EP0084809B1 - Dispersion of acryl plastics - Google Patents

Dispersion of acryl plastics Download PDF

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Publication number
EP0084809B1
EP0084809B1 EP19830100223 EP83100223A EP0084809B1 EP 0084809 B1 EP0084809 B1 EP 0084809B1 EP 19830100223 EP19830100223 EP 19830100223 EP 83100223 A EP83100223 A EP 83100223A EP 0084809 B1 EP0084809 B1 EP 0084809B1
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EP
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Prior art keywords
weight
acrylic
formaldehyde
dispersion
dispersions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19830100223
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German (de)
French (fr)
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EP0084809A3 (en
EP0084809A2 (en
Inventor
Herbert Paul Dr. Dipl.-Chem. Fink
Heiner Kniese
Norbert Dr. Dipl.-Chem. Sütterlin
Klaus Müller
Werner Dr. Dipl.-Chem. Siol
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Publication of EP0084809A2 publication Critical patent/EP0084809A2/en
Publication of EP0084809A3 publication Critical patent/EP0084809A3/en
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2549—Coating or impregnation is chemically inert or of stated nonreactance
    • Y10T442/2566—Organic solvent resistant [e.g., dry cleaning fluid, etc.]

Definitions

  • the invention relates to aqueous plastic dispersions which contain no formaldehyde and no acrylonitrile and do not release these substances when the dispersion or the plastic is heated.
  • the invention further relates to its application for solidifying textile fabrics.
  • acrylic plastic dispersions are used, which contain N-methylolamide groups or formaldehyde condensation resins as crosslinking agents and / or whose plastic content can be partially made up of acrylonitrile.
  • These dispersions or the plastics contained therein release - at least when heated - small amounts of formaldehyde or acrylonitrile, which is particularly undesirable if products equipped with them are to be used in the food or clothing sector.
  • the content of acrylonitrile or formaldehyde-releasing substances has so far been considered indispensable in order to give the products equipped with the dispersions sufficient resistance to chemical cleaning agents.
  • EP-A 12 032 discloses a formaldehyde-free and acrylonitrile-free acrylate dispersion which is suitable for solidifying predominantly hydrophilic fiber structures.
  • the plastic part of the dispersion is largely made up of plasticizing monomers, such as higher acrylic or methacrylic acid esters, and the rest of it made up of plasticizing monomers, such as styrene or methyl methacrylate, and from an unsaturated carboxylic acid.
  • plasticizing monomers such as higher acrylic or methacrylic acid esters
  • plasticizing monomers such as styrene or methyl methacrylate
  • Acrylic or methacrylamide or hydroxyalkyl esters of acrylic or methacrylic acid or mixtures thereof can also be used as further comonomers to build up the dispersed plastic. This does not lead to a decisive improvement in the resistance to organic solvents.
  • the fiber structures solidified with these binders can therefore not be used for purposes in which they come into contact with organic solvents, plasticizers or plastic articles produced therewith.
  • Similar binders are proposed in EP-A 12 033 for hydrophobic fiber structures; they have the same disadvantages.
  • Acrylonitrile and formaldehyde-free acrylic plastic dispersions suitable for solidifying fiber structures should be improved in such a way that the fiber structures solidified therewith have sufficient resistance to the solvents used in chemical cleaning and to plasticizers.
  • the properties of such fiber structures which have been produced using conventional, self-crosslinking acrylic resin dispersions can be used as a yardstick for sufficient resistance.
  • These dispersions always contain N-methylolamide groups, from which small amounts of formaldehyde can be split off, and in some cases acrylonitrile.
  • the task is accomplished by acrylic plastic dispersions with the composition of the plastic specified in the main claim.
  • the following table compares the evaluation results that were obtained on textile fabrics that had been solidified with various binders under standardized test conditions.
  • One test consists in determining the loss of binders during chemical cleaning with trichlorethylene at 20 ° C.
  • the swelling is determined after storage for 4 hours in methyl isobutyl ketone at room temperature. This test reveals the sensitivity to plasticizers. In both cases, low numerical values are aimed for.
  • a conventional self-crosslinking acrylic dispersion and various other acrylic dispersions were used as binders, which are free of acrylonitrile and formaldehyde-releasing substances and which were made from a mixture of higher acrylic and methacrylic esters as well as a hydroxyalkyl ester, an unsaturated carboxylic acid and optionally with acrylamide. It is shown that the sensitivity of the solidified fiber structures to organic cleaning agents and plasticizers is considerably greater than when using known self-crosslinking acrylic dispersions and leads to results which are practically unusable.
  • Test specimens are an impregnated and dried at 80 ° C polyester fabric with a binder layer of 50 wt .-% in the determination of the binder loss and in the determination of the methyl isobutyl ketone absorption polymer films of 30 x 30 mm in size and 0.5 mm in thickness, which by drying the dispersion at 35 ° C and condensing at 140 ° C for 5 min.
  • the resistance to organic cleaning agents and plasticizers is significantly increased if small amounts of a multifunctional crosslinking agent are involved in the build-up of the binder.
  • a multifunctional crosslinking agent in principle, it is of course known that the resistance of a binder to organic solvents and plasticizers can be improved by crosslinking.
  • the crosslinking impairs the film formation, it has hitherto been regarded as essential to bring about the crosslinking, for example by means of N-methylolamide groups, only after the film has been formed when heated.
  • the plastics according to the invention are therefore only crosslinked to such a small extent that perfect film formation is possible. It was not to be expected that such low crosslinking could have a lasting effect on the resistance to organic solvents and plasticizers.
  • the increased resistance is not based solely on the crosslinking, but rather on a synergistic interaction of the crosslinking agent with the amide groups and hydroxyalkyl ester groups. It is not known how this synergism comes about, but it turns out that each of the three components mentioned is indispensable for the high durability achieved.
  • the new dispersions can be used successfully wherever self-crosslinking acrylic plastic dispersions with N-methylolamide groups have previously been used.
  • the consolidation of textile fabrics is a preferred area of application.
  • the predominant structural component a) consists of the acrylic or methacrylic esters characterized in the main claim, some, but generally not more than half, of which can be replaced by styrene.
  • acrylic and methacrylic acid alkyl esters those having at least 4 carbon atoms in the alkyl radical are particularly preferred, in particular n-butyl acrylate and methacrylate and 2-ethylhexyl acrylate.
  • High proportions of these esters ensure a low minimum film formation temperature (according to DIN 53 787) and a low dynamic freezing temperature (according to DIN 53 445).
  • the minimum film formation temperature of the dispersion is preferably below 70 ° C. and the dynamic freezing temperature of the films produced therefrom is preferably below 400C.
  • ester component a As is known, styrene and the lower alkyl esters of methacrylic acid increase these values, while they are reduced by acrylic acid esters and higher methacrylic acid esters.
  • Esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid can be used as the hydroxyalkyl ester component b). They contain at least 2 and generally no more than 12, preferably at most 4 carbon atoms in the hydroxyalkyl radical.
  • Preferred monomers of this type are hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate and 4-hydroxybutyl acrylate and methacrylate.
  • the preferred proportion of component b) in the copolymer is 3 to 15% by weight.
  • Acrylic and / or methacrylamide are used in an amount of 1 to 10, preferably 2 to 6% by weight.
  • Crosslinking comonomers d) with at least two polymerizable carbon double bonds can be compounds which contain double bonds of the same or different reactivity.
  • the former are acrylic and methacrylic esters of glycols, such as ethylene glycol, diethylene glycol, 1,4-butanediol; Methylene bis-acrylamide and methacrylamide, divinylbenzene, diallyl phthalate and triallyl cyanurate.
  • Crosslinking monomers with different reactivity of the double bonds are e.g. Vinyl methacrylate, allyl acrylate and allyl methacrylate.
  • the amount of the crosslinking comonomer depends on its crosslinking activity, which depends on the reactivity of the double bonds and on the molecular weight of the monomer. With proportions below 0.05% by weight, calculated on the weight of the copolymer, the desired improvement in solvent resistance is generally not achieved to a sufficient extent. If the proportion exceeds 3% by weight, film formation can be disturbed. Within the range of 0.5 to 3% by weight, the solvent resistance of the films increases with increasing crosslinking and is appropriately chosen so high that the film formation is just not affected.
  • the preferred content of crosslinking monomers is 0.1 to 1% by weight.
  • Unsaturated carboxylic acids do not necessarily have to be involved in the structure of the copolymer, but a proportion of up to 5% by weight, based on the weight of the copolymer, can improve the stability of the dispersion. Fractions of 0.5 to 3% by weight are usually sufficient for this.
  • Acrylic or methacrylic acid is preferably used.
  • Other usable unsaturated polymerizable mono- or dicarboxylic acids are crotonic acid, maleic acid, fumaric acid and itaconic acid.
  • the dispersions according to the invention can be produced by the known methods of emulsion polymerization in the presence of the anionic, nonionic or cationic emulsifiers and water-soluble radical-forming initiators customary in this case.
  • Anionic emulsifiers or combinations of anionic and nonionic emulsifiers are preferably used.
  • the average particle diameter (weight average) can be between 20 and 2000 nm and is preferably 100 to 500 nm.
  • the solids content is preferably between 50 and 70% of the total weight.
  • the preferred field of application for the dispersions according to the invention is the solidification of textile fabrics. These include nonwovens, wadding, fabrics and knitted fabrics made from natural or synthetic fibers or their mixtures. Amounts of, for example, 1 to over 100% by weight of plastic, based on the weight of the fiber, can be used for consolidation. 10 to 30% by weight are preferably used for nonwoven bonding.
  • the method of introduction depends in a known manner on the nature of the fiber structure and the amount of dispersion to be applied.
  • the usual application methods such as spraying, impregnation, splashing, knife coating, can be used in a known manner.
  • the treated fiber material should be dried at temperatures above 100 ° C., preferably in the range from 120 to 160 ° C.
  • BTV denotes the binder loss (in% by weight, based on binder weight) of a polyester fabric consolidated with 50% by weight (based on fiber weight) of binder when treated with trichlorethylene in a laboratory washing machine.
  • MIBK absorption denotes the swelling when stored in methyl isobutyl ketone for 4 hours at 20 ° C., measured in% by weight, based on the binder weight.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Nonwoven Fabrics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polymerisation Methods In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft wäßrige Kunststoffdispersionen, die keinen Formaldehyd und kein Acrylnitril enthalten und diese Stoffe beim Erhitzen der Dispersion oder des Kunststoffes nicht freisetzen. Die Erfindung betrifft weiterhin ihre Anwendung zum Verfestigen von textilen Flächengebilden. Für diesen Zweck werden Acrylkunststoffdispersionen eingesetzt, die N-Methylolamidgruppen oder Formaldehydkondensationsharze als Vernetzungsmittel enthalten und/oder deren Kunststoffanteil zum Teil aus Acrylnitril aufgebaut sein kann. Diese Dispersionen oder die darin enthaltenen Kunststoffe geben - zumindest beim Erhitzen -kleine Mengen von Formaldehyd oder Acrylnitril ab, was insbesondere dann unerwünscht ist, wenn damit ausgerüstete Produkte im Nahrungsmittel-oder Bekleidungsbereich eingesetzt werden sollen. Der Gehalt an Acrylnitril bzw. Formaldehyd abgebenden Stoffen galt bisher als unverzichtbar, um den mit den Dispersionen ausgerüsteten Produkten eine ausreichende Beständigkeit gegen chemische Reinigungsmittel zu verleihen.The invention relates to aqueous plastic dispersions which contain no formaldehyde and no acrylonitrile and do not release these substances when the dispersion or the plastic is heated. The invention further relates to its application for solidifying textile fabrics. For this purpose, acrylic plastic dispersions are used, which contain N-methylolamide groups or formaldehyde condensation resins as crosslinking agents and / or whose plastic content can be partially made up of acrylonitrile. These dispersions or the plastics contained therein release - at least when heated - small amounts of formaldehyde or acrylonitrile, which is particularly undesirable if products equipped with them are to be used in the food or clothing sector. The content of acrylonitrile or formaldehyde-releasing substances has so far been considered indispensable in order to give the products equipped with the dispersions sufficient resistance to chemical cleaning agents.

Es besteht daher ein Bedarf an wäßrigen Kunststoffdispersionen, die frei von Formaldehyd, formaldehydabgebenden Stoffen und Acrylnitril sind und trotzdem die Herstellung reinigungsbeständiger verfestigter Fasergebilde gestatten.There is therefore a need for aqueous plastic dispersions which are free from formaldehyde, formaldehyde-releasing substances and acrylonitrile and nevertheless permit the production of solid fiber structures which are resistant to cleaning.

Stand der TechnikState of the art

Aus der EP-A 12 032 ist eine formaldehyd- und acrylnitrilfreie Acrylatdispersion bekannt, die sich zum Verfestigen von überwiegend hydrophilen Fasergebilden eignet. Der Kunststoffanteil der Dispersion ist zum größten Teil aus weichmachenden Monomeren, wie höheren Acryl- oder Methacrylsäureestern, und zum übrigen Teil aus hartmachenden Monomeren, wie Styrol oder Methylmethacrylat, sowie aus einer ungesättigten Carbonsäure aufgebaut. Derartige Dispersionen sind seit langer Zeit bekannt. Damit ausgerüstete textile Flächengebilde haben den Nachteil, daß sie gegenüber den in der chemischen Reinigung gebräuchlichen Lösungsmitteln wenig beständig sind. Als weitere Comonomere können zum Aufbau des dispergierten Kunststoffes Acryl- oder Methacrylamid oder Hydroxyalkylester der Acryl-oder Methacrylsäure oder Gemische davon mitverwendet werden. Dadurch wird keine entscheidende Verbesserung der Beständigkeit gegenüber organischen Lösungsmitteln erreicht. Die mit diesen Bindemitteln verfestigten Fasergebilde können daher nicht für Zwecke verwendet werden, bei denen sie mit organischen Lösungsmitteln, Kunststoff-Weichmachern oder damit hergestellten Kunststoff-artikeln in Berührung kommen. Ähnliche Bindemittel werden in der EP-A 12 033 für hydrophobe Fasergebilde vorgeschlagen; sie haben die gleichen Nachteile.EP-A 12 032 discloses a formaldehyde-free and acrylonitrile-free acrylate dispersion which is suitable for solidifying predominantly hydrophilic fiber structures. The plastic part of the dispersion is largely made up of plasticizing monomers, such as higher acrylic or methacrylic acid esters, and the rest of it made up of plasticizing monomers, such as styrene or methyl methacrylate, and from an unsaturated carboxylic acid. Such dispersions have been known for a long time. Textile fabrics equipped with this have the disadvantage that they are not very resistant to the solvents commonly used in chemical cleaning. Acrylic or methacrylamide or hydroxyalkyl esters of acrylic or methacrylic acid or mixtures thereof can also be used as further comonomers to build up the dispersed plastic. This does not lead to a decisive improvement in the resistance to organic solvents. The fiber structures solidified with these binders can therefore not be used for purposes in which they come into contact with organic solvents, plasticizers or plastic articles produced therewith. Similar binders are proposed in EP-A 12 033 for hydrophobic fiber structures; they have the same disadvantages.

Aufgabe und LösungTask and solution

Zum Verfestigen von Fasergebilden geeignete, acrylnitril- und formaldehydfreie Acrylkunststoffdispersionen sollen dahingehend verbessert werden, daß die damit verfestigten Fasergebilde eine ausreichende Beständigkeit gegenüber den in der chemischen Reinigung verwendeten Lösungsmitteln und gegenüber Weichmachungsmitteln haben. Als Maßstab für eine ausreichende Beständigkeit können die Eigenschaften solcher Fasergebilde herangezogen werden, die mit herkömmlichen, selbstvernetzenden Acrylharzdispersionen hergestellt worden sind. Diese Dispersionen enthalten stets N-Methylolamidgruppen, aus denen kleine Mengen Formaldehyd abgespalten werden können, sowie in manchen Fällen Acrylnitril. Die gestellte Aufgabe wird durch Acrylkunststoffdispersionen mit der im Hauptanspruch angegebenen Zusammensetzung des Kunststoffes erfüllt.Acrylonitrile and formaldehyde-free acrylic plastic dispersions suitable for solidifying fiber structures should be improved in such a way that the fiber structures solidified therewith have sufficient resistance to the solvents used in chemical cleaning and to plasticizers. The properties of such fiber structures which have been produced using conventional, self-crosslinking acrylic resin dispersions can be used as a yardstick for sufficient resistance. These dispersions always contain N-methylolamide groups, from which small amounts of formaldehyde can be split off, and in some cases acrylonitrile. The task is accomplished by acrylic plastic dispersions with the composition of the plastic specified in the main claim.

Vorteil der ErfindungAdvantage of the invention

In der nachfolgenden Tabelle werden Bewertungsergebnisse gegenübergestellt, die an textilen Flächengebilden, die mit verschiedenen Bindemitteln verfestigt worden waren, unter standardisierten Prüfungsbedingungen erhalten wurden. Die eine Prüfung besteht in der Ermittlung des Verlustes an Bindemitteln bei der chemischen Reinigung mit Trichloräthylen bei 20°C. Bei der anderen Prüfung wird die Quellung bei der 4-stündigen Lagerung in Methylisobutylketon bei Raumtemperatur bestimmt. Diese Prüfung läßt die Empfindlichkeit gegen Weichmachungsmittel erkennen. In beiden Fällen werden niedrige Zahlenwerte angestrebt.The following table compares the evaluation results that were obtained on textile fabrics that had been solidified with various binders under standardized test conditions. One test consists in determining the loss of binders during chemical cleaning with trichlorethylene at 20 ° C. In the other test, the swelling is determined after storage for 4 hours in methyl isobutyl ketone at room temperature. This test reveals the sensitivity to plasticizers. In both cases, low numerical values are aimed for.

Als Bindemittel wurde eine herkömmliche selbstvernetzende Acryldispersion sowie verschiedene andere Acryldispersionen eingesetzt, die von Acrylnitril und Formaldehyd abgebenden Stoffen frei sind und die aus einem Gemisch höherer Acryl- und Methacrylester sowie einem Hydroxyalkylester, einer ungesättigten Carbonsäure und gegebenenfalls mit Acrylamid hergestellt worden sind. Es zeigt sich, daß die Empfindlichkeit der verfestigten Fasergebilde gegenüber organischen Reinigungsmitteln und Weichmachungsmitteln wesentlich größer als bei der Verwendung bekannter selbstvernetzender Acryldispersionen ist und zu praktisch unbrauchbaren Resultaten führt.A conventional self-crosslinking acrylic dispersion and various other acrylic dispersions were used as binders, which are free of acrylonitrile and formaldehyde-releasing substances and which were made from a mixture of higher acrylic and methacrylic esters as well as a hydroxyalkyl ester, an unsaturated carboxylic acid and optionally with acrylamide. It is shown that the sensitivity of the solidified fiber structures to organic cleaning agents and plasticizers is considerably greater than when using known self-crosslinking acrylic dispersions and leads to results which are practically unusable.

Prüfkörper sind bei der Bestimmung des Binderverlustes ein imprägniertes und bei 80°C getrocknetes Polyestergewebe mit einer Binderauflage von 50 Gew.-% und bei der Bestimmung der Methylisobutylketonaufnahme Polymerisatfilme von 30 x 30 mm Größe und 0,5 mm Dicke, die durch Eintrocknen der Dispersion bei 35°C und Kondensieren bei 140°C während 5 min hergestellt worden sind.

Figure imgb0001
Test specimens are an impregnated and dried at 80 ° C polyester fabric with a binder layer of 50 wt .-% in the determination of the binder loss and in the determination of the methyl isobutyl ketone absorption polymer films of 30 x 30 mm in size and 0.5 mm in thickness, which by drying the dispersion at 35 ° C and condensing at 140 ° C for 5 min.
Figure imgb0001

Überraschenderweise wird die Beständigkeit gegenüber organischen Reinigungsmitteln und Weichmachungsmitteln wesentlich erhöht, wenn am Aufbau des Bindemittels geringe Mengen eines mehrfunktionellen Vernetzungsmittels beteiligt sind. Grundsätzlich ist es natürlich bekannt, daß die Beständigkeit eines Bindemittels gegenüber organischen Lösungsmitteln und Weichmachungsmitteln durch Vernetzung verbessert werden kann. Da die Vernetzung jedoch die Filmbildung beeinträchtigt, wurde es bisher als unerläßlich angesehen, die Vernetzung, beispielsweise mittels N-Methylolamidgruppen erst nach der Filmbildung beim Erhitzen herbeizuführen. Die erfindungsgemäßen Kunststoffe werden daher nur in so geringem Maße vernetzt, daß eine einwandfreie Filmbildung möglich ist. Es war nicht zu erwarten, daß eine solche geringe Vernetzung die Beständigkeit gegen organische Lösungsmittel und Weichmachungsmittel nachhaltig beeinflussen könnte. Tatsächlich beruht die erhöhte Beständigkeit auch nicht allein auf der Vernetzung, sondern auf einer synergistischen Zusammenwirkung des Vernetzungsmittels mit den Amidgruppen und Hydroxyalkylestergruppen. Es ist nicht bekannt, wie dieser Synergismus zustande kommt, jedoch zeigt es sich, daß jeder der drei genannten Bestandteile für die erzielte hohe Beständigkeit unerläßlich ist.Surprisingly, the resistance to organic cleaning agents and plasticizers is significantly increased if small amounts of a multifunctional crosslinking agent are involved in the build-up of the binder. In principle, it is of course known that the resistance of a binder to organic solvents and plasticizers can be improved by crosslinking. However, since the crosslinking impairs the film formation, it has hitherto been regarded as essential to bring about the crosslinking, for example by means of N-methylolamide groups, only after the film has been formed when heated. The plastics according to the invention are therefore only crosslinked to such a small extent that perfect film formation is possible. It was not to be expected that such low crosslinking could have a lasting effect on the resistance to organic solvents and plasticizers. In fact, the increased resistance is not based solely on the crosslinking, but rather on a synergistic interaction of the crosslinking agent with the amide groups and hydroxyalkyl ester groups. It is not known how this synergism comes about, but it turns out that each of the three components mentioned is indispensable for the high durability achieved.

Gewerbliche AnwendbarkeitIndustrial applicability

Dank der erhöhten Beständigkeit der aus den erfindungsgemäßen Dispersionen erzeugten Filme gegenüber organischen Lösungsmitteln und Weichmachungsmitteln können die neuen Dispersionen überall da mit Erfolg eingesetzt werden, wo bisher selbstvernetzende Acrylkunststoffdispersionen mit N-Methylolamidgruppen eingesetzt wurden. Die Verfestigung von textilen Flächengebilden ist ein bevorzugtes Anwendungsge- , biet.Thanks to the increased resistance of the films produced from the dispersions according to the invention to organic solvents and plasticizers, the new dispersions can be used successfully wherever self-crosslinking acrylic plastic dispersions with N-methylolamide groups have previously been used. The consolidation of textile fabrics is a preferred area of application.

Herstellung der erfindungsgemäßen DispersionenPreparation of the dispersions according to the invention

Die überwiegende Aufbaukomponente a) besteht aus den im Hauptanspruch gekennzeichneten Acryl- oder Methacrylestern, die teilweise, in der Regel jedoch nicht mehr als zur Hälfte, durch Styrol ersetzt sein können. Unter den Acryl- und Methacrylsäurealkylestern sind solche mit mindestens 4 C-Atomen im Alkylrest besonders bevorzugt, insbesondere n-Butyl-acrylat und -methacrylat und 2-Äthylhexylacrylat. Hohe Anteile dieser Ester gewährleisten eine niedrige Mindestfilmbildungstemperatur (nach DIN 53 787) und eine niedrige dynamische Einfriertemperatur (nach DIN 53 445). Die minimale Filmbildungstemperatur der Dispersion liegt vorzugsweise unter 70°C und die dynamische Einfriertemperatur der daraus hergestellten Filme vorzugsweise unter 400C. Diese Werte werden im wesentlichen durch die Wahl der Esterkomponente a) festgelegt. Bekanntlich wirken Styrol und die niederen Alkylester der Methacrylsäure erhöhend auf diese Werten, während sie durch Acrylsäureester und höhere Methacrylsäureester herabgesetzt werden.The predominant structural component a) consists of the acrylic or methacrylic esters characterized in the main claim, some, but generally not more than half, of which can be replaced by styrene. Among the acrylic and methacrylic acid alkyl esters, those having at least 4 carbon atoms in the alkyl radical are particularly preferred, in particular n-butyl acrylate and methacrylate and 2-ethylhexyl acrylate. High proportions of these esters ensure a low minimum film formation temperature (according to DIN 53 787) and a low dynamic freezing temperature (according to DIN 53 445). The minimum film formation temperature of the dispersion is preferably below 70 ° C. and the dynamic freezing temperature of the films produced therefrom is preferably below 400C. These values are essentially determined by the choice of the ester component a). As is known, styrene and the lower alkyl esters of methacrylic acid increase these values, while they are reduced by acrylic acid esters and higher methacrylic acid esters.

Als Hydroxyalkylester-Komponente b) können Ester der Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure oder Itakonsäure eingesetzt werden. Die enthalten wenigstens 2 und im allgemeinen nicht mehr als 12, vorzugsweise höchstens 4 C-Atome im Hydroxyalkylrest. Bevorzugte Monomere dieser Art sind Hydroxyäthylacrylat und -methacrylat, 2-Hydroxypropylacrylat und -methacrylat und 4-Hydroxybutylacrylat und -methacrylat. Der bevorzugte Mengenanteil der Komponente b) an dem Mischpolymerisat beträgt 3 bis 15 Gew.-%.Esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid can be used as the hydroxyalkyl ester component b). They contain at least 2 and generally no more than 12, preferably at most 4 carbon atoms in the hydroxyalkyl radical. Preferred monomers of this type are hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate and 4-hydroxybutyl acrylate and methacrylate. The preferred proportion of component b) in the copolymer is 3 to 15% by weight.

Acryl- und/oder Methacrylamid werden in einer Menge von 1 bis 10, vorzugsweise 2 bis 6 Gew.-% eingesetzt.Acrylic and / or methacrylamide are used in an amount of 1 to 10, preferably 2 to 6% by weight.

Als vernetzende Comonomere d) mit wenigstens zwei polymerisierbaren KohlenstoffDoppelbindungen können Verbindungen eingesetzt werden, die Doppelbindungen von gleicher oder unterschiedlicher Reaktivität enthalten. Beispiele für die ersteren sind Acryl- und Methacrylester von Glykolen, wie Äthylenglykol, Diäthylenglykol, Butandiol-1,4; Methylen-bis-acrylamid und -methacrylamid, Divinylbenzol, Diallylphthalat und Triallylcyanurat. Vernetzende Monomere mit unterschiedlicher Reaktivität der Doppelbindungen sind z.B. Vinylmethacrylat, Allylacrylat und Allylmethacrylat. Die Menge des vernetzenden Comonomeren richtet sich nach seiner Vernetzungswirksamkeit, die von der Reaktivität der Doppelbindungen und vom Molekulargewicht des Monomeren abhängt. Bei Anteilen unter 0,05 Gew.-%, berechnet auf das Gewicht des Mischpolymerisats, wird die erwünschte Verbesserung der Lösungsmittelbeständigkeit im allgemeinen nicht in ausreichendem Maße erreicht. Bei Anteilen über 3 Gew.-% kann die Filmbildung gestört werden. Innerhalb des Bereiches von 0,5 bis 3 Gew.-% nimmt die Lösungsmittelbeständigkeit der Filme mit steigender Vernetzung zu und wird zweckmäßig so hoch gewählt, daß die Filmbildung gerade noch nicht beeinträchtigt wird. Der bevorzugte Gehalt an vernetzenden Monomeren beträgt 0,1 bis 1 Gew.-%.Crosslinking comonomers d) with at least two polymerizable carbon double bonds can be compounds which contain double bonds of the same or different reactivity. Examples of the former are acrylic and methacrylic esters of glycols, such as ethylene glycol, diethylene glycol, 1,4-butanediol; Methylene bis-acrylamide and methacrylamide, divinylbenzene, diallyl phthalate and triallyl cyanurate. Crosslinking monomers with different reactivity of the double bonds are e.g. Vinyl methacrylate, allyl acrylate and allyl methacrylate. The amount of the crosslinking comonomer depends on its crosslinking activity, which depends on the reactivity of the double bonds and on the molecular weight of the monomer. With proportions below 0.05% by weight, calculated on the weight of the copolymer, the desired improvement in solvent resistance is generally not achieved to a sufficient extent. If the proportion exceeds 3% by weight, film formation can be disturbed. Within the range of 0.5 to 3% by weight, the solvent resistance of the films increases with increasing crosslinking and is appropriately chosen so high that the film formation is just not affected. The preferred content of crosslinking monomers is 0.1 to 1% by weight.

Ungesättigte Carbonsäuren brauchen am Aufbau des Mischpolymerisats nicht unbedingt beteiligt zu sein, jedoch kann ein Anteil bis zu 5 Gew.- %, bezogen auf das Gewicht des Mischpolymerisats, die Stabilität der Dispersion verbessern. Anteile von 0,5 bis 3 Gew.-% sind dafür meistens ausreichend. Vorzugsweise werden Acryl- oder Methacrylsäure verwendet. Andere verwendbare ungesättigte polymerisierbare Mono- oder Dicarbonsäuren sind Crotonsäure, Maleinsäure, Fumarsäure und Itakonsäure.Unsaturated carboxylic acids do not necessarily have to be involved in the structure of the copolymer, but a proportion of up to 5% by weight, based on the weight of the copolymer, can improve the stability of the dispersion. Fractions of 0.5 to 3% by weight are usually sufficient for this. Acrylic or methacrylic acid is preferably used. Other usable unsaturated polymerizable mono- or dicarboxylic acids are crotonic acid, maleic acid, fumaric acid and itaconic acid.

In begrenzten Mengen, die 20 Gew.-% nicht überschreiten, können weitere Monomere am Aufbau des Mischpolymerisats beteiligt sein, sofern es sich nicht um Acryl- oder Methacrylnitril handelt und keine Formaldehyd abspaltenden Gruppen darin enthalten sind. Darunter sind solche Gruppen zu verstehen, die zumindest beim Erwärmen zur Freisetzung von Formaldehyd führen können. Hierzu zählen vor allem N-Methylolamidgruppen, sowie verkappte Methylolgruppen, wie Mannich-Basen oder N-Amid-methylol-alkyl- äther. Für die Zwecke der Erfindung sind zusätzliche Monomerkomponenten f) in der Regel nicht erforderlich, können aber zweckmäßig sein, wenn damit bestimmte Aufgaben erfüllt werden. Als Beispiel sei der Einbau von N-Vinylimidazol oder von Dialkylaminoalkylestern der Acryl- oder Methacrylsäure oder von deren Salzen genannt. Diese Comonomeren verbessern in Anteilen von z.B. 1-5 Gew.-% die Affinität des Kunststoffes gegenüber Cellulosefasern. Beispiele weiterer, für andere Zwecke mitverwendbarer Comonomerer sind N-Vinylpyrrolidon, Vinylacetat und andere Vinylester, Vinylchlorid, Vinylidenchlorid, Butadien, Äthylen und Propylen.In limited amounts, which do not exceed 20% by weight, other monomers can be involved in the construction of the copolymer, provided that it is not acrylonitrile or methacrylonitrile and does not contain any formaldehyde-releasing groups. These are to be understood as groups which, at least when heated, can lead to the release of formaldehyde. These include, above all, N-methylolamide groups and also blocked methylol groups, such as Mannich bases or N-amide-methylol-alkyl ethers certain tasks are fulfilled. An example is the incorporation of N-vinylimidazole or of dialkylaminoalkyl esters of acrylic or methacrylic acid or of their salts. These comonomers improve in proportions e.g. 1-5 wt .-% the affinity of the plastic for cellulose fibers. Examples of further comonomers which can be used for other purposes are N-vinylpyrrolidone, vinyl acetate and other vinyl esters, vinyl chloride, vinylidene chloride, butadiene, ethylene and propylene.

Die erfindungsgemäßen Dispersionen können nach den bekannten Verfahren der Emulsionspolymerisation in Gegenwart der dabei gebräuchlichen anionischen, nicht-ionischen oder kationischen Emulgiermittel und wasserlöslicher radikalbildender Initiatoren erzeugt werden. Vorzugsweise werden anionische Emulgatoren oder Kombinationen von anionischen und nichtionischen Emulgatoren verwendet. Der mittlere Teilchendurchmesser (Gewichtsmittelwert) kann zwischen 20 und 2000 nm liegen und beträgt vorzugsweise 100 bis 500 nm. Der Feststoffgehalt liegt vorzugsweise zwischen 50 und 70% des Gesamtgewichts.The dispersions according to the invention can be produced by the known methods of emulsion polymerization in the presence of the anionic, nonionic or cationic emulsifiers and water-soluble radical-forming initiators customary in this case. Anionic emulsifiers or combinations of anionic and nonionic emulsifiers are preferably used. The average particle diameter (weight average) can be between 20 and 2000 nm and is preferably 100 to 500 nm. The solids content is preferably between 50 and 70% of the total weight.

Anwendungapplication

Das bevorzugte Anwendungsgebiet für die erfindungsgemäßen Dispersionen ist das Verfestigen von textilen Flächengebilden. Dazu gehören Faservliese, Watten, Gewebe und Gewirke aus natürlichen oder synthetischen Fasern oder deren Gemischen. Zur Verfestigung können Mengen von beispielsweise 1 bis über 100 Gew.-% Kunststoff, bezogen auf das Fasergewicht angewendet werden. Zur Vliesverfestigung werden vorzugsweise 10 bis 30 Gew.-% eingesetzt. Das Verfahren der Einbringung richtet sich in bekannter Weise nach der Beschaffenheit des Fasergebildes und der aufzubringenden Menge der Dispersion.The preferred field of application for the dispersions according to the invention is the solidification of textile fabrics. These include nonwovens, wadding, fabrics and knitted fabrics made from natural or synthetic fibers or their mixtures. Amounts of, for example, 1 to over 100% by weight of plastic, based on the weight of the fiber, can be used for consolidation. 10 to 30% by weight are preferably used for nonwoven bonding. The method of introduction depends in a known manner on the nature of the fiber structure and the amount of dispersion to be applied.

Die üblichen Auftragsmethoden, wie Sprühen, Imprägnieren, Pflatschen, Rakeln, können in bekannter Weise angewendet werden. Die Trocknung des behandelten Fasermaterials sollte bei Temperaturen über 100 °C erfolgen, vorzugsweise im Bereich von 120 bis 160°C.The usual application methods, such as spraying, impregnation, splashing, knife coating, can be used in a known manner. The treated fiber material should be dried at temperatures above 100 ° C., preferably in the range from 120 to 160 ° C.

Andere flächige Substrate, wie Papier, Holz, Kunststoffolien, Bleche, u.dergl. können mit den erfindungsgemäßen Dispersionen, gegebenenfalls nach Pigmentierung, beschichtet werden und werden dann ebenfalls bei Temperaturen über 100°C getrocknet. Während der Trocknung verfestigt sich der Film und erhält seine hohe Beständigkeit gegen organische Lösungsmittel und organische Weichmachungsmittel.Other flat substrates, such as paper, wood, plastic films, sheets, etc. can be coated with the dispersions according to the invention, optionally after pigmentation, and are then likewise dried at temperatures above 100 ° C. The film solidifies during drying and maintains its high resistance to organic solvents and organic plasticizers.

BeispieleExamples Herstellungsverfahren der Dispersionen nach Beispielen 1 bis 6.Production process of the dispersions according to Examples 1 to 6.

In einem 1 I-Rundkolben, mit Rührer und Kontaktthermometer ausgerüstet, wurden 155 Teile vollentsalztes Wasser unter Rühren auf 80 °C erhitzt und mit 0,16 Teilen einer 90%igen sulfonierten äthoxylierten Alkyl-arylol-maleinsäure, gelöst, in 5 Teilen Butylmethacrylat, sowie mit 5 Teilen einer 4%igen Ammoniumperoxodisulfatlösung versetzt. Dann wurde nach einer Pause von 4 Minuten bei 80°C innerhalb von 4 Stunden eine Emulsion aus:

  • 240 Teilen vollentsalztem Wasser
  • 1 Teil 90%iger sulfonierter äthoxylierter Alkyl-arylol-maleinsäure
  • 0,9 Teilen Ammoniumperoxodisulfat
  • 395 Teilen der Monomerenmischung gemäß nachfolgender Tabelle zugetropft. Anschließend wurde die Temperatur 2 weitere Stunden auf 80 °C gehalten. Danach wurde auf Raumtemperatur abgekühlt und der pH-Wert durch Zugabe von Phosphorsäure auf einen Wert von 2,2 eingestellt. Es wurden stabile, koagulatfreie Dispersionen erhalten.
In a 1 liter round-bottom flask equipped with a stirrer and contact thermometer, 155 parts of demineralized water were heated to 80 ° C. with stirring and dissolved in 5 parts of butyl methacrylate with 0.16 part of a 90% sulfonated ethoxylated alkyl-arylol-maleic acid. and mixed with 5 parts of a 4% ammonium peroxodisulfate solution. Then, after a pause of 4 minutes at 80 ° C, an emulsion was formed within 4 hours:
  • 240 parts of deionized water
  • 1 part of 90% sulfonated ethoxylated alkyl arylol maleic acid
  • 0.9 parts of ammonium peroxodisulfate
  • 395 parts of the monomer mixture were added dropwise according to the table below. The temperature was then kept at 80 ° C. for a further 2 hours. The mixture was then cooled to room temperature and the pH was adjusted to 2.2 by adding phosphoric acid. Stable, coagulate-free dispersions were obtained.

In der nachfolgenden Tabelle sind in den beiden rechten Spalten Ergebnisse der anwendungstechnischen Prüfung der Dispersionen angegeben. "BTV" bezeichnet den Binderverlust (in Gew.-%, bezogen auf Bindergewicht) eines mit 50 Gew.-% (bezogen auf Fasergewicht) Binder verfestigten Polyestergewebes bei der Behandlung mit Trichloräthylen in einer Laborwaschmaschine. Mit «MIBK-Aufnahme» ist die Quellung bei 4-stündiger Lagerung in Methylisobutylketon bei 20°C, gemessen in Gew.-%, bezogen auf Bindergewicht, bezeichnet.The following table shows the results of the performance test of the dispersions in the two columns on the right. " BTV " denotes the binder loss (in% by weight, based on binder weight) of a polyester fabric consolidated with 50% by weight (based on fiber weight) of binder when treated with trichlorethylene in a laboratory washing machine. “MIBK absorption” denotes the swelling when stored in methyl isobutyl ketone for 4 hours at 20 ° C., measured in% by weight, based on the binder weight.

Herstellungsverfahren der Dispersionen nach Beispielen 7 bis 11.Production process of the dispersions according to Examples 7 to 11.

In einem 1 I Rundkolben, mit Rührer und Kontaktthermometer ausgerüstet, wurden 155 Teile vollentsalztes Wasser sowie 0,06 Teile eines Emulgators, der durch Umsetzung von 1 Mol Tributylphenol mit 7 Mol Äthylenoxid, Sulfatierung und Überführung in das Natriumsalz erhalten worden ist, unter Rühren auf 800C erhitzt und mit 5 Teilen einer 4%igen Ammoniumperoxodisulfatlösung versetzt. Dann wurden bei 80°C innerhalb von 4 Stunden eine Emulsion aus

  • 240 Teilen vollentsalztem Wasser 2 Teilen des oben beschriebenen Emulgators 0,9 Teilen Ammoniumperoxodisulfat
  • 400 Teilen der Monomerenmischung gemäß nachfolgender Tabelle zugetropft. Anschließend wurde die Temperatur 2 weitere Stunden auf 80°C gehalten. Danach wurde auf Raumtemperatur abgekühlt und der pH-Wert mit Phosphorsäure auf 2,2 eingestellt.
In a 1 liter round-bottom flask equipped with a stirrer and contact thermometer, 155 parts of fully demineralized water and 0.06 part of an emulsifier, which had been obtained by reacting 1 mol of tributylphenol with 7 mol of ethylene oxide, sulfation and conversion into the sodium salt, were stirred on 800C heated and mixed with 5 parts of a 4% ammonium peroxodisulfate solution. Then an emulsion was formed at 80 ° C within 4 hours
  • 240 parts of deionized water 2 parts of the emulsifier described above 0.9 parts of ammonium peroxodisulfate
  • 400 parts of the monomer mixture were added dropwise according to the table below. The temperature was then kept at 80 ° C. for a further 2 hours. The mixture was then cooled to room temperature and the pH was adjusted to 2.2 using phosphoric acid.

Es wurden stabile, koagulatfreie Dispersionen erhalten.

Figure imgb0002
Stable, coagulate-free dispersions were obtained.
Figure imgb0002

Beispiel 3 (Vergleichsversuch ohne vernetzendes Comonomeres)Example 3 (comparative experiment without crosslinking comonomer)

Figure imgb0003
Figure imgb0003

Beispiel 4 (Vergleichsversuch ohne vernetzendes Comonomer)Example 4 (comparative experiment without crosslinking comonomer)

Figure imgb0004
Figure imgb0004

Beispiel 5 (Vergleichsversuch ohne vernetzendes Comonomer und ohne Amidkomponente)Example 5 (comparative experiment without crosslinking comonomer and without amide component)

Figure imgb0005
Figure imgb0005

Beispiel 6 (Vergleichsversuch ohne (Meth)acrylamid)Example 6 (comparative experiment without (meth) acrylamide)

Figure imgb0006
Figure imgb0006

Beispiel 7Example 7

Figure imgb0007
Figure imgb0007

Beispiel 8Example 8

Figure imgb0008
Figure imgb0008

Beispiel 9Example 9

Figure imgb0009
Figure imgb0009

Beispiel 10Example 10

Figure imgb0010
Figure imgb0010

Beispiel 11Example 11

Figure imgb0011
Figure imgb0011

Claims (4)

1. Acrylic plastics dispersion free from formaldehyde, substances which give off formaldehyde and acrylnitrile, containing in the aqueous phase a dispersed mixed polymer synthesised from
a) 70-96.95% by weight of alkyl esters of acrylic and/or methacrylic acid with 1 to 18 carbon atoms in the alkyl group or a mixture thereof with styrene,
b) 2-30% by weight of hydroxyalkylesters of an unsaturated polymerisable mono- or dicarbonic acid having at least 2 carbon atoms in the hydroxyalkyl group,
c) 1-10% by weight of acrylamide or methacrylamide,
d) 0.05-3% by weight of cross-linking comonomers having at least 2 polymerisable double bonds,
e) 0-5% by weight of unsaturated polymerisable mono- or dicarbonic acids and optionally,
f) 0-20% by weight of other comonomers which do not contain any nitrile groups or any groups which cleave formaldehyde.
2. Plastics dispersion as claimed in claim 1, characterised by a minimum film forming temperature of below 70 °C.
3. Plastics dispersion as claimed in claim 2, characterised by a dynamic freezing temperature of the dispersed copolymer of less than 40°C.
4. Use of plastics dispersion as claimed in claims 1 to 3 for reinforcing flat textile structures.
EP19830100223 1982-01-23 1983-01-13 Dispersion of acryl plastics Expired EP0084809B1 (en)

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