EP0054573B1 - Process for the consolidation of fibrous material with dispersions of synthetic resin - Google Patents

Process for the consolidation of fibrous material with dispersions of synthetic resin Download PDF

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Publication number
EP0054573B1
EP0054573B1 EP80108012A EP80108012A EP0054573B1 EP 0054573 B1 EP0054573 B1 EP 0054573B1 EP 80108012 A EP80108012 A EP 80108012A EP 80108012 A EP80108012 A EP 80108012A EP 0054573 B1 EP0054573 B1 EP 0054573B1
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EP
European Patent Office
Prior art keywords
plastics
dispersion
weight
methacrylic acid
acrylic
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EP80108012A
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German (de)
French (fr)
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EP0054573A1 (en
Inventor
Herbert Dr. Fink
Klaus Dr. Hübner
Egon Grumbach
Hans Ottofrickenstein
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Priority to EP80108012A priority Critical patent/EP0054573B1/en
Priority to AT80108012T priority patent/ATE11681T1/en
Priority to DE8080108012T priority patent/DE3070134D1/en
Publication of EP0054573A1 publication Critical patent/EP0054573A1/en
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Publication of EP0054573B1 publication Critical patent/EP0054573B1/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

Definitions

  • the invention relates to a method for solidifying fiber structures by treatment with aqueous plastic dispersions.
  • the choice of the plastic dispersions to be used depends, among other things, on whether the finished fiber structure should be resistant to organic solvents. If this is not the case, plastic dispersions can be used which are free of formaldehyde-releasing substances and whose plastic content is essentially composed, for example, of alkyl esters of acrylic or methacrylic acid, vinyl esters and / or styrene and small amounts of ⁇ , ⁇ -unsaturated carboxylic acids.
  • plastic dispersions are used that can be crosslinked after coating or soaking and drying at elevated temperatures.
  • the crosslinking is achieved either by adding water-soluble aminoplast resins to the dispersions of the type mentioned above or by using plastic dispersions in the formation of which condensable formaldehyde derivatives, in particular N-methylolacrylamide or methacrylamide, are involved.
  • consolidated nonwovens are already known, for the manufacture of which plastic dispersions were used which are free of formaldehyde or of formaldehyde-releasing substances. They are produced with a content of 1 to 8 wt .-% units of an unsaturated carboxylic acid and subsequently neutralized with alkali. This does not significantly improve the sensitivity of the binder to solvents or plasticizers.
  • the invention has for its object to provide fiber structures with an equipment that is at least limited solvent-resistant or block-free or tack-free, and to do this use an aqueous plastic dispersion that is free of formaldehyde-releasing substances and whose plastic content consists predominantly of alkyl esters of acrylic or methacrylic acid, as well as small amounts of a, ⁇ -unsaturated carboxylic acids.
  • the stated object can be achieved with a plastic dispersion of this type, which can be added in the initial charge and under using the feed process using 1-4% by weight acrylic or / and methacrylic acid, based on the total weight of polymerizable compounds Addition of the other monomers has been prepared in the feed, the acrylic or methacrylic acid being used in the form of an alkali or ammonium salt.
  • the monomers as such or in the form of an aqueous emulsion are gradually run under polymerization conditions to a template in which the polymerization takes place.
  • the initial charge consists of an aqueous phase which generally contains a water-soluble polymerization initiator and one or more emulsifiers.
  • the improved solvent resistance of the coatings or impregnations produced in accordance with the invention depends on the fact that, in the preparation of the plastic dispersion to be used, acrylic or methacrylic acid in the form of its alkali metal or ammonium salt is dissolved in the initial charge.
  • Equivalent plastic dispersions cannot be prepared by gradually adding the acrylic or methacrylic acid or its salts together with the other monomers during the feed process or by adding the acrylic or methacrylic acid as such to the initial charge and only neutralizing it after the polymerization.
  • plastic dispersions which are free of formaldehyde-releasing substances by the process indicated above is known from OE-PS 236 643 and from FR-A-1 157 265.
  • the plastic dispersions produced in this way have not yet been used to solidify fiber structures.
  • the impregnations and coatings obtained would be characterized by improved resistance to organic solvents.
  • Plastic dispersions with a minimum film-forming temperature below 25 ° C. and with a Txmax value of the dispersed plastic (according to DIN 53445) below 50 ° C. are used with particular advantage for the process of the invention.
  • the plastic portion of the dispersion is preferably composed of more than 50% by weight of acrylic acid alkyl esters with 1-8 C atoms in the alkyl radical and for the most part predominantly from methacrylic acid alkyl esters with 1-4 C atoms in the alkyl radical.
  • Other water-insoluble monomers, such as. B. styrene, vinyl acetate or vinylidene chloride, can be involved in minor amounts in the construction of the plastic.
  • the share of Acrylic and / or methacrylic acid copolymerized in salt form is preferably 2-3% by weight calculated as free acid and based on the weight of the plastic.
  • the alkali salts are preferably the sodium and potassium salts.
  • the ammonium salts can be from ammonia or from organic amines, such as. B. ethanolamine.
  • the preferred method for producing the plastic dispersion is the emulsion feed method.
  • Part of the amount of water provided as the aqueous phase of the dispersion is placed in the polymerization vessel and the salt of acrylic and / or methacrylic acid is dissolved therein. be solved.
  • the initial charge is brought to a temperature suitable for carrying out the polymerization, preferably to about 50 to 80 ° C.
  • the monomers to be polymerized with the exception of acrylic or methacrylic acid, are emulsified, for which purpose a further amount of an emulsifier is expediently used.
  • the monomer emulsion is gradually run into the receiver over the course of several hours while the polymerization is taking place at the same time.
  • Additional polymerization initiators can be added continuously or in individual additions during the polymerization.
  • the amount of water and monomers are preferably matched to one another in such a way that a 40-60% dispersion is obtained.
  • the use of emulsifiers can optionally be dispensed with.
  • the monomers, apart from the acrylic acid or methacrylic acid salt, can also be added gradually in non-emulsified form. In this case, the entire water phase is added to the template at the beginning of the process.
  • the fiber structures that are consolidated according to the invention can consist of natural fibers, man-made fibers or of mixtures of different types of fibers.
  • the consolidation of mineral fiber structures, e.g. B. made of glass fibers or rock wool comes into consideration.
  • Flat fiber structures are essentially equipped; these include woven fabrics, knitted fabrics, non-woven fabrics, and papers, in particular absorbent base papers and cardboards.
  • the plastic dispersion can be applied as a coating on the surface of the fiber structure.
  • the fiber structure is preferably treated with the plastic dispersion in such a way that an impregnation that solidifies the entire cross section is achieved.
  • the amount of plastic dispersion used for solidification depends on the intended use of the solidified fiber structure.
  • a preferred application of the invention is the consolidation of light nonwovens with a basis weight of not more than 60 g / m2.
  • the dispersion can be applied to or introduced into the fiber structure by impregnation, spraying, splashing, brushing or printing. Depending on the application method used, the dispersion can be applied as a dilute liquor, for example with a binder content of 15 to 30% by weight, or as a thickened paste or as a foam. Conventional thickening agents, such as cellulose derivatives or water-soluble synthetic polymers, can be reacted in the pastes; the binder content is preferably 20 to 40% by weight.
  • the coated or impregnated fiber structure is dried. Conventional flat web dryers, cylinder dryers or screen drum dryers can be used for this.
  • the treated fiber structure is less prone to sticking to warm metal surfaces than products equipped with purely thermoplastic dispersions.
  • the so-called “binder tri wash loss”, abbreviated to BTV, is suitable, the determination of which is explained in more detail in the examples under IV. While the impregnation with dispersions which contain no carboxylate groups or in which the proportion of alkali metal carboxylate groups has not been incorporated in the manner described here gives BTV values of 80-100%, the binder loss in the fiber structures impregnated by the process of the invention results in reduced a fraction of that value. Even with an alkali methacrylate content of 1% (calculated as methacrylic acid, based on the plastic weight), a BTV value between 30 and 50% is achieved.
  • BKV Binder-Kochwasch-loss
  • the BKV value proves to a large extent depending on the drying temperature. After drying at room temperature, BKV values of up to 70% are observed. After drying or reheating at temperatures between 80 and 120 ° C - especially with a low carboxylate content - only binder losses of a few percent can be determined.
  • binder losses In the preferred range of 2-3% by weight carboxylate units, binder losses of between 4 and 10% by weight occur.
  • the binder losses depend on the type of fiber material and the plastic dispersion; the values mentioned here apply to a polyester fabric which was equipped with 50% by weight of a plastic dispersion composed of methyl methacrylate and butyl acrylate as the main components.
  • the mixture is stirred at 80 ° C. for one hour and then cooled to room temperature. A dispersion with a solids content of 45% is formed. To produce 50% dispersions, the water content is reduced accordingly.
  • Comparative dispersion C prepared in accordance with Example 10, but with the addition of methacrylic acid in the form of the free acid together with the monomer feed.
  • Comparative dispersion D prepared like comparative dispersion C, but neutralized the methacrylic acid units with the equivalent amount of KOH after completion of the polymerization.
  • Comparative dispersion E prepared as in Example 10, but gradual addition of the potassium methacrylate simultaneously with the addition of the other monomers.
  • a polyester fabric with a basis weight of 100 g / m 2 of polyester staple fibers is impregnated with a dispersion at room temperature and squeezed to a liquor absorption of 80 to 100% (based on the weight of the fabric) using a laboratory pad.
  • the moist fabric strip is dried in a tensioned state for 5 minutes at 120 ° C in a forced-air drying cabinet.
  • a sample measuring 18 x 18 cm is agitated with 125 ml of trichlorethylene at 20 ° C for 80 min, then rinsed with 100 ml of trichlorethylene and dried at 80 ° for 30 min. After storage for half an hour at room temperature, the sample is weighed out. The weight loss is determined in percent, based on the weight of the binder in the sample used.
  • a sample of 18 x 18cm size is 10 min at 90 ° with 125 ml of an aqueous wash liquor containing 3 g of Marseille soap and 2 g of calc. Soda contains, agitated, then rinsed once with hot water at 90 ° C and once with cold water and dried at 90 ° C for 30 min. 30 minutes after drying, the sample is weighed and the binder loss in percent, based on the weight of the binder in the sample used, is determined.
  • the comparative dispersions show that without neutralization of the carboxyl groups of the binder polymer (comparative dispersion C), very high binder losses occur in the tri-wash. These losses are significantly reduced by neutralization, while the losses in hot water only increase insignificantly despite the increased polarity of the binder. With subsequent neutralization (comparative dispersion D), particularly low binder losses are found, but the tests described under 111 indicate a high sensitivity of the film to plasticizers. With a uniform addition of the methacrylic acid salt (comparative dispersion E), the binder losses are higher than when used in the template according to the invention (example 10), but significantly lower than in the case of non-neutralized binder resin. In addition, the swelling in the plasticizer (see under 111) is unfavorably high.

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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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

1. Process for strengthening fibrous structures by treating them with aqueous plastics dispersions which are free from formaldehyde-releasing substances and the plastics content of which is made up predominantly of alkyl esters of acrylic or methacrylic acid and small quantities of alpha,beta-unsaturated carboxylic acids, and subsequent drying, characterised in that the process is carried out with a plastics dispersion which is prepared by taking an aqueous phase containing 1 to 4% by weight, based on the total weight of polymerisable compounds involved in the composition of the dispersion, of acrylic and/or methacrylic acid dissolved in the form of the alkali metal salts or ammonium salts thereof, and gradually adding the other monomers, either as they are or in the form of an aqueous emulsion, under polymerisation conditions to the aqueous phase in which the polymerisation takes place.

Description

Die Erfindung betrifft ein Verfahren zum Verfestigen von Fasergebilden durch Behandeln mit wässrigen Kunststoffdispersionen. Die Wahl der dafür zu verwendenden Kunststoffdispersionen. Die Waahl der dafür zu verwendenden Kunststoffdispersionen hängt unter anderem davon ab, ob das ausgerüstete Fasergebilde gegenüber organischen Lösungsmitten beständig sein soll. Wenn das nicht der Fall ist, können Kunststoffdispersionen eingesetzt werden, die frei von formaldehydabgebenden Substanzen sind und deren Kunststoffanteil beispielsweise im wesentlichen aus AIkylestern der Acryl- oder Methacrylsäure, Vinylestern und/oder Styrol sowie geringen Mengen a,ß-ungesättigten Carbonsäuren aufgebaut ist. Wird dagegen Beständigkeit gegen organische Lösungsmittel oder Weichmacher gefordert, so werden Kunststoffdispersionen eingesetzt, die sich nach dem Beschichten oder Tränken und Trocknen bei erhöhten Temperaturen vernetzen lassen. Die Vernetzung wird entweder dadurch erreicht, dass man zu den Dispersionen der oben genannten Art wasserlösliche Aminoplastharze zusetzt oder Kunststoffdispersionen einsetzt, an deren Aufbau kondensationsfähige Formaldehydderivate, insbesondere N-Methylolacrylamid oder -methacrylamid, beteiligt sind.The invention relates to a method for solidifying fiber structures by treatment with aqueous plastic dispersions. The choice of the plastic dispersions to be used for this. The choice of the plastic dispersions to be used depends, among other things, on whether the finished fiber structure should be resistant to organic solvents. If this is not the case, plastic dispersions can be used which are free of formaldehyde-releasing substances and whose plastic content is essentially composed, for example, of alkyl esters of acrylic or methacrylic acid, vinyl esters and / or styrene and small amounts of α, β-unsaturated carboxylic acids. If, on the other hand, resistance to organic solvents or plasticizers is required, plastic dispersions are used that can be crosslinked after coating or soaking and drying at elevated temperatures. The crosslinking is achieved either by adding water-soluble aminoplast resins to the dispersions of the type mentioned above or by using plastic dispersions in the formation of which condensable formaldehyde derivatives, in particular N-methylolacrylamide or methacrylamide, are involved.

Beim Erhitzen der lmprägnierung oder Beschichtung tritt durch Kondensationsreaktionen Vernetzung ein, wodurch der Kunststoff in Lösungsmitteln unlöslich wird. Gleichzeitig wird Formaldehyd frei, der in die Abluft gelangt, aus der er wegen seines unangenehmen Geruchs herausfiltriert werden muss.When the impregnation or coating is heated, crosslinking occurs as a result of condensation reactions, as a result of which the plastic becomes insoluble in solvents. At the same time, formaldehyde is released, which gets into the exhaust air, from which it has to be filtered out due to its unpleasant smell.

Eine vollständige Unlöslichkeit des Bindemittels in organischen Lösungsmitteln ist bei vielen Anwendungen von verfestigten Fasergebilden nicht erforderlich. Oft werden Dispersionen von selbstvernetzenden Kunststoffen nur deshalb verwendet, weil die daraus entstehenden Filme weniger dazu neigen, an warmen Metalloberflächen anzukleben, z.B. auf einem Trockenzylinder. Eine schwache Vernetzung ist oft ausreichend um den Blockpunkt von weichen Beschichtungen zu erhöhen. Man war jedoch auch in den Fällen, in denen eine schwache Vernetzung ausreicht, auf die beim Erhitzen formaldehydabgebenden Kunststoffdispersionen angewiesen.Complete insolubility of the binder in organic solvents is not necessary in many applications of solidified fiber structures. Dispersions of self-crosslinking plastics are often used only because the resulting films are less likely to stick to warm metal surfaces, e.g. on a drying cylinder. Weak crosslinking is often sufficient to increase the blocking point of soft coatings. However, even in cases where weak crosslinking is sufficient, the plastic dispersions which give off formaldehyde when heated were relied on.

Aus der EP-A 12 033 sind bereits verfestigte Faservliese bekannt, zu deren Herstellung Kunststoffdispersionen verwendet wurden, die frei von Formaldehyd oder von formaldehydabgebenden Substanzen sind. Sie sind mit einem Gehalt von 1 bis 8 Gew.-% Einheiten einer ungesättigten Carbonsäure hergestellt und nachträglich mit Alkali neutralisiert worden. Die Empfindlichkeit des bindemittels gegenüber Lösungs- bzw. Weichmachungsmitteln wird dadurch nicht entscheidend verbessert.From EP-A 12 033, consolidated nonwovens are already known, for the manufacture of which plastic dispersions were used which are free of formaldehyde or of formaldehyde-releasing substances. They are produced with a content of 1 to 8 wt .-% units of an unsaturated carboxylic acid and subsequently neutralized with alkali. This does not significantly improve the sensitivity of the binder to solvents or plasticizers.

Der Erfindung liegt die Aufgabe zugrunde, Fasergebilde mit einer Ausrüstung zu versehen, die wenigstens begrenzt lösungsmittelbeständig bzw. blockfrei oder klebfrei ist, und hierzu eine wässrige Kunststoffdispersion einzusetzen, die frei von Formaldehydabgebenden Substanzen ist und deren Kunststoffanteil überwiegend aus Alkylestern der Acryl- oder Methacrylsäure, sowie geringen Mengen a,ß-ungesättigten Carbonsäuren aufgebaut ist.The invention has for its object to provide fiber structures with an equipment that is at least limited solvent-resistant or block-free or tack-free, and to do this use an aqueous plastic dispersion that is free of formaldehyde-releasing substances and whose plastic content consists predominantly of alkyl esters of acrylic or methacrylic acid, as well as small amounts of a, β-unsaturated carboxylic acids.

Es wurde gefunden, dass man die genannte Aufgabe mit einer solchen Kunsstoffdispersion lösen kann, die nach dem Zulaufverfahren unter Einsatz von 1-4 Gew.-% Acryl- oder/und Methacrylsäure, bezogen auf das Gesamtgewicht an polymerisierbaren Verbindungen, in der Vorlage und unter Zugabe der übrigen Monomeren im Zulauf hergestellt worden ist, wobei die Acryl- bzw. Methacrylsäure in Form eines Alkali- oder Ammoniumsalzes eingesetzt worden ist. Beim Zulaufverfahren werden die Monomeren als solche oder in Form einer wässrigen Emulsion allmählich unter Polymerisationsbedingungen zu einer Vorlage zulaufen gelassen, in der die Polymerisation stattfindet. Die Vorlage besteht aus einer wässrigen Phase, die in der Regel einen wasserlöslichen Polymerisationsinitiator und ein oder mehrere Emulgiermittel enthält. Überraschenderweise hängt die verbesserte Lösungsmittelbeständigkeit der erfindungsgemäss erzeugten Beschichtungen oder Imprägnierungen davon ab, dass sich bei der Herstellung der zu verwenden- ..10 Kunststoffdispersion nach dem Zulaufverfahin die Acryl- oder Methacrylsäure in Form ihres Alkali- oder Ammoniumsalzes in der Vorlage gelöst befindet. Gleichwertige Kunststoffdispersionen lassen sich nicht dadurch herstellen, dass man die Acryl- oder Methacrylsäure oder ihre Salze zusammen mit den übrigen Monomeren beim Zulaufverfahren allmählich zusetzt oder dass man die Acryl- oder Methacrylsäure als solche in die Vorlage gibt und erst nach der Polymerisation neutralisiert.It has been found that the stated object can be achieved with a plastic dispersion of this type, which can be added in the initial charge and under using the feed process using 1-4% by weight acrylic or / and methacrylic acid, based on the total weight of polymerizable compounds Addition of the other monomers has been prepared in the feed, the acrylic or methacrylic acid being used in the form of an alkali or ammonium salt. In the feed process, the monomers as such or in the form of an aqueous emulsion are gradually run under polymerization conditions to a template in which the polymerization takes place. The initial charge consists of an aqueous phase which generally contains a water-soluble polymerization initiator and one or more emulsifiers. Surprisingly, the improved solvent resistance of the coatings or impregnations produced in accordance with the invention depends on the fact that, in the preparation of the plastic dispersion to be used, acrylic or methacrylic acid in the form of its alkali metal or ammonium salt is dissolved in the initial charge. Equivalent plastic dispersions cannot be prepared by gradually adding the acrylic or methacrylic acid or its salts together with the other monomers during the feed process or by adding the acrylic or methacrylic acid as such to the initial charge and only neutralizing it after the polymerization.

Die Herstellung von Kunststoffdispersionen, die frei von formaldehydabgebenden Substanzen sind, nach dem oben angegebenen Verfahren ist zwar aus der OE-PS 236 643 und aus der FR-A-1 157 265 bekannt. Die so hergestellten Kunststoffdispersionen sind jedoch noch nicht zum Verfestigen von Fasergebilden eingesetzt worden. Es war auch nicht vorauszusehen, dass die dabei erhaltenen Imprägnierungen und Beschichtungen sich durch eine verbesserte Beständigkeit gegenüber organischen Lösungsmitteln auszeichnen würden.The production of plastic dispersions which are free of formaldehyde-releasing substances by the process indicated above is known from OE-PS 236 643 and from FR-A-1 157 265. However, the plastic dispersions produced in this way have not yet been used to solidify fiber structures. Nor could it have been foreseen that the impregnations and coatings obtained would be characterized by improved resistance to organic solvents.

Mit besonderem Vorteil werden für das Verfahren der Erfindung Kunststoffdispersionen mit einer Mindest-Filmbildungstemperatur unter 25°C und mit einem Txmax-Wert des dispergierten Kunststoffes (nach DIN 53445) unter 50°C eingesetzt. Der Kunststoffanteil der Dispersion ist vorzugsweise zu mehr als 50 Gew.-% aus Acrylsäureaklylestern mit 1-8 C-Atomen im Alkylrest und zum übrigen Teil überwiegend aus Methacrylsäurealkylestern mit 1-4 C-Atomen im Alkylrest aufgebaut. Andere wasserunlösliche Monomere, wie z. B. Styrol, Vinylacetat oder Vinylidenchlorid, können in untergeordneten Mengen am Aufbau des Kunststoffes beteiligt sein. Der Anteil der in Salzform einpolymerisierten Acryl- und/oder Methacrylsäure beträgt vorzugsweise 2-3 Gew.-% berechnet als freie Säure und bezogen auf das Gewicht des Kunststoffes. Als Alkalisalze kommen vorzugsweise die Natrium- und Kaliumsalze in Betracht. Die Ammoniumsalze können sich von Ammoniak oder von organischen Aminen, wie z. B. Äthanolamin, ableiten.Plastic dispersions with a minimum film-forming temperature below 25 ° C. and with a Txmax value of the dispersed plastic (according to DIN 53445) below 50 ° C. are used with particular advantage for the process of the invention. The plastic portion of the dispersion is preferably composed of more than 50% by weight of acrylic acid alkyl esters with 1-8 C atoms in the alkyl radical and for the most part predominantly from methacrylic acid alkyl esters with 1-4 C atoms in the alkyl radical. Other water-insoluble monomers, such as. B. styrene, vinyl acetate or vinylidene chloride, can be involved in minor amounts in the construction of the plastic. The share of Acrylic and / or methacrylic acid copolymerized in salt form is preferably 2-3% by weight calculated as free acid and based on the weight of the plastic. The alkali salts are preferably the sodium and potassium salts. The ammonium salts can be from ammonia or from organic amines, such as. B. ethanolamine.

Das bevorzugte Verfahren zur Herstellung der Kunststoffdispersion ist das Emulsions-Zulaufverfahren. Dabei wird ein Teil der als wässrige Phase der Dispersion vorgesehenen Wassermenge im Polymerisationsgefäss vorgelegt und das Salz der Acryl- und/oder Methacryisäure darin gelöst: Ausserdem kann in der Vorlage ein üblicher anionischer oder nichtionischer Emulgator und ein wasserlöslicher Polymerisationsinitiator, wie Kalium-oder Ammoniumperoxidisulfat, gelöst werden. Man bringt die Vorlage auf eine zur Durchführung der Polymerisation geeignete Temperatur, vorzugsweise etwa auf 50 bis 80°C. In dem übrigen Teil der Wasserphase werden die zu polymerisierenden Monomeren mit Ausnahme der Acryl-oder Methacrylsäure emulgiert, wozu zweckmässig eine weitere Menge an einem Emulgiermittel verwendet wird. Im Laufe von mehreren Stunden lässt man die Monomerenemulsion allmählich in die Vorlage einlaufen, während gleichzeitig die Polymerisation stattfindet. Während der Polymerisation kann kontinuierlich oder in einzelnen Zugaben weiterer Polymerisationsinitiator zugefügt werden. Die Wasser- und Monomerenmenge werden vorzugsweise so aufeinander abgestimmt, dass eine 40- bis 60%ige Dispersion entsteht. Auf die Verwendung von Emulgiermitteln kann gegebenenfals verzichtet werden. Die Monomeren, ausser dem Acrylsäure- oder Methacrylsäuresalz, können auch in nicht emulgierter Form allmählich zugesetzt werden. In diesem Falle wird die gesamte Wasserphase zu Beginn des Verfahrens in die Vorlage gegeben.The preferred method for producing the plastic dispersion is the emulsion feed method. Part of the amount of water provided as the aqueous phase of the dispersion is placed in the polymerization vessel and the salt of acrylic and / or methacrylic acid is dissolved therein. be solved. The initial charge is brought to a temperature suitable for carrying out the polymerization, preferably to about 50 to 80 ° C. In the remaining part of the water phase, the monomers to be polymerized, with the exception of acrylic or methacrylic acid, are emulsified, for which purpose a further amount of an emulsifier is expediently used. The monomer emulsion is gradually run into the receiver over the course of several hours while the polymerization is taking place at the same time. Additional polymerization initiators can be added continuously or in individual additions during the polymerization. The amount of water and monomers are preferably matched to one another in such a way that a 40-60% dispersion is obtained. The use of emulsifiers can optionally be dispensed with. The monomers, apart from the acrylic acid or methacrylic acid salt, can also be added gradually in non-emulsified form. In this case, the entire water phase is added to the template at the beginning of the process.

Es empfiehlt sich, zu Beginn der Polymerisation eine Emulgatorkonzentration nahe oder unterhalb der kritischen Mizellbildungskonzentration einzustellen und erforderlichenfalls weiteren Emulgator während oder nach der Polymerisation zuzusetzen. Dadurch lässt sich die Teilchengrösse der Latexpartikel und die Viskosität der Dispersion beeinflussen.It is advisable to set an emulsifier concentration near or below the critical micelle formation concentration at the start of the polymerization and, if necessary, to add further emulsifier during or after the polymerization. This allows the particle size of the latex particles and the viscosity of the dispersion to be influenced.

Die Fasergebilde, die erfindungsgemäss verfestigt werden, können aus Naturfasern, Chemiefasern oder aus Gemischen verschiedener Faserarten bestehen. Auch die Verfestigung von mineralischen Fasergebilden, z. B. aus Glasfasern oder Steinwolle, kommt in Betracht. Im wesentlichen werden flächige Fasergebilde ausgerüstet; dazu gehören Gewebe, Gewirke, Faservliese, sowie Papiere, insbesondere saugfähige Rohpapiere und Pappen. Die Kunststoffdispersion kann als Beschichtung auf die Oberfläche des Fasergebildes aufgetragen werden. Vorzugsweise wird das Fasergebilde mit der Kunststoffdispersion so behandelt, dass eine den gesamten Querschnitt verfestigende Imprägnierung erreicht wird. Die Menge der zum Verfestigen verwendeten Kunststoffdispersion richtet sich nach dem Verwendungszweck des verfestigten Fasergebildes. Sie kann von einer leichten Verfestigung mit 5-20 % Kunststofftrockengewicht, bezogen auf das Fasergewicht, bis zu einer Kunststoff-Füllung mit 100 Gew.-% Kunststoff, bezogen auf das Fasergewicht, oder mehr reichen. Eine bevorzugte Anwendungsform der Erfindung ist die Verfestigung von leichten Faservliesen mit einem Flächengewicht nicht über 60 g/qm. Die Dispersion kann durch Imprägnieren, Besprühen, Pflatschen, Streichen oder Drucken auf das Fasergebilde aufgebracht bzw. in dieses eingebracht werden. Je nach dem angewandten Auftragsverfahren kann die Dispersion als verdünnte Flotte, beispielsweise mit einem Bindergehalt von 15 bis 30 Gew.-%, oder als verdickte Paste oder als Schaum aufgebracht werden. In den Pasten können übliche Verdikkungsmittel, wie Cellulosederivate oder wasserlösliche synthetische Polymere, umgesetzt werden, der Bindergehalt liegt vorzugsweise bei 20 bis 40 Gew.-%.The fiber structures that are consolidated according to the invention can consist of natural fibers, man-made fibers or of mixtures of different types of fibers. The consolidation of mineral fiber structures, e.g. B. made of glass fibers or rock wool comes into consideration. Flat fiber structures are essentially equipped; these include woven fabrics, knitted fabrics, non-woven fabrics, and papers, in particular absorbent base papers and cardboards. The plastic dispersion can be applied as a coating on the surface of the fiber structure. The fiber structure is preferably treated with the plastic dispersion in such a way that an impregnation that solidifies the entire cross section is achieved. The amount of plastic dispersion used for solidification depends on the intended use of the solidified fiber structure. It can range from a slight consolidation with 5-20% dry plastic weight, based on the fiber weight, to a plastic filling with 100% by weight plastic, based on the fiber weight, or more. A preferred application of the invention is the consolidation of light nonwovens with a basis weight of not more than 60 g / m2. The dispersion can be applied to or introduced into the fiber structure by impregnation, spraying, splashing, brushing or printing. Depending on the application method used, the dispersion can be applied as a dilute liquor, for example with a binder content of 15 to 30% by weight, or as a thickened paste or as a foam. Conventional thickening agents, such as cellulose derivatives or water-soluble synthetic polymers, can be reacted in the pastes; the binder content is preferably 20 to 40% by weight.

Nach der Behandlung mit der Kunststoffdispersion wird das beschichtete oder getränkte Fasergebilde getrocknet. Hierzu können übliche Flachbahntrockner, Zylindertrockner oder Siebtrommeltrockner verwendet werden. Das behandelte Fasergebilde neigt weniger zum Kleben an warmen Metalloberflächen als mit rein thermoplastischen Dispersionen ausgerüstete Produkte.After the treatment with the plastic dispersion, the coated or impregnated fiber structure is dried. Conventional flat web dryers, cylinder dryers or screen drum dryers can be used for this. The treated fiber structure is less prone to sticking to warm metal surfaces than products equipped with purely thermoplastic dispersions.

Als Mass für die Beständigkeit gegen organische Lösungsmittel eignet sich der sogenannte «Binder-Tri-Waschverlust», abgekürzt BTV, dessen Bestimmung in den Beispielen unter IV näher erläutert ist. Während die Imprägnierung mit Dispersionen, die keine Carboxylatgruppen enthalten oder in denen der Anteil an Alkalicarboxylatgruppen nicht in der hier beschriebenen Weise eingebaut worden ist, BTV-Werte von 80-100% ergibt, wird der Binderverlust bei den nach dem Verfahren der Erfindung imprägnierten Fasergebilden auf einen Bruchteil dieses Wertes herabgesetzt. Schon bei einem Alkali-Methacrylat-Gehalt von 1 % (berechnet als Methacrylsäure, bezogen auf das Kunststoffgewicht) wird ein BTV-Wert zwischen 30 und 50% erreicht. Bei einer Steigerung des Alkali-Methacrylatgehaltes auf 2 bis 3% sinkt der Binderverlust auf 20 bis 25% ab. Bei weiterer Erhöhung des Carboxylatgehaltes bleibt der Binderverlust auf niedrigem Niveau, jedoch nimmt die Wasserempfindlichkeit der Imprägnierung zu. Eine geeignete Masszahl für die Wasserempfindlichkeit ist der sogenannte «Binder-Kochwasch-Verlust», abgekürzt BKV, dessen Bestimmung in den Beispielen unter IV ausführlich beschrieben ist. Der BKV-Wert erweist sich in starkem Masse abhängig von der Trocknungstemperatur. Nach der Trocknung bei Raumtemperatur werden BKV-Werte bis zu 70% beobachtet. Nach dem Trocknen oder Nacherhitzen bei Temperaturen zwischen 80 und 120°C sind - insbesondere bei niedrigem Carboxylatgehalt - nur noch Binderverluste von wenigen Prozent festzustellen. In dem bevorzugten Bereich von 2-3 Gew.-% Carboxylateinheiten treten Binderverluste zwischen 4 und 10 Gew.-% auf. Selbstverständlich hängen die Binderverluste von der Art des Fasermaterials und der Kunststoffdispersion ab; die hier genannten Werte gelten für ein Polyestergewebe, das mit 50 Gew.-% einer aus Methylmethacrylat und Butylacrylat als Hauptkomponenten aufgebauten Kunststoffdispersion ausgerüstet war.As a measure of the resistance to organic solvents, the so-called “binder tri wash loss”, abbreviated to BTV, is suitable, the determination of which is explained in more detail in the examples under IV. While the impregnation with dispersions which contain no carboxylate groups or in which the proportion of alkali metal carboxylate groups has not been incorporated in the manner described here gives BTV values of 80-100%, the binder loss in the fiber structures impregnated by the process of the invention results in reduced a fraction of that value. Even with an alkali methacrylate content of 1% (calculated as methacrylic acid, based on the plastic weight), a BTV value between 30 and 50% is achieved. When the alkali methacrylate content is increased to 2 to 3%, the binder loss decreases to 20 to 25%. If the carboxylate content is increased further, the binder loss remains at a low level, but the water sensitivity of the impregnation increases. A suitable measure of water sensitivity is the so-called “Binder-Kochwasch-loss”, abbreviated BKV, the determination of which is described in detail in the examples under IV. The BKV value proves to a large extent depending on the drying temperature. After drying at room temperature, BKV values of up to 70% are observed. After drying or reheating at temperatures between 80 and 120 ° C - especially with a low carboxylate content - only binder losses of a few percent can be determined. In the preferred range of 2-3% by weight carboxylate units, binder losses of between 4 and 10% by weight occur. Of course, the binder losses depend on the type of fiber material and the plastic dispersion; the values mentioned here apply to a polyester fabric which was equipped with 50% by weight of a plastic dispersion composed of methyl methacrylate and butyl acrylate as the main components.

BeispieleExamples

I. Herstellung der Dispersionen - allgemeine ArbeitsweiseI. Preparation of the dispersions - general procedure

In einem Polymerisationsgefäss mit Rührwerk, Rückflusskühler und Thermometer werden bei 80°C vorgelegt:

Figure imgb0001
Figure imgb0002
 The following are placed in a polymerization vessel with agitator, reflux condenser and thermometer at 80 ° C:
Figure imgb0001
Figure imgb0002

Innerhalb 4 Std. wird in diese Lösung bei 80°C unter Rühren eine zuvor hergestellte Emulsion eingetropft, die aus folgenden Bestandteilen besteht:

Figure imgb0003
Within 4 hours, a previously prepared emulsion is added dropwise to this solution at 80 ° C. with stirring, which consists of the following components:
Figure imgb0003

Nach Abschluss des Zulaufs wird noch eine Stunde bei 80°C gerührt und danach auf Raumtemperatur abgekühlt. Es entsteht eine Dispersion mit 45% Feststoffgehalt. Zur Herstellung 50%iger Dispersionen wird der Wasseranteil entsprechend vermindert.

Figure imgb0004
After the feed is complete, the mixture is stirred at 80 ° C. for one hour and then cooled to room temperature. A dispersion with a solids content of 45% is formed. To produce 50% dispersions, the water content is reduced accordingly.
Figure imgb0004

II. Herstellung von VergleichsdispersionenII. Preparation of comparative dispersions

Es wurde die unter I. beschriebene Arbeitsweise angewendet, soweit nicht anders angegeben.The procedure described under I. was used, unless otherwise stated.

Vergleichsdispersion-A und B entsprechend Beispielen 1 und 2, jedoch wurde das Kalium-Methacrylat in der Monomer-Zulaufemulsion gelöst.

Figure imgb0005
Comparative dispersion A and B according to Examples 1 and 2, but the potassium methacrylate was dissolved in the monomer feed emulsion.
Figure imgb0005

Vergleichsdispersion C, hergestellt entsprechend Beispiel 10, jedoch unter Zugabe der Methacrylsäure in Form der freien Säure zusammen mit dem Monomerzulauf.Comparative dispersion C, prepared in accordance with Example 10, but with the addition of methacrylic acid in the form of the free acid together with the monomer feed.

Vergleichsdispersion D, hergestellt wie Vergleichsdispersion C, jedoch die Methacrylsäureeinheiten nach Abschluss der Polymerisation mit der äquivalenten Menge KOH neutralisiert.Comparative dispersion D, prepared like comparative dispersion C, but neutralized the methacrylic acid units with the equivalent amount of KOH after completion of the polymerization.

Vergleichsdispersion E, hergestellt entsprechend Beispiel 10, jedoch allmähliche Zugabe des Kaliummethacrylats gleichzeitig mit dem Zulauf der übrigen Monomeren.

Figure imgb0006
Comparative dispersion E, prepared as in Example 10, but gradual addition of the potassium methacrylate simultaneously with the addition of the other monomers.
Figure imgb0006

111. Quellverhalten von Filmen aus Dispersion nach Beispiel 10 und den Vergleichsdispersionen C, D und E111. Swelling behavior of films from dispersion according to Example 10 and the comparative dispersions C, D and E

Etwa 1 mm dicke Schichten der Dispersionen werden im Trockenschrank bei 39°C zu einem 0,5mm dicken Film eingetrocknet und danach 5 Minuten auf 140°C erhitzt. Zur Prüfung der Quellbarkeit durch Trichloräthylen werden gewogene Teilstücke der Filme bei 20°C 2 Stunden lang quellen gelassen. Andere Teilstücke werden 72 Stunden bei 35°C in Dibutylphthalat quellen gelassen. Dann werden die gequollenen Filme herausgenommen, von anhaftender Flüssigkeit befreit und die Gewichtszunahme in Prozent des Ausgangsgewichts ermittelt:

Figure imgb0007
Approximately 1 mm thick layers of the dispersions are dried in a drying cabinet at 39 ° C. to form a 0.5 mm thick film and then heated to 140 ° C. for 5 minutes. To test the swellability by trichlorethylene, weighed sections of the films are left to swell at 20 ° C. for 2 hours. Other sections will be 72 hours which swelled at 35 ° C in dibutyl phthalate. Then the swollen films are removed, freed of adhering liquid and the weight gain is determined as a percentage of the initial weight:
Figure imgb0007

IV.Verfestigung von FasergebildenIV. Consolidation of fiber structures

Ein Polyestergewebe mit einem Flächengewicht von 100 g/m2 aus Polyesterstapelfasern wird mit einer Dispersion bei Zimmertemperatur getränkt und mittels eines Laborfoulards auf eine Flottenaufnahme von 80 bis 100% (bezogen auf das Gewicht des Gewebes) abgequetscht. Der feuchte Gewebestreifen wird im gespannten Zustand hängend 5 Minuten bei 120°C im Umlufttrockenschrank getrocknet.A polyester fabric with a basis weight of 100 g / m 2 of polyester staple fibers is impregnated with a dispersion at room temperature and squeezed to a liquor absorption of 80 to 100% (based on the weight of the fabric) using a laboratory pad. The moist fabric strip is dried in a tensioned state for 5 minutes at 120 ° C in a forced-air drying cabinet.

Um die Beständigkeit der Imprägnierung gegenüber den in der Chemischreinigung und in der Kochwäsche herrschenden Bedingungen zu prüfen, werden ausgewogene Probestücke des imprägnierten Gewebes in einer Laborwaschmaschine («Linitestgerät», eingetr. Warenzeichen) mit Trichloräthylen bzw. einer Waschlauge behandelt.In order to test the resistance of the impregnation to the conditions prevailing in the dry cleaning and in the hot wash, balanced test pieces of the impregnated fabric are treated in a laboratory washing machine (“Linitestgerät”, registered trademark) with trichlorethylene or a wash liquor.

Prüfbedingungen:Test conditions: Triwäsche:Tri wash:

Eine Probe von 18 x 18cm Grösse wird 80 min bei 20°C mit 125 ml Trichloräthylen bewegt, anschliessend mit 100 ml Trichloräthylen gespült und 30 min bei 80° getrocknet. Nach halbstündiger Lagerung bei Raumtemperatur wird die Probe ausgewogen. Der Gewichtsverlust wird in Prozent, bezogen auf das Gewicht des Bindemittels in der eingesetzten Probe, bestimmt.A sample measuring 18 x 18 cm is agitated with 125 ml of trichlorethylene at 20 ° C for 80 min, then rinsed with 100 ml of trichlorethylene and dried at 80 ° for 30 min. After storage for half an hour at room temperature, the sample is weighed out. The weight loss is determined in percent, based on the weight of the binder in the sample used.

Kochwäsche:Cooking linen:

Eine Probe von 18 x 18cm Grösse wird 10 min bei 90° mit 125 ml einer wässrigen Waschflotte, die je Liter 3 g Marseiller Seife und 2 g calc. Soda enthält, bewegt, anschliessend einmal mit 90°C heissem und einmal mit kaltem Wasser gespült und 30 min bei 90°C getrocknet. 30 min nach der Trocknung wird die Probe gewogen und der Binderverlust in Prozent, bezogen auf das Gewicht des Bindemittels in der eingesetzten Probe, bestimmt.

Figure imgb0008
A sample of 18 x 18cm size is 10 min at 90 ° with 125 ml of an aqueous wash liquor containing 3 g of Marseille soap and 2 g of calc. Soda contains, agitated, then rinsed once with hot water at 90 ° C and once with cold water and dried at 90 ° C for 30 min. 30 minutes after drying, the sample is weighed and the binder loss in percent, based on the weight of the binder in the sample used, is determined.
Figure imgb0008

Die Vergleichsdispersionen zeigen, dass ohne Neutralisation der Carboxylgruppen des Binderpolymeren (Vergleichsdispersion C) sehr hohe Binderverluste bei der Triwäsche auftreten. Durch Neutralisation werden diese Verluste erheblich herabgesetzt, während die Kochwaschverluste trotz gestiegener Polarität des Binders nur unerheblich zunehmen. Bei nachträglicher Neutralisation (Vergleichsdispersion D) werden zwar besonders niedrige Binderverluste gefunden, jedoch zeigen die unter 111 beschriebenen Prüfungen eine hohe Empfindlichkeit des Films gegenüber Weichmachern an. Bei gleichmässiger Zugabe des methacrylsauren Salzes (Vergleichsdispersion E) sind die Binderverluste höher als beim Einsatzt in der Vorlage gemäss der Erfindung (Beispiel 10), jedoch bedeutend niedriger als bei nicht neutralisiertem Binderharz. Dageben ist die Quellung im Weichmacher (siehe unter 111) ungünstig hoch.The comparative dispersions show that without neutralization of the carboxyl groups of the binder polymer (comparative dispersion C), very high binder losses occur in the tri-wash. These losses are significantly reduced by neutralization, while the losses in hot water only increase insignificantly despite the increased polarity of the binder. With subsequent neutralization (comparative dispersion D), particularly low binder losses are found, but the tests described under 111 indicate a high sensitivity of the film to plasticizers. With a uniform addition of the methacrylic acid salt (comparative dispersion E), the binder losses are higher than when used in the template according to the invention (example 10), but significantly lower than in the case of non-neutralized binder resin. In addition, the swelling in the plasticizer (see under 111) is unfavorably high.

Claims (8)

1. Process for strengthening fibrous structures by treating them with aqueous plastics dispersions which are free from formaldehyde-releasing substances and the plastics content of which is made up predominantly of alkyl esters of acrylic or methacrylic acid and small quantities of α,ß- unsaturated carboxylic acids, and subsequent drying, characterised in that the process is carried out with a plastics dispersion which is prepared by taking an aqueous phase containing 1 to 4% by weight, based on the total weight of polymerisable compounds involved in the composition of the dispersion, of acrylic and/or methacrylic acid dissolved in the form of the alkali metal salts or ammonium salts thereof, and gradually adding the other monomers, either as they are or in the form of an aqueous emulsion, under polymerisation conditions to the aqueous phase in which the polymerisation takes place.
2. Process as claimed in claim 1, characterised in that a plastics dispersion is used which contains a proportion of acrylic or methacrylic acid polymerised therein in the form of a salt of from 2 to 3% by weight, based on the plastics content.
3. Process as claimed in claims 1 and 2, characterised in that a plastics dispersion which forms a film at 25°C is,used, having a TAmax value for the dispersed plastics of below 50°C.
4. Process as claimed in claims 1 to 3, characterised in that a plastics dispersion is used which is made up of more than 50% by weight, based on the plastics content, of alkyl acrylates with 1 to 8 carbon atoms in the alkyl group, the remainder being predominantly alkyl methacrylates with 1 to 4 carbon atoms in the alkyl group.
5. Process as claimed in claims 1 to 4, characterised in that at least 10 parts of dry weight of plastics are used as the aqueous plastics dispersion for each 100 parts by weight of fibres.
6. Process as claimed in claims 1 to 5, characterised in that woven fabrics and fibre matting made from textile fibres or paper are used as the fibrous structures.
7. Process as claimed in claim 6, characterised in that fibre matting with a weight per unit area of not more than 60 g/m2 is used for strengthening.
8. Process as claimed in claims 1 to 7, characterised in that the fibrous structure ist treated with the plastics dispersion by impregnation, spraying, coating, padding or printing.
EP80108012A 1980-12-18 1980-12-18 Process for the consolidation of fibrous material with dispersions of synthetic resin Expired EP0054573B1 (en)

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EP80108012A EP0054573B1 (en) 1980-12-18 1980-12-18 Process for the consolidation of fibrous material with dispersions of synthetic resin
AT80108012T ATE11681T1 (en) 1980-12-18 1980-12-18 PROCESS FOR STRENGTHENING FIBER STRUCTURES WITH PLASTIC DISPERSIONS.
DE8080108012T DE3070134D1 (en) 1980-12-18 1980-12-18 Process for the consolidation of fibrous material with dispersions of synthetic resin

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