächenendgewicht von 50 g/m², in allen Fällen 33 Gew.%. Anschließend wurden 50 mm breite Streifen dieser Vliesstoffe, bei einer freien Einspannlänge von 10 cm, wassernaß und nach Heißsiegelung (Siegelbedingungen: 2 sec, 170°C, 6 bar, Siegelfläche 5 cm², Siegelung Unterseite eines Streifens gegen Oberseite eines Streifens) zur Ermittlung der Höchstzugkraft (parallel zur Faservorzugsrichtung) in Analogie zur DIN 53857 einem Streifenzug­versuch ausgesetzt. Die Ergebnisse zeigt Tabelle 1. Tabelle 1 enthält zusätzlich das Ergebnis eines Vergleichsversuchs V, bei dem an Stelle der erfindungsgemäßen Kunstharzdispersionen eine 20 gew.%ige Kunstharzdispersion eingesetzt wurde, die durch Verdünnen einer Dispersion gemäß Herstellungsbeispiel 4 aus der EP 19169 erhalten worden war. Tabelle 1 Höchstzugkraft [N] wassernaß nach Siegelung B2 33 19,3 B3 47 15,0 V 55 0
B) Wie A), das Faservlies bestand jedoch aus Viscose-Fasern der Länge 40 mm und einer durchschnittlichen Faserfeinheit von 3,3 dtex. Die Ergebnisse zeigt Tabelle 2. Tabelle 2 Höchstzugkraft [N] wassernaß nach Siegelung B2 33 8,8 B3 38 11,6 V 39 0
A) A lengthwise (fiber orientation preferably in one direction, the longitudinal direction) non-woven fabric made of polyester fibers of length 40 mm and an average fiber fineness of 1.7 dtex (1 dtex corresponds to a fiber mass of 1 · 10⁻⁴ g with a fiber length of 1 m) was carried out in independent tests with the synthetic resin dispersions B2 and B3, which previously had a uniform solids content of 20% by weight. had been diluted, soaked, brought to separate the excess dispersion portion between two counter-rotating rollers and then exposed to a temperature of 150 ° C for 4 min. The binder content of the nonwovens thus obtained was 33% by weight in all cases with a final weight of 50 g / m 2. 50 mm wide strips of these nonwovens were then, with a free clamping length of 10 cm, wet with water and after heat sealing (sealing conditions: 2 sec, 170 ° C., 6 bar, sealing surface 5 cm², sealing underside of a strip against the top of a strip) to determine the Maximum tensile force (parallel to the preferred fiber direction) exposed to a strip tensile test in analogy to DIN 53857. The results are shown in Table 1. Table 1 also contains the result of a comparative test V, in which a 20% by weight synthetic resin dispersion was used instead of the synthetic resin dispersions according to the invention, which had been obtained by diluting a dispersion according to Preparation Example 4 from EP 19169. Table 1 Maximum tensile force [N] wet with water after sealing B2 33 19.3 B3 47 15.0 V 55 0
B) Like A), but the nonwoven fabric consisted of viscose fibers 40 mm in length and an average fiber fineness of 3.3 dtex. The results are shown in Table 2. Maximum tensile force [N] wet with water after sealing B2 33 8.8 B3 38 11.6 V 39 0

Claims (3)

1. Wäßrige Kunstharzdispersionen, dadurch erhältlich, daß man eine wäßrige Ausgangsdispersion eines Polymerisats A, das eine Glasüber­gangstemperatur von -50 bis +60°C aufweist und aus monoethylenisch ungesättigten Monomeren, die, Carboxylgruppen und deren Derivate ausgenommen, keine weiteren polymerisierbaren oder miteinander konden­sierbare Gruppierungen tragen, und gegebenenfalls Butadien aufgebaut ist, und eine wäßrige Lösung eines Polymerisats B, das im wesentlichen aus N-Hydroxycarboxymethylamiden der Acryl- und/oder Methacrylsäure und/oder aus wasserlöslichen Salzen dieser N-Hydroxycarboxymethylamide aufgebaut ist, am Beginn, im Verlauf und/oder nach Fertigstellung der Herstellung der wäßrigen Ausgangsdispersion mit der Maßgabe zusammen­gibt, daß der Feststoffanteil des Polymerisats B, bezogen auf die Gesamtmenge aus Polymerisat A und Polymerisat B, 0,5 bis 10 Gew.% beträgt.1. Aqueous synthetic resin dispersions, obtainable by preparing an aqueous starting dispersion of a polymer A which has a glass transition temperature of -50 to + 60 ° C and from monoethylenically unsaturated monomers which, with the exception of carboxyl groups and their derivatives, no further polymerizable or condensable groups wear, and optionally butadiene is built up, and an aqueous solution of a polymer B which is essentially composed of N-hydroxycarboxymethylamides of acrylic and / or methacrylic acid and / or of water-soluble salts of these N-hydroxycarboxymethylamides, at the beginning, in the course and / or after completion of the preparation of the aqueous starting dispersion with the proviso that the solids content of polymer B, based on the total amount of polymer A and polymer B, is 0.5 to 10% by weight. 2. Verfahren zur Herstellung von wäßrigen Kunstharzdispersionen gemäß Anspruch 1, dadurch gekennzeichnet, daß man am Beginn, im Verlauf und/oder nach Fertigstellung der Herstellung einer wäßrigen Ausgangs­dispersion eines Polymerisats A diese Ausgangsdispersion und eine wäßrige Lösung eines Polymerisats B mit der Maßgabe zusammengibt, daß der Feststoffanteil des Polymerisats B, bezogen auf die Gesamtmenge aus Polymerisat A und Polymerisat B, 0,5 bis 10 Gew.% beträgt.2. A process for the preparation of aqueous synthetic resin dispersions according to claim 1, characterized in that at the beginning, in the course and / or after completion of the preparation of an aqueous starting dispersion of a polymer A, this starting dispersion and an aqueous solution of a polymer B are combined with the proviso that the solids content of polymer B, based on the total amount of polymer A and polymer B, is 0.5 to 10% by weight. 3. Verwendung von wäßrigen Kunstharzdispersionen gemäß Anspruch 1 als Bindemittel zur Herstellung von Vliesstoffen aus Faservliesen.3. Use of aqueous synthetic resin dispersions according to claim 1 as binders for the production of nonwovens from nonwoven fabrics.
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FI901813A0 (en) 1990-04-10
EP0392353A3 (en) 1991-08-07
DE59005048D1 (en) 1994-04-28
ES2062150T3 (en) 1994-12-16
US5081178A (en) 1992-01-14
NO176718B (en) 1995-02-06

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