EP0020884A1 - Manufacture of flat flexible products based on mineral fibres - Google Patents

Manufacture of flat flexible products based on mineral fibres Download PDF

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Publication number
EP0020884A1
EP0020884A1 EP80101762A EP80101762A EP0020884A1 EP 0020884 A1 EP0020884 A1 EP 0020884A1 EP 80101762 A EP80101762 A EP 80101762A EP 80101762 A EP80101762 A EP 80101762A EP 0020884 A1 EP0020884 A1 EP 0020884A1
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EP
European Patent Office
Prior art keywords
weight
water
monomers
fiber
dispersion
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.)
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EP80101762A
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German (de)
French (fr)
Inventor
Gerhard Ladisich
Hanns Dr. Bössler
Hans Hauser
Helmut Dr. Moroff
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Publication of EP0020884A1 publication Critical patent/EP0020884A1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates

Definitions

  • binders In the production of flexible fabrics such as paper, cardboard and non-woven fabrics from fibers by wet means, binders must be used in order to achieve sufficient strength.
  • binders are often used in the form of aqueous dispersions which the pulp '. added and precipitated at a later stage.
  • the quality of the binders has primarily been subject to requirements from a manufacturing point of view.
  • the degree to which the binders or the polymeric components are used generally plays an important role from an ecological and commercial point of view.
  • the focus of interest was the needs and requirements of the paper industry.
  • DE-AS 12 09 867 specifies a process in which, before dewatering, the anionic and cationic, thermoplastic plastics (latices) are added to the aqueous, optionally ground pulp slurry, one after the other, by known incorporation and / or polymerization of ionic compounds electrically neutral monomers are anionic or cationic.
  • DE-OS 26 1.9 310 proposes conversely, by adding an anionic, water-soluble hydrophilic polymer - preferably poly (meth) acrylic acid, polymeric itaconic acid - and / or salts thereof before adding the polymer latex, which can be quite conventional, to separate the latex for fiber suspension.
  • Alum must be added to the fiber slurries (except in the case of asbestos).
  • the water-soluble polymers should contain more than 60% by weight of acid and less than 40% by weight of other copolymerizable monomers.
  • US Pat. No. 2,995,512 teaches the clarification of colloidal aqueous dispersions by adding water-soluble cationic polymers to anionic disperse phases and vice versa.
  • DE-OS 27 10 966 an anionically stabilized aqueous dispersion of a carboxyl group-containing resin with a carboxyl group content of at least 6 wt.
  • DE-OS 27 10 996 also gives indications that — by means of the composition of the binder and the amount of binder, the mineral fiber papers that can be produced according to the application can be made either hard and rigid or soft and pliable.
  • the primary manufacturing requirements primarily the 100% separation of the binder on the mineral fibers, are also largely met.
  • the present invention has for its object to provide a method that gives mineral fiber-based fabrics good tear and splitting strength as well as flexibility and kink resistance. In addition, sufficient initial wet strength, good drainage and clear waste water with the lowest possible foam tendency are expected.
  • R 1 is an alkyl radical having at least 2 carbon atoms, preferably 4 to 18 Carbon atoms and optionally crosslinkable polymerizable monomers and optionally copolymerizable monomers, especially those with an influence known as "film-curing" on the overall polymer, to a lesser extent.
  • acrylic esters of the formula I in which R 1 is a C 4 radical, such as isobutyl or in particular n-butyl, or in which R 1 is 2-ethylhexyl, or mixtures thereof.
  • the proportion of the acrylic ester of the formula I is at least 50% by weight, based on the total polymer, preferably in the range from 60 to 95% by weight, particularly preferably in the range 70-93% by weight.
  • the proportion of crosslinkable monomers in the cationic acrylic dispersion is such that a sufficient crosslinking effect occurs in order to prevent the film from blocking at high temperatures or high air humidity.
  • crosslinkable monomers In general, the proportion of crosslinkable monomers does not exceed a value of 15% by weight, based on the total polymer in the cationic dispersion. As a standard value e.g. a content of 3 to 10 wt .-% can be considered.
  • crosslinkable monomers are to be understood primarily as self-crosslinking systems.
  • Suitable self-crosslinking monomers are primarily, for example, those with an N-methylolamide or ether, along with nitrile and carboxyl groups.
  • N-methylolacrylamide N-methylolmethacrylamide, N-alkoxymethylacrylamide and N-alkoxymethylmethacrylamide, for example N-athoxymethyl methacrylamide and N-butoxymethyl methacrylamide.
  • N-methylol methacrylamide is preferred, optionally in combination with methacrylamide.
  • self-crosslinking monomers also come with two or more reactive double bonds in the molecule, for example glycol dimethacrylate, 1,4-butanediol dimethacrylate, ethylene dimethacrylate, triglycol dimethacrylate, trimethylolpropane trimethacrylate or allyl compounds such as allyl methacrylate or allyl cyanurate, triallyl cyanurate and the like.
  • the monomers which can be copolymerized in smaller proportions, especially those with an influence on the overall polymer known as film-hardening, generally make up between 0 and 40% by weight, preferably between 0 and 30% by weight, based on the polymer content of the cationic acrylic dispersion .
  • the film can be given increasing hardness depending on the requirements.
  • copolymerizable monomers examples include esters of methacrylic acid with C 1 to C 4 alcohols, styrene, ⁇ -methylstyrene, vinyl chloride, vinylidene chloride, vinyl esters of fatty acids, such as vinyl acetate, vinyl propionate. If necessary, flame retardant additives can also be added to the agents according to the invention in minor amounts.
  • water-soluble polyanionic compounds are suitable as precipitants (cf. Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, vol. 11, pp. 581-586, Verlag Chemie).
  • examples include polymers or copolymers of acrylic acid, in particular with electrically neutral monomers, especially with acrylamide, in the form of suitable salts, for example the sodium salt, and also those of methacrylic acid and maleic acid.
  • the average molecular weight is usually 5-10 million.
  • copolymers of acrylic acid with acrylamide in the form of their sodium salts are suitable.
  • the preparation of the polymers which are used according to the invention can be carried out in a manner known per se, e.g. done in emulsion polymerization in water. (See H. Rauch-Puntigam, Th. Völker, "Acryl- und Methacryl -educationen; Springer-Verlag 1967).
  • the procedure can be carried out according to the one-pot ("batch") or preferably according to the monomer feed or emulsion feed process.
  • water, emulsifier and initiator water-soluble initiators such as hydrogen peroxide, perborate, persulfate and azo compounds
  • emulsion feed process an emulsion is first prepared from monomers, water, emulsifier and initiator and part of it is heated in the polymerization kettle. After the onset of polymerization, the remaining emulsion is slowly metered in from the feed tank.
  • emulsifiers e.g. Salts of long-chain amines in amounts of normally 0.5-6% by weight, based on the amount of water, are used.
  • the method according to the invention can be carried out based on the known methods of technology:
  • Mineral fibers such as glass fibers or rock wool and their mixture with glass fibers, as well as asbestos and mixtures with natural fibers such as cellulose fibers, for example fibers obtained from waste paper and fiber waste and textile fibers themselves, are particularly suitable as carrier fibers for the flexible sheetlike structures of the invention.
  • the fiber thickness is usually in the range of 5 - 20 ⁇ m, the fiber length is generally 3 to 7 mm. Shorter fibers result in fabrics of lower strength.
  • the dry fiber can be suspended, for example, with about 100 times its weight in water.
  • the amount of binder depends on the requirements. Binder contents of 2.5-10% by weight, calculated as the dry weight of the binder resin, based on the dry weight of the fibers j , already meet the stated requirements in many cases. However, the proportion of binder can also be increased up to about 100% of the fiber weight. Methods for producing cationic dispersions are known.
  • the cationic acrylic dispersions used according to the invention generally contain 10-60% by weight, preferably about 30 to 55% by weight, of binder in the aqueous phase which contains a cationic dispersant.
  • non-ionic dispersants are generally between 0.5 and 6% by weight in the water phase.
  • non-ionic dispersants can also be used in an amount of about 1-3% by weight will.
  • Compounds with a surfactant character are preferably used as nonionic dispersants, such as oxyethylated fatty acids, fatty alcohols or alkylphenols, but also protective colloids such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone or polyalkylene oxides and block copolymers of ethylene oxide and propylene oxide are suitable.
  • the cationic acrylic dispersion diluted to the appropriate solids content, is metered into the fiber suspension and evenly distributed for a certain time, about 3-5 minutes.
  • the anionic precipitant in aqueous solution is then expediently metered in with stirring.
  • the suitable amount can usually be easily determined by preliminary tests.
  • the concentration of the flocculant can be of the order of magnitude ⁇ 1% by weight. Shortly after the precipitant is evenly distributed in the mass, the binder is completely deposited on the mineral fibers. After the precipitation, the serum is completely clear. You can also add the precipitant and then the binder to the fiber-water mixture.
  • the fiber-water mixture can now be used in the usual way
  • the draining water is clear and practically free of binders.
  • the fabric thus obtained is introduced into a drying zone, where the crosslinkable binder also hardens.
  • the mineral fiber-based fabrics obtained according to the invention can be used, for example, as filter material or for production of largely chemical and heat resistant protective suits. They mainly serve as a carrier layer for various types of coated materials, such as rot-resistant bitumen cardboard, plastic floor coverings or synthetic leather-like materials.
  • Example 1 50 g of dry rock wool fibers (length 3 - 5 mm) are suspended in 10 l of water. 30 g of the dispersion of Example 1 diluted to 25 fat content are added to this suspension After approx. 1 min. 8.5 ml of a 0.2% solution of a copolymer of acrylamide and the Na salt are added to this suspension. added to the acrylic acid (commercial product PRAESTCL® 2935/73), whereby flocculation occurs. Then 2000 ml of this substance / water mixture are dewatered on a sieve (No. 0.100 DIN 4188), a clear waste water being obtained.
  • the flexible stone wool fleece obtained has a weight per unit area of approximately 320 g / m 2.
  • the flexible fabrics manufactured according to the invention largely meet the requirements mentioned at the beginning. They are characterized by high flexibility with very good strength properties. The process is particularly characterized by the rapid drainage and the absolutely clear wastewater obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

A cationic, stabilised acrylic dispersion having a glass transition temperature Tg (dyn) of less than 20 DEG C and a polyanionic coagulant are added to a mineral fibre stock-water mixture with subsequent sheet formation, drainage and drying.

Description

Bei der Herstellung von flexiblen Flächengebilden wie Papieren, Pappen und Faservliesen aus Fasern auf nassem Wege müssen, um eine ausreichende Festigkeit zu erreichen, Bindemittel verwendet werden.In the production of flexible fabrics such as paper, cardboard and non-woven fabrics from fibers by wet means, binders must be used in order to achieve sufficient strength.

Diese Bindemittel werden oft in Form wäßriger Dispersionen angewandt, die dem Faserbrei'. zugesetzt und in einem späteren Stadium ausgefällt werden.These binders are often used in the form of aqueous dispersions which the pulp '. added and precipitated at a later stage.

An die Qualität der Bindemittel sind primär Anforderungen unter herstellungstechnischen Gesichtspunkten gestellt worden. So spielt zum Beispiel der Grad der Ausnutzung der Bindemittel bzw. der polymeren Anteile allgemein unter ökologischen und kommerziellen Gesichtspunkten eine gewichtige Rolle. Im Vordergrund des Interesses standen dabei die Bedürfnisse und Anforderungen der Papierindustrie.The quality of the binders has primarily been subject to requirements from a manufacturing point of view. For example, the degree to which the binders or the polymeric components are used generally plays an important role from an ecological and commercial point of view. The focus of interest was the needs and requirements of the paper industry.

Die Technik hat im Verlauf der Entwicklung mit neutralen, kationischen und anionisch eingestellten Kunststoffen als Zusätzen zu Faserstoffen gearbeitet. Eine entscheidende Rolle spielt der Grad der Kunststoffretention im Verhältnis zum Kunststoffanteil in den Fasergebilden. Bei vielen Verfahren wird ein Polymerlatex dem wäßrigen Faserbrei zugesetzt und dann gefällt oder koaguliert. Bei den Fasern, beispielsweise den für die Papier- und die Vliesstoffherstellung überwiegend verwendeten Fasern ist ein Koagulierungsmittel erforderlich. Bei Asbestfasern wird hingegen in der Regel kein Koagulierungsmittel benötigt.In the course of development, the technology worked with neutral, cationic and anionically adjusted plastics as additives to fiber materials. The degree of plastic retention in relation to the proportion of plastic in the fiber structures plays a decisive role. In many processes, a polymer latex becomes the aqueous pulp added and then precipitated or coagulated. A coagulant is required for the fibers, for example the fibers predominantly used for the manufacture of paper and nonwovens. With asbestos fibers, however, no coagulant is usually required.

Die DE-AS 12 09 867 gibt ein Verfahren an, bei dem man dem wäßrigen, gegebenenfalls gemahlenen Faserstoffbrei vor der Entwässerung solche anionische und kationische, thermoplastische Kunststoffe (Latices) hintereinander hinzufügt, die durch bekanntes Einlagern und/oder Einpolymerisieren von ionischen Verbindungen in an sich elektrisch neutrale Monomere anionisch oder kationisch eingestellt sind. In der genannten DE-AS werden Polymerisate, Mischpolymerisate oder Gemische von Polymerisaten von Vinyl- bzw. Vinylidenchlorid, Vinylacetat, Styrol, Acrylsäureester, Acrylnitril, Olefinen sowie Kautschuklatex als Latices aufgeführt, denen durch Einlagern von anionischen bzw. kationischen Emulgatoren oder durch Einlagern bzw. Einpolymerisieren von geringen Teilen eines Carboxyl- bzw. Aminogruppenenthaltenden Monomeren ein bestimmter Ladungssinn vermittelt wird, jedoch sind nur reine Vinylverbindungen belegt. In der US-PS 3 748 223 wird ein verbessertes Verfahren zur Einarbeitung von Latexpolymerisat in wäßriger Dispersion in Fasern gelehrt, wobei im Polymerlatex ein anionisches wasserlösliches Polymerisat, z.B. Polyacrylsäure verwendet wird. Die Aufgabe war dabei vorwiegend eine Verbesserung der Abscheidung der Polymerisate in den Fasern.DE-AS 12 09 867 specifies a process in which, before dewatering, the anionic and cationic, thermoplastic plastics (latices) are added to the aqueous, optionally ground pulp slurry, one after the other, by known incorporation and / or polymerization of ionic compounds electrically neutral monomers are anionic or cationic. In the cited DE-AS, polymers, copolymers or mixtures of polymers of vinyl or vinylidene chloride, vinyl acetate, styrene, acrylic acid esters, acrylonitrile, olefins and rubber latex are listed as latices, which are caused by incorporation of anionic or cationic emulsifiers or by incorporation or Polymerization of small parts of a monomer containing carboxyl or amino groups gives a certain sense of charge, but only pure vinyl compounds are documented. U.S. Patent No. 3,748,223 teaches an improved process for incorporating latex polymer in aqueous dispersion into fibers wherein an anionic water soluble polymer, e.g. Polyacrylic acid is used. The main task was to improve the separation of the polymers in the fibers.

Die DE-OS 26 1.9 310 schlägt umgekehrt vor, durch Zugabe eines anionischen, wasserlöslichen hydrophilen Polymerisats - vorzugsweise von Poly(meth)acrylsäure, polymerer Itaconsäure - und/oder deren Salze vor der Zugabe des Polymer-Latex, der durchaus konventionell sein kann, zur Fasersuspension die Abscheidung des Latex durchzuführen. Den Faseraufschlämmungen muß (außer im Falle des Asbests) Alaun zugesetzt werden. Die wasserlöslichen Polymerisate sollen mehr als 60 Gew.-% Säure und weniger als 40 Gew.-% an anderen copolymerisierbaren Monomeren enthalten.DE-OS 26 1.9 310 proposes conversely, by adding an anionic, water-soluble hydrophilic polymer - preferably poly (meth) acrylic acid, polymeric itaconic acid - and / or salts thereof before adding the polymer latex, which can be quite conventional, to separate the latex for fiber suspension. Alum must be added to the fiber slurries (except in the case of asbestos). The water-soluble polymers should contain more than 60% by weight of acid and less than 40% by weight of other copolymerizable monomers.

Das US-P 2 995 512 lehrt die Klärung kolloidaler wäßriger Dispersionen durch Zusatz wasserlöslicher kationischer Polymerer zu anionischen dispersen Phasen und umgekehrt.US Pat. No. 2,995,512 teaches the clarification of colloidal aqueous dispersions by adding water-soluble cationic polymers to anionic disperse phases and vice versa.

In der DE-OS 27 10 966 wird einem mineralfaserhaltigen Stoff-Wassergemisch eine anionisch-stabilisierte wäßrige Dispersion eines carboxylgruppenhaltigen Harzes mit einem Carboxylgruppengehalt von mindestens 6 Gew.-% und ein wasserlösliches makromolekulares, stickstoffhaltiges, polykationisches Fällungsmittel zugesetzt und anschließend Blattbildung durchgeführt. Die DE-OS 27 10 996 gibt auch Hinweise darauf, daß-vermittels der Zusammensetzung des Bindemittels und der Bindemittelmenge die anmeldegemäß herstellbaren Mineralfaserpapiere entweder hart und starr oder weich und schmiegsam eingestellt werden können.In DE-OS 27 10 966, an anionically stabilized aqueous dispersion of a carboxyl group-containing resin with a carboxyl group content of at least 6 wt. DE-OS 27 10 996 also gives indications that — by means of the composition of the binder and the amount of binder, the mineral fiber papers that can be produced according to the application can be made either hard and rigid or soft and pliable.

Die primären herstellungstechnischen Anforderungen, in erster Linie die möglichst hundertprozentige Abscheidung des Bindemittels auf den Mineralfasern, werden ebenfalls weitgehend erfüllt.The primary manufacturing requirements, primarily the 100% separation of the binder on the mineral fibers, are also largely met.

Die Skala der Anforderungen ist aber damit noch nicht erschöpft. Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zu schaffen, das Flächengebilden auf Mineralfaserbasis gute Reiß- und Spaltfestigkeit sowie Flexibilität und Knickfestigkeit verleiht. Darüber hinaus werden eine ausreichende initiale Naßfestigkeit, gute Entwässerung und klares Abwasser mit möglichst geringer Schaumneigung erwartet.However, the scale of the requirements is not yet exhausted. The present invention has for its object to provide a method that gives mineral fiber-based fabrics good tear and splitting strength as well as flexibility and kink resistance. In addition, sufficient initial wet strength, good drainage and clear waste water with the lowest possible foam tendency are expected.

Es wurde nun gefunden, daß. man im Naßverfahren flexible Flächengebilde auf Mineralfaserbasis erhält, welche die genannten Anforderungen in hohem Maße erfüllt, wenn man dem mineralfaserhaltigen Stoff-Wasser-Gemisch eine kationische Acryldispersion mit einer Glasübergangstemperatur Tg (dyn) > + 20°C (gemäß DIN 7724), vorzugsweise > + 15°C zugibt und anschließend mittels wasserlöslicher polyanionischer Verbindungen (Flockungsmittel) die Fällung vornimmt. Die erfindungsgemäß verwendbaren, kationischen Acryldispersionen sind vorzugsweise so aufgebaut, daß sie als Hauptkomponente (bezogen auf das Gesamtpolymere) mindestens einen Acrylsäureester der Formel I CH2=CH - COOR1, worin R1 für einen Alkylrest mit mindestens 2 Kohlenstoffatomen, vorzugsweise 4 bis 18 Kohlenstoffatomen steht sowie gegebenenfalls vernetzbare polymerisationsfähige Monomere und gegebenenfalls copolymerisierbare Monomere, speziell solche mit einem als "filmhärtend" bekannten Einfluß auf das Gesamtpolymerisat zu geringeren Anteilen enthalten.It has now been found that. one obtains flexible sheet materials based on mineral fibers in the wet process, which fulfills the above-mentioned requirements to a high degree when the cationic acrylic dispersion with a glass transition temperature Tg (dyn)> + 20 ° C (according to DIN 7724), preferably>, is added to the mineral-fiber-containing mixture of substances and water + 15 ° C and then carries out the precipitation using water-soluble polyanionic compounds (flocculants). The cationic acrylic dispersions which can be used according to the invention are preferably structured such that they have at least one acrylic acid ester of the formula I CH 2 = CH - COOR 1 as the main component (based on the total polymer ) , in which R 1 is an alkyl radical having at least 2 carbon atoms, preferably 4 to 18 Carbon atoms and optionally crosslinkable polymerizable monomers and optionally copolymerizable monomers, especially those with an influence known as "film-curing" on the overall polymer, to a lesser extent.

Besonders bevorzugt sind die Acrylester der Formel I, worin R1 für einen C4-Rest, wie Isobutyl oder insbesondere n-Butyl steht, oder worin R1 für 2-Äthylhexyl steht, bzw. Mischungen derselben.Particularly preferred are the acrylic esters of the formula I in which R 1 is a C 4 radical, such as isobutyl or in particular n-butyl, or in which R 1 is 2-ethylhexyl, or mixtures thereof.

Der Anteil an dem Acrylester der Formel I liegt bei mindestens 50 Gew.-%, bezogen auf das Gesamtpolymerisat, vorzugsweise im Bereich von 60 bis 95 Gew.-%, besonders bevorzugt im Bereich 70 - 93 Gew.-%.The proportion of the acrylic ester of the formula I is at least 50% by weight, based on the total polymer, preferably in the range from 60 to 95% by weight, particularly preferably in the range 70-93% by weight.

Der Anteil an vernetzbaren Monomeren an der kationischen Acryldispersion ist so bemessen, daß eine ausreichende Vernetzungswirkung eintritt, um das Blocken des Films bei hohen Temperaturen bzw. hoher Luftfeuchtigkeit zu verhindern.The proportion of crosslinkable monomers in the cationic acrylic dispersion is such that a sufficient crosslinking effect occurs in order to prevent the film from blocking at high temperatures or high air humidity.

Im allgemeinen übersteigt der Anteil an vernetzbaren Monomeren nicht einen Wert von 15 Gew.-%, bezogen auf das Gesamtpolymerisat in der kationischen Dispersion. Als Normwert kann z.B. ein Gehalt von 3 bis 10 Gew.-% angesehen werden. Unter "vernetzbaren Monömeren" seien im Zusammenhang mit der vorliegenden Erfindung in erster Linie selbstvernetzende Systeme verstanden.In general, the proportion of crosslinkable monomers does not exceed a value of 15% by weight, based on the total polymer in the cationic dispersion. As a standard value e.g. a content of 3 to 10 wt .-% can be considered. In the context of the present invention, “crosslinkable monomers” are to be understood primarily as self-crosslinking systems.

Als eigenvernetzende Monomere kommen primär beispielsweise solche mit einer N-Methylolamid bzw. -äther, daneben Nitril-und Carboxylgruppen infrage.Suitable self-crosslinking monomers are primarily, for example, those with an N-methylolamide or ether, along with nitrile and carboxyl groups.

Genannte seien N-Methylolacrylamid, N-Methylolmethacrylamid, N-Alkoxymethylacrylamid und N-Alkoxymethylmethacrylamid, z.B. N-Athoxymethylmethacrylamid und N-Butoxymethylmethacrylamid. Bevorzugt ist N-Methylolmethacrylamid, gegebenenfalls in Kombination mit Methacrylamid. Schließlich kommen als eigenvernetzende Nonomere auch solche mit zwei oder mehr reaktiven Doppelbindungen im Molekül infrage, z.B. Glykoldimethacrylat, 1,4-Butandioldimethacrylat, Athylendimethacrylat, Triglykoldimethacrylat, Trimethylolpropantrimethacrylat oder Allylverbindungen, wie z.B. Allylmethacrylat oder Allylcyanurat, Triallylcyanurat u.ä.Mentioned are N-methylolacrylamide, N-methylolmethacrylamide, N-alkoxymethylacrylamide and N-alkoxymethylmethacrylamide, for example N-athoxymethyl methacrylamide and N-butoxymethyl methacrylamide. N-methylol methacrylamide is preferred, optionally in combination with methacrylamide. Finally, self-crosslinking monomers also come with two or more reactive double bonds in the molecule, for example glycol dimethacrylate, 1,4-butanediol dimethacrylate, ethylene dimethacrylate, triglycol dimethacrylate, trimethylolpropane trimethacrylate or allyl compounds such as allyl methacrylate or allyl cyanurate, triallyl cyanurate and the like.

Die gegebenenfalls in geringeren Anteilen copolymerisierbaren Monomeren, speziell solche mit einem als filmhärtend bekannten Einfluß auf das Gesamtpolymerisat, machen im allgemeinen zwischen 0 und 40 Gew.-%, vorzugsweise zwischen 0 und 30 Gew.-%, bezogen auf den Polymerisatgehalt der kationischen Acryldispersion aus. Durch dosierten Zusatz der copolymerisierbaren Monomeren kann man dem Film je nach den Anforderungen eine steigende Härte verleihen.The monomers which can be copolymerized in smaller proportions, especially those with an influence on the overall polymer known as film-hardening, generally make up between 0 and 40% by weight, preferably between 0 and 30% by weight, based on the polymer content of the cationic acrylic dispersion . By adding the copolymerizable monomers in a metered manner, the film can be given increasing hardness depending on the requirements.

Als Beispiel solcher copolymerisierbaren Monomeren seien Ester der Methacrylsäure mit C1 bis C4-Alkoholen, Styrol, α-Methylstyrol, Vinylchlorid, Vinylidenchlorid, Vinylester von Fettsäuren, wie Vinylacetat, Vinylpropionat genannt. Gegebenenfalls können den erfindungsgemäßen Mitteln noch flammfestmachende Zusätze in untergeordneten Mengen zugefügt werden.Examples of such copolymerizable monomers are esters of methacrylic acid with C 1 to C 4 alcohols, styrene, α-methylstyrene, vinyl chloride, vinylidene chloride, vinyl esters of fatty acids, such as vinyl acetate, vinyl propionate. If necessary, flame retardant additives can also be added to the agents according to the invention in minor amounts.

Als Fällungsmittel kommen erfindungsgemäß wasserlösliche polyanionische Verbindungen infrage (vgl. Ullmann's Enzyklopädie der technischen Chemie, 4. Auflage, Bd. 11, S. 581 - 586, Verlag Chemie). Genannt seien z.B. Polymerisate bzw. Copolymerisate der Acrylsäure, insbesondere mit elektrisch neutralen Monomeren, speziell mit Acrylamid,in Form geeigneter Salze, beispielsweise des Natriumsalzes, daneben solche der Methacrylsäure und der Maleinsäure. Das mittlere Molekulargewicht beträgt dabei in der Regel 5 - 10 Millionen. Besonders geeignet sind handelsübliche Copolymerisate der Acrylsäure mit Acrylamid in Form ihrer Natriumsalze.According to the invention, water-soluble polyanionic compounds are suitable as precipitants (cf. Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, vol. 11, pp. 581-586, Verlag Chemie). Examples include polymers or copolymers of acrylic acid, in particular with electrically neutral monomers, especially with acrylamide, in the form of suitable salts, for example the sodium salt, and also those of methacrylic acid and maleic acid. The average molecular weight is usually 5-10 million. Especially Commercially available copolymers of acrylic acid with acrylamide in the form of their sodium salts are suitable.

Die Herstellung der Polymerisate, die erfindungsgemäß verwendet werden, kann in an sich bekannter Weise z.B. in Emulsionspolymerisation in Wasser erfolgen. (Vgl. H. Rauch-Puntigam, Th. Völker, "Acryl- und Methacryl-Verbindungen; Springer-Verlag 1967).The preparation of the polymers which are used according to the invention can be carried out in a manner known per se, e.g. done in emulsion polymerization in water. (See H. Rauch-Puntigam, Th. Völker, "Acryl- und Methacryl -verbindungen; Springer-Verlag 1967).

Die Durchführung kann nach dem Eintopf-("Batch"-) oder vorzugsweise nach dem Monomerenzulauf- oder dem Emulsionszulaufverfahren erfolgen. Beim Monomerenzulaufverfahren werden im Polymerisationskessel Wasser, Emulgator und Initiator (wasserlösliche Initiatoren wie Wasserstoffperoxid, Perborat, Persulfat und Azoverbindungen) bei erhöhter Temperatur (80 - 100°C) vorgelegt und aus einem zweiten Kessel Monomeres langsam zudosiert. Beim Emulsionszulaufverfahren wird zunächst aus Monomeren, Wasser, Emulgator und Initiator eine Emulsion hergestellt und ein Teil davon im Polymerisationskessel aufgeheizt. Nach Einsetzen der Polymerisation wird aus dem Zulaufkessel die restliche Emulsion langsam zudosiert.The procedure can be carried out according to the one-pot ("batch") or preferably according to the monomer feed or emulsion feed process. In the monomer feed process, water, emulsifier and initiator (water-soluble initiators such as hydrogen peroxide, perborate, persulfate and azo compounds) are placed in the polymerization kettle at elevated temperature (80-100 ° C.) and monomer is slowly metered in from a second kettle. In the emulsion feed process, an emulsion is first prepared from monomers, water, emulsifier and initiator and part of it is heated in the polymerization kettle. After the onset of polymerization, the remaining emulsion is slowly metered in from the feed tank.

Als Emulgatoren können z.B. Salze langkettiger Amine in Mengen von normalerweise 0,5 - 6 Gew.-%, bezogen auf die Wässermenge, Verwendung finden.As emulsifiers e.g. Salts of long-chain amines in amounts of normally 0.5-6% by weight, based on the amount of water, are used.

Die Durchführung des erfindungsgemäßen Verfahrens kann in Anlehnung an die bekannten Verfahren der Technik vorgenommen werden:The method according to the invention can be carried out based on the known methods of technology:

Als Trägerfasern für die flexiblen Flächengebilde der Erfindung kommen vor allem Mineralfasern wie Glasfasern oder Steinwolle und deren Gemisch mit Glasfasern, daneben auch Asbest sowie Gemische mit Naturfasern, wie z.B. Cellulosefasern, beispielsweise aus Altpapier und Faserabfällen gewonnene Fasern sowie textile Fasern selbst infrage. Die Faserdicke liegt in der Regel im Bereich von 5 - 20 µm, die Faserlänge im allgemeinen bei 3 bis 7 mm. Bei kürzeren Fasern ergeben sich Flächengebilde von geringerer Festigkeit. Die trockene Faser kann beispielsweise mit etwa dem 100-fachen ihres Gewichts an Wasser suspendiert werden. Die Bindemittelmenge richtet sich nach den gestellten Anforderungen. Bindergehalte von 2,5 - 10 Gew.-%, berechnet als Trockengewicht des Binderharzes, bezogen auf das Trockengewicht der Fasernjerfüllen bereits vielfach die genannten Anforderungen. Jedoch kann der Binderanteil darüber hinaus, bis etwa 100 des Fasergewichts gesteigert werden. Verfahren zur Herstellung kationischer Dispersionen sind bekannt.Mineral fibers such as glass fibers or rock wool and their mixture with glass fibers, as well as asbestos and mixtures with natural fibers such as cellulose fibers, for example fibers obtained from waste paper and fiber waste and textile fibers themselves, are particularly suitable as carrier fibers for the flexible sheetlike structures of the invention. The fiber thickness is usually in the range of 5 - 20 µm, the fiber length is generally 3 to 7 mm. Shorter fibers result in fabrics of lower strength. The dry fiber can be suspended, for example, with about 100 times its weight in water. The amount of binder depends on the requirements. Binder contents of 2.5-10% by weight, calculated as the dry weight of the binder resin, based on the dry weight of the fibers j , already meet the stated requirements in many cases. However, the proportion of binder can also be increased up to about 100% of the fiber weight. Methods for producing cationic dispersions are known.

Die erfindungsgemäß verwendeten kationischen Acryldispersionen enthalten in der Regel 10 - 60 Gew.-%, vorzugsweise etwa 30 bis 55 Gew.-% Bindemittel in wäßriger Phase, die ein kationisches Dispergiermittel enthält.The cationic acrylic dispersions used according to the invention generally contain 10-60% by weight, preferably about 30 to 55% by weight, of binder in the aqueous phase which contains a cationic dispersant.

Typische Beispiele für kationische Dispergiermittel sind beispielsweise C12-C14-Fettamin-salze, Cocosaminhydro= chlorid oder Cetyltrimethylammoniumchlorid.Typical examples of cationic dispersants are for example C 12 -C 14 fatty amine salts, Cocosaminhydro = chloride or cetyltrimethylammonium chloride.

Sie sind in der Wasserphase in der Regel zwischen 0,5 und 6 Gew.-%. Daneben können noch nicht-ionogene Dispergiermittel in einer Menge von etwa 1 - 3 Gew.-% verwendet werden. Als nicht-ionogene Dispergiermittel werden bevorzugt Verbindungen mit Tensidcharakter eingesetzt, wie oxäthylierte Fettsäuren, Fettalkohole oder Alkylphenole, aber auch Schutzkolloide wie Polyvinylalkohol, Polyacrylamid, Polyvinylpyrrolidon oder Polyalkylenoxide sowie Blockmischpolymerisate von Äthylenoxid und Propylenoxid sind geeignet.They are generally between 0.5 and 6% by weight in the water phase. In addition, non-ionic dispersants can also be used in an amount of about 1-3% by weight will. Compounds with a surfactant character are preferably used as nonionic dispersants, such as oxyethylated fatty acids, fatty alcohols or alkylphenols, but also protective colloids such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone or polyalkylene oxides and block copolymers of ethylene oxide and propylene oxide are suitable.

Die auf den geeigneten Festgehalt verdünnte kationische Acryldispersion wird der Fasersuspension zudosiert und eine gewisse Zeit, etwa 3 - 5 Min. gleichmäßig verteilt. Dann wird zweckmäßig unter Rühren das anionische Fällungsmittel in wäßriger Lösung zudosiert. Die geeignete Menge läßt sich in der Regel leicht durch Vorversuche ermitteln. Die Konzentration des Flockungsmittels kann dabei in der Größenordnung < 1 Gew.-% liegen. Kurz.nachdem das Fällungsmittel gleichmäßig in der Masse verteilt ist, schlägt sich das Bindemittel vollständig auf den Mineralfasern nieder. Nach erfolgter Fällung ist das Serum völlig klar. Man kann auch zunächst das Fällungsmittel und danach das Bindemittel zum Faserstoff-Wasser-Gemisch geben.The cationic acrylic dispersion, diluted to the appropriate solids content, is metered into the fiber suspension and evenly distributed for a certain time, about 3-5 minutes. The anionic precipitant in aqueous solution is then expediently metered in with stirring. The suitable amount can usually be easily determined by preliminary tests. The concentration of the flocculant can be of the order of magnitude <1% by weight. Shortly after the precipitant is evenly distributed in the mass, the binder is completely deposited on the mineral fibers. After the precipitation, the serum is completely clear. You can also add the precipitant and then the binder to the fiber-water mixture.

Das Faserstoff-Wasser-Gemisch kann nunmehr in üblicherThe fiber-water mixture can now be used in the usual way

Weise in einem Rundsieb oder Langsieb zugeführt werden.Be fed in a circular sieve or Fourdrinier sieve.

Das abfließende Wasser ist klar und praktisch frei von Bindemitteln. Das so erhaltene Flächengebilde wird in eine Trockenzone eingeleitet, wo auch die Härtung des vernetzbaren Bindemittels stattfindet.The draining water is clear and practically free of binders. The fabric thus obtained is introduced into a drying zone, where the crosslinkable binder also hardens.

Die erfindungsgemäß erhaltenen Flächengebilde auf Mineralfaserbasis können z.B. als Filtermaterial oder zur Herstellung von weitgehend chemikalien- und hitzebeständigen Schutzanzügen verwendet werden. Vorwiegend dienen sie als Trägerschicht für verschiedenartige beschichtete Werkstoffe, z.B. fäulnisbeständige Bitumenpappe, Kunststoff-Bodenbeläge oder kunstlederartige Werkstoffe.The mineral fiber-based fabrics obtained according to the invention can be used, for example, as filter material or for production of largely chemical and heat resistant protective suits. They mainly serve as a carrier layer for various types of coated materials, such as rot-resistant bitumen cardboard, plastic floor coverings or synthetic leather-like materials.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung, sollen aber den nachgesuchten Schutz in keiner Weise einschränken.The following examples serve to illustrate the invention but are not intended to limit the protection sought in any way.

Die Mengenangaben beziehen sich auf Gewichtsteile.The quantities given relate to parts by weight.

BeispieleExamples A Herstellung der Dispersion, allgemeine VerfahrensweiseA Preparation of the dispersion, general procedure

Eine wäßrige Emulsion aus 100 Teilen Monomeren (Zusammensetzung siehe Tabelle), 1,45 Tle C14-Fettaminhydrochlorid und 0,2 % Tle Wasserstoffperoxid (30 %ig) in 60 Tle Wasser wird bei 85°C innerhalb von 5 Stunden in eine Lsg. ausAn aqueous emulsion of 100 parts of monomers (for composition, see table), 1.45 parts of C 14 fatty amine hydrochloride and 0.2% of hydrogen peroxide (30% strength) in 60 parts of water is dissolved in a solution at 85 ° C. in the course of 5 hours. out

40 Tle Wasser, 0,05 Tle Wasserstoffperoxid, 0,005 Tle FeC13 und 0,5 Tle C14-Fettaminhydrochlord eingetropft. Nach Polymerisationsende werden 3 Tle eines Adduktes aus i-Nonylphenol und 100 Tle Äthylenoxid zugesetzt. Man erhält eine Dispersion von etwa 50 % Fettstoffgehalt.40 parts of water, 0.05 parts of hydrogen peroxide, 0.005 parts of Fe C13 and 0.5 parts of C 14 fatty amine hydrochloride were added dropwise. After the end of the polymerization, 3 parts of an adduct of i-nonylphenol and 100 parts of ethylene oxide are added. A dispersion of about 50% fat content is obtained.

Figure imgb0001
Figure imgb0001

Beispiel 5Example 5

50 g trockene Steinwollefasern (Länge 3 - 5 mm) werden in 10 1 Wasser suspendiert. Dieser Suspension werden 30 g der auf 25 Fettstoffgehalt verdünnten Dispersion von Beispiel 1 zugesetzt Nach ca. 1 min. werden dieser Suspension 8,5 ml einer 0,2 %igen Lsg. eines Copolymerisates aus Acrylamid und dem Na-Salz. der Acrylsäure (Handelsprodukt PRAESTCL® 2935/73) zugesetzt, wobei eine Flockung eintritt. Anschließend werden 2000 ml dieses Stoff-/Wassergemisches auf einem Sieb (Nr. 0,100 DIN 4188) entwässert, wobei ein klares Abwasser erhalten wird. Das erhaltene flexible Steinwollevlies hat ein Flächengewicht von ca. 320 g/m2. 50 g of dry rock wool fibers (length 3 - 5 mm) are suspended in 10 l of water. 30 g of the dispersion of Example 1 diluted to 25 fat content are added to this suspension After approx. 1 min. 8.5 ml of a 0.2% solution of a copolymer of acrylamide and the Na salt are added to this suspension. added to the acrylic acid (commercial product PRAESTCL® 2935/73), whereby flocculation occurs. Then 2000 ml of this substance / water mixture are dewatered on a sieve (No. 0.100 DIN 4188), a clear waste water being obtained. The flexible stone wool fleece obtained has a weight per unit area of approximately 320 g / m 2.

Bei den weiteren Beispielen kann gemäß Beispiel 5 verfahren werden.

Figure imgb0002
The other examples can be carried out according to example 5.
Figure imgb0002

Die erfindungsgemäß hergestellten flexiblen Flächengebilde erfüllen weitgehend die eingangs genannten Forderungen. Sie zeichnen sich durch hohe Flexibilität bei sehr guten Festigkeitseigenschaften aus. Das Verfahren zeichnet sich besonders durch die rasche Entwässerung und das hierbei erhaltene, absolut klare Abwasser aus.The flexible fabrics manufactured according to the invention largely meet the requirements mentioned at the beginning. They are characterized by high flexibility with very good strength properties. The process is particularly characterized by the rapid drainage and the absolutely clear wastewater obtained.

Claims (3)

1. Verfahren zur Herstellung flexibler Flächengebilde auf Mineralfaserbasis durch Blattbildung aus einem mineralfaserhaltigen Stoff-Wasser-Gemisch unter Zusatz eines Bindemittels, durch Entwässerung auf einem Sieb und anschließende Trocknung,
dadurch gekennzeichnet,
daß man dem mineralfaserhaltigen Stoff-Wasser-Gemisch eine kationische stabilisierte Acryldispersion mit einer Glasübergangstemperatur Tg (dyn) (nach DIN 7724) kleiner 20°C und ein wasserlösliches polyanionisches Fällungsmittel zusetzt und anschließend die Blattbildung durchführt.1. Process for the production of flexible sheet materials based on mineral fibers by sheet formation from a mineral-fiber-containing mixture of substances and water with the addition of a binder, by dewatering on a sieve and subsequent drying,
characterized,
that a cationic stabilized acrylic dispersion with a glass transition temperature Tg (dyn) (according to DIN 7724) less than 20 ° C. and a water-soluble polyanionic precipitant are added to the mineral fiber-containing mixture of substances and water and then the sheet formation is carried out. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die kationisch stabilisierte Acryldispersion als Hauptkomponente mindestens einen Acrylester der Formel I GH2 = CH - COOR1, worin R1 für einen Alkylrest mit mindestens 2, vorzugsweise 4 - 18 Kohlenstoffatomen steht sowie gegebenenfalls in geringeren Mengen vernetzbare, polymerisationsfähige Monomere und gegebenenfalls weitere copolymerisierbare Monomere enthält.2. The method according to claim 1, characterized in that the cationically stabilized acrylic dispersion as the main component at least one acrylic ester of the formula I GH 2 = CH - COOR 1 , wherein R 1 is an alkyl radical having at least 2, preferably 4 - 18 carbon atoms and optionally in contains minor amounts of crosslinkable, polymerizable monomers and optionally further copolymerizable monomers. 3. Verfahren gemäß den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß der Anteil an dem Acrylester der Formel I, bezogen auf das Gesamtpolymerisat in der Dispersion mindestens 50 Gew.-%, vorzugsweise 60 - 95 Gew.-%, speziell 70 - 93 Gew.-% und der Anteil an vernetzbaren Monomeren weniger als 15 Gew.-%, vorzugsweise 3 bis 10 Gew.-%, der Anteil an weiteren copolymerisierbaren Monomeren 0 - 40 Gew.-%, vorzugsweise 0 - 30 Gew.-% beträgt.3. Process according to claims 1 and 2, characterized in that the proportion of the acrylic ester of the formula I, based on the total polymer in the dispersion, is at least 50% by weight, preferably 60-95% by weight, especially 70-93 % By weight and the proportion of crosslinkable monomers is less than 15% by weight, preferably 3 to 10% by weight, the proportion of further copolymerizable monomers is 0-40% by weight, preferably 0-30% by weight .
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US4775586A (en) * 1987-02-17 1988-10-04 Armstrong World Industries, Inc. Paper, paper products, films composites and other silicate-polymer, construction materials
JPS646197A (en) * 1987-06-19 1989-01-10 Denki Kagaku Kogyo Kk Production of inorganic fibrous paper
DE3942528A1 (en) * 1989-12-22 1991-06-27 Didier Werke Ag METHOD FOR PRODUCING A FIBER LIGHT STONE AND FIBER LIGHT STONE

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DE1209867B (en) * 1961-10-21 1966-01-27 Waldhof Zellstoff Fab Process for the production of flat fiber material such as paper, cardboard, cellulose boards or the like with a high content of thermoplastics
US3779862A (en) * 1971-12-21 1973-12-18 Armstrong Cork Co Flexible, intermediate temperature, mineral wool board
DE2230985B2 (en) * 1972-06-24 1974-05-22 Roehm Gmbh, 6100 Darmstadt Process for the production of plastic-filled papers
EP0003481A2 (en) * 1978-02-02 1979-08-22 Dow Chemical (Europe) S.A. Highly filled sheets and method of preparation thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1209867B (en) * 1961-10-21 1966-01-27 Waldhof Zellstoff Fab Process for the production of flat fiber material such as paper, cardboard, cellulose boards or the like with a high content of thermoplastics
US3779862A (en) * 1971-12-21 1973-12-18 Armstrong Cork Co Flexible, intermediate temperature, mineral wool board
DE2230985B2 (en) * 1972-06-24 1974-05-22 Roehm Gmbh, 6100 Darmstadt Process for the production of plastic-filled papers
EP0003481A2 (en) * 1978-02-02 1979-08-22 Dow Chemical (Europe) S.A. Highly filled sheets and method of preparation thereof

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