DE2806863A1 - LATEX MIXTURE - BINDING AGENT FOR THE MANUFACTURE OF ASBESTOS PANELS AND - FILMS - Google Patents

Description

Feb. 17, 1978 P 12 361

140 West 51st Street, New York, New York 10020, USA

Latex mixture - binding agent! Preparation for the Manufacture of asbestos sheets and foils

The invention relates to new binders! Preparations for Joining of asbestos fibers and asbestos aggregates and the asbestos sheets or foils made from them. Both Binder preparations are latex mixtures in which the dispersed phase contains or consists from (1) 80 to 99.5% by weight of a conventional rubber binder and (2) 0.5 to 20% by weight of a copolymer or terpolymer of an α, ß-unsaturated carboxylic acid, an alkyl ester of an α, ß-unsaturated carboxylic acid and optionally an ethylenically unsaturated organic termonomer, as defined herein, by mixing Asbestos fibers with the binder preparation according to the invention "

8 QS 8 3 S / Ό ^! g 4 p

TELEPHONE (ΟΘΘ) 22 38 62

TELEX OB-2938O

TELECOPER

The asbestos sheets or foils produced are evenly coated with the synthetic rubber.

The invention relates to a binder preparation for asbestos fibers, which is a latex mixture in which the dispersed phase contains or consists of (l) 80 to 99.5% by weight of a conventional synthetic rubber binder and (2) 0, 5 to 20% by weight of a copolymer or terpolymer latex which contains (a) 30 to 85 parts by weight of an unsaturated carboxylic acid of the formula CH ₀ = C - COOH

² i

where R is methyl or ethyl, (b) 5 to 50 parts by weight of an unsaturated carboxylic acid ester of the formula CH = C - CuOR ₁

¹ ii

"2

in which R 1 is alkyl having 1 to 8 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, and R _{0 is} hydrogen, methyl or ethyl, and (c) 0 to 20 parts by weight of an ethylenically unsaturated organic monomer which is mixed with the above monomers (i ) uXll) is copolymerizable, with the formation of a stable latex.

The termonomer (III) ^ which is critical to manufacture of terpolymers with the properties sought after according to the invention can be represented by the following formula will

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C = G III

! I.

X ₂

where R_ is hydrogen, methyl, ethyl or halogen, such as chlorine, bromine, iodine or fluorine, X _{1 is} hydrogen or C_-C- ^ Alko xycarbonyl and X "is a representative selected from the group aryl, aminocarbonyl, cyano, C -Cr- Alkoxy, carboxy, C ₁ -C ₁ carbonyl, halogen, acyl, aldehyde, keto, isocyanato, C ^ -Cgheterocycle, Cj-C-ralkylene, halomethylene, acetomethylene, suIfo, Cj-Cr-alkoxysilane and hydrogen mean »

A preferred idea of the invention is a binding agent tel preparation for asbestos fibers, which is characterized is that it contains or consists of a latex mixture in which the dispersed phase contains or consists of (1) about 80 to about 99.5 weight percent of a synthetic rubber; and (2) about 0.5 to about 20 weight percent of a highly carboxylated one Polishing. The highly carboxylated polymer is is a copolymer or terpolymer that contains (1) an α, ß-unsaturated carboxylic acid, (2) an alkyl ester of a α, β-unsaturated carboxylic acid and optionally (3) an ethylenically unsaturated organic monomer, which with the monomers (1) u, (2) is copolymerizable to form a stable latex.

The highly carboxylated latex and the conventional rubber binder latex are mixed together under

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Formation of an excellent binder preparation or - -Composition for use in the manufacture of asbestos fibers and asbestos sheets or foils. The product is characterized by a superior bond between the fibers. It also drains the water from the asbestos slurries which contain the latex mixtures according to the invention, greatly accelerated.

Asbestos sheets or sheets suitable for use as a substrate for vinyl floor coverings are generally used made from fibers having a length within the range of 0.08 to 0.32 cm (1/32 to 1/8 of an inch). Fibers this length are classified as Grades 5, 6, and 7 by the Quebec Asbestos Producers Association. These varieties and their mixtures are generally used in the manufacture of asbestos sheets, occasionally however, other fibers such as cellulose fibers are also incorporated.

The desired amount of asbestos fibers, generally 0.3 to 8% by weight based on the total weight of the slurry, is added to water to form a slurry. The slurry is then in a hydropulper, a Jordan apparatus, a Dutchman or refined in a disc refiner. The water is at this point hot (38 ° C) and it is recycled from the wet end of the papermaking machine. After the fiber bundles have been broken, the slurry is transferred to a tank in which the binder

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Latex is added. The mixture is then formed into sheets or foils or plates and the sheets or foils or plates are then pressed and dried.

The conventional rubber binder latex used in the latex blends of the present invention is it is usually a carboxylated styrene / butadiene latex, of 50 to 70% by weight of styrene, 30 to 50% by weight of butadiene and 0 to 5% by weight of a carboxylic acid monomer such as Acrylic acid, methacrylic acid, fumaric acid or itaconic acid. Alternatively, the latex can be a copolymer of acrylonitrile and butadiene, a neoprene latex, or any of the other known synthetic rubber latexes Act. The latices can also contain emulsifiers, chain transfer agents, preservatives and other modifiers.

The highly carboxylated latices used according to the invention can by a 1-stage low temperature emulsion polymerization process can be produced as described in more detail below. Those obtained in this polymerization Polymers consist of or contain the following repeating units?

RI CH ₂ -C

COOH

CH ₉ - C 2 ι

COOR

0983S / 0 8 i

and if necessary

X ₁

wherein R, R ₁ ,
have services.

-Ar-

HO

R-

and X _{2 have} the meanings given above

In a preferred embodiment of the invention, the highly carboxylated latex should be those given below Contain components in the following proportions:

1) 30 to 85, preferably 50 to 80% by weight in the case of copolymer latices and 50 to 70 wt.% for terpolymer latices of an α, β-monoethylenically unsaturated carboxylic acid of Forsiel I * preferably methacrylic acid, ^ thacrylic acid or a mixture of which with other unsaturated carboxylic acids such as acrylic acid. The amount of other unsaturated carboxylic acids that can be used in such mixtures can vary up to 50% or more of these mixtures, depending on the concentration and hydrophobic nature of the carboxylic acid ester units in the resulting polymers. With increasing concentration and / or hydrophobic nature of the Esters, increasing amounts of these other unsaturated carboxylic acids, such as acrylic acid, can be used, up to such a degree that a stable latex can still be obtained j

2) 5 to 50, preferably 20 to 50% by weight in the case of copolymer latices and 20 to 30% by weight for terpolymer latices

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at least one alkyl ester of an α, β-unsaturated carboxylic acid, A predominant part of this ester 1 to 8 Has carbon atoms in the alkyl group;

3) 0 to 20, preferably 3 to 8% by weight of an ethylenic unsaturated organic termonomers of the formula III » Termonomers of the formula III include, for example the following monomers: styrene, vinyl toluene, chlorostyrene, acrylamide, methacrylamide, N-isopropylacrylamide, acrylonitrile, methacrylonitrile, Vinylidenecyanide, methyl vinyl ether, ethyl vinyl ether, Butyl vinyl ether, half acid ethyl maleate, half acid hexylraaleate, half acid ethyl fumarate, half acid ethyl itaconate, Diethyl maleate, dibutyl maleate, diethyl fumarate, vinyl chloride, Vinylidene chloride, vinyl bromide, vinylidene fluoride, vinyl acetate, vinyl propionate, vinyl chloracate, vinyl banzoate, vinyl thioacetate, Acrolein, methacrolein, methyl vinyl ketone, ethyl vinyl ketone ^ tsopropenyl methyl ketone, Vinyl isocyanate, isopropenyl isocyanate, vinyl isothiocyanate, N-vinyl-2-pyrrolidone, N-vinyl-2-oxazolidinone, Vinyl furan, indene, 2,3-dihydrofuran, vinyl succinimide, Butadiene, isoprene, chloroprene, allyl chloride, allyl acetate, allyl laurate, methallyl chloride, vinyl sulfonic acid, Sodium vinyl sulfonate, vinyl triethoxysilane, vinyl triisopropoxysilane, Ethylene and propylene.

Of course, all of the above percentages relate to the total weight of the copolymer and they result total 100%.

In addition to the abovementioned types of termonomers, minor Amounts of a bifunctional, ethylenically unsaturated

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crosslinking monomers are added to the mixture · This monomer must be able to operate under free radical conditions to polymerize so as to produce different fats of the To covalently bond polymers to each otherExamples of such polyfunctional monomers are divinylbenzene, Polyethylene glycol dimethacrylate and methylenebisacrylamide " Other monomers that make the polymer curable (by heat treatment) or otherwise crosslinkable can also be used as comonomers such as methylolacrylamide, glycidyl methacrylate or epoxybutadiene can be used »

The preferred method of polymerization is essentially one by free. Radical catalyzed discontinuous (batch) polymerization of monomers, which are dispersed in the aqueous phase with suitable surface-active agents and protective colloids · Recommended becomes a redox initiator system, exothermic polymerization is carried out under an inert gas and it is completed after a period of 10 minutes to 2 hours. The particles of the latex obtained in this way have an extremely small size and a high anionic surface charge. The emulsions generally have a solids content of 10% and preferably from 20% to 50% Particle size of the emulsion can range from 500 Angstroms or less to 3000 Angstroms or greater. The reaction temperature used depends mainly on the polymerization catalyst used and the used monomers. In general, the polymerization will take place at a temperature within the range carried out from 5 to 120 ° C. If the

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Catalyst is a redox system is the recommended initiation temperature range is from 5 to 8O ⁰ C, preferably at 15 to 6O ⁰ C.

It is advisable to avoid oxygen, for example. wisely under a neutral gas, such as nitrogen or argon, to work · Sometimes it can be beneficial to get the response to be carried out under increased or reduced pressure.

The polymerization can expediently take place in a 1-stage process be carried out, with all components being fed to the reaction vessel at the same time. Since the Polymerization reaction is exothermic, its beginning can be detected by the increasing temperature, which is a Consequence of the addition of the reactants is. When the polymerization has progressed to such a degree that the consumption of the monomers has practically ended (completely), the end point is determined by the interruption of the rise in temperature, followed by a drop in temperature. The time required for the above process can be within the range of 10 minutes to 2 hours lie.

Chain transfer agents can be used to regulate the average molecular weight of the polymer will. Preferred agents are mercaptans such as t-dodecyl mercaptan.

The terpolymers are produced in an emulsion system. The term "emulsion" as used herein means

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-JW-

a real colloidal dispersion of terpolymers in water,

The polymerization is carried out in the presence of a catalyst or initiator, preferably one which serves as a heat activated source of free radicals. Examples of such catalysts are peracetic acid, Hydrogen peroxide, persulfates, perphosphates, perborates and percarbonates The preferred catalyst is ammonium persulfate, since it gives efficient reaction rates and contains a volatile cation. The used The amount of initiator is normally 0.03 to 3.0, preferably 0.25 to 0.5% by weight, based on the total weight of the Monomers. The initiator is preferably a redox combination of the water-soluble persulfate as an oxidizing component and a hydrosulfite (e.g. sodium hydrosulfite) as a reducing component of the redox combination. Instead of the hydrosulfites can also what soluble bisulfites, metabisulfites or thiosulfates, reducing sugars or fofaldehyde sulfoxalate are used. Other typical redox combinations can also be used, such as sodium azide and ceric ammonium sulfate and titanium trichloride and hydroxylamine ,, can be used. Generally useful proportions of the specified Persulphate hydrosulphite systems are 0.01 to 1.0% oxidising Component and 0.15 to 1.5% of reducing component, based on the amount of monomers.

The redox combination can be activated further by the presence of polyvalent metal ions in the

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lower oxidation level, e.g. iron (II) sulfate or Copper (I) sulfate. The preferred amount of these metal salts can be between 5 and 10 ppm by weight, based on the total amount of monomers.

The aqueous medium for the polymerization contains some emulsifying agents to help disperse the monomers in the to support the aqueous medium and to protect the particles formed. Salts of sulfonic acids with a higher one Molecular weights such as alkylaryl sodium sulfonates are very well suited for this purpose, although other surfactants are also Means can be used with good results.

The amount of surfactant used can vary considerably, but is generally from 0.1 to 10, preferably from 0.2 to 1.0% by weight, based on the total weight of the comonomers. Additives such as alcohols can also be used to improve the solubilization of the water-insoluble components. The concentration of these materials may be between 0.1 and 2.0 wt "%, based on the weight of the comonomers, vary · The emulsion may also contain a small amount of a protective colloid such as water soluble cellulose derivatives, Po Iy (vinylpyrrolidone), Alkalimetallpolyacrylate or water-soluble Alginates . The amount of such colloid used may be within the range of, for example, 0.1 to 2, preferably 0.5 to 1% .

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To achieve significant improvements in the physical properties of the slurry and the finished product Plate or film is only a small amount of highly carboxylated Latex required. The highly carboxylated latex can be mixed with a conventional rubber binder latex be mixed, provided that the two are compatible with each other. Such mixtures can only be 0.5 to to 20 parts of the highly carboxylated additive polymer in 100 parts, based on the dry weight. the preferred amount of the highly carboxylated polymer is 1 to 8 parts per 100 parts of total polymer dry weight. The slurry obtained with asbestos and 15 parts of binder contains 20 to 800 ppm of highly carboxylated polymer « The exact amount of the highly carboxylated polymer, which is necessary to achieve the desired properties depends on the properties of the binder latex, with which it is mixed.

Asbestos felt latices are judged by manufacture of handmade plates or foils and carrying out a conventional paper test. A mixture of 25 parts asbestos Quebec variety 5 and 75 parts asbestos of Quebec variety 7 are mixed in water (38 C) to a consistency of about 5% dispersed. The slurry is blown using a 6.35 cm (2.5 inch) split disc propeller for 8 minutes stirred at 1000 rpm. Enough latex is added to make 15 parts of polymer in 100 parts of asbestos, and that Stirring is continued for 7 minutes. The resulting slurry is uniform and homogeneous and suitable for manufacture of leaves or plates in a Williams

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Sheet-making form suitable after being diluted to a consistency of 3%. The leaves resp. Plates are then pressed on a Williams hydraulic press and dried on a standard Williaras leaf dryer.

Water (of 35 C) is added to the material to bring the consistency to 2% · The drainage of the water from the Asbestos slurries are made using a Schopper-Riegler grind -Test device measured. Low numbers indicate rapid drainage.

The tensile strengths are determined by pulling 2.54 cm (1 inch) strips of the sheet on an Instron 1130 test device with a crosshead speed of 5.1 cm (2 inch) / min. A cold test is carried out at room temperature (21 ° C) by heating the strip to 190 ° C a hot test carried out; after the sample for 18 hours has been soaked with butyl benzyl phthalate to soften the plasticizer simulate which can be used with some vinyl coatings for the production of floor coverings, a plasticizer tensile test is carried out.

The invention is illustrated in more detail by the following examples, but without being limited to it. The parts, percentages, proportions and Unless otherwise stated, other quantities relate to weight.

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example 1

Manufacture ejme ^ Äthjrlacr ^ latj / Methacr ^ l ^ äu ^ £ 90 / lO2 -_

Device: 3 liter resin kettle equipped with a mechanical stirrer, a reflux condenser, a thermometer
and a gas introduction pipe.

Procedure: Were under a nitrogen protective gas atmosphere the following reaction components in the order given below and in the amounts given below introduced with stirring:

1694.2 g of distilled water

8.6 g Siponate DS-IO, 25% (product of the company

Alcolac Co.)
6.4 g n-butanol
42.9 g methacrylic acid
386.1 g of ethyl acrylate

0.123g divinylbenzene (60%)

1.71g of a 10% ammonium persulfate solution

2.86 g of a 0.1% iron (II) sulfate solution

At this point the stirring was stopped and 2.14 g of a 10% solution of concentrated sodium hydrosulfite were obtained (Lykopon) introduced. Slow stirring was started five minutes later as a slight rise in temperature (from 19 ° to 21 ° C) indicated that the reaction had already started. Five minutes later ^ at 26 C, the

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- J8--

The stirring speed was set at 150 rpm. Thereafter, the temperature rose steadily and reached ten minutes later at 56 C its maximum. The system was then allowed to cool to room temperature and the product, a free flowing one milky latex, was discharged through a sieve with a licensed mesh size of 0.15 mm (100 mesh).

Example 2

An emulsion copolymer was prepared by the method described in Example 1, but this time the Ratio of methacrylic acid to ethyl acrylate 5Οϊ5Ο (based on on weight).

Example 3

An emulsion copolymer was prepared by the method described in Example 1, but this time the Ratio of methacrylic acid to ethyl acrylate 70-30 (based on on weight).

Example 4

Following the procedure given in Example 1, an emulsion polymer was prepared. The polymer consisted of Methacrylic acid, ethyl acrylate and a termonomer. The percentages of the components were 70, 28 and 2% by weight, respectively. The termonomer was acrylamide.

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Example 5

An emulsion polymer was prepared according to the procedure given in Example 4, but this time using acrylonitrile as the termonomer and the percentages of the components 66.28 and 6? ₄ were.

Example 6

An emulsion polymer was prepared according to the procedure given in Example 5, this time as the termonomer n-Butyl vinyl ether was used.

Example 7

In a manner similar to that given in Example 5, an emulsion polymer was produced produced, this time being chlorostyrene as the termonomic was used.

Example 8

Similar to Example 5, an emulsion polymer was prepared, this time the termonomic being diethyl maleate was used.

Example 9

Similar to Example 5, an emulsion polymer was prepared, this time using 2-ethylhexyl hemic acid maleate as the termonomer was used.

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«Μ

Example 10

Similar to Example 5, an emulsion polymer was prepared, this time the termonomer being isobutylvinyl · ether was used.

Example 11

Similar to Example 5, an emulsion terpolymer was made this time using styrene as the termonomic.

Example 12

Similar to Example 5, an emulsion terpolymer was made produced, this time as termonomers triethoxyvinyl · silane was used.

Example 13

Similar to Example 5, an emulsion polymer was prepared, this time the termonomer being vinyl acetate was used.

Example 14

Similar to Example 5, an emulsion polymer was prepared, this time the termonomer N-vinyl-2-pyrro · lidon was used.

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Example 15

The latices of Examples 1 to 3 contained 20% solids. These latices were made with a caroxylated styrene / butadiene (COD) (60% styrene, 36% butadiene and 4% fumaric acid) latex with a solids content of 40% mixed so that the total solids obtained contained 92% of the COD latex and 8% of the highly carboxylated polymer. These Mixtures were made using the method described above for asbestos sheet manufacture tested. The latex mixtures showed the influence of the methacrylic acid content of the highly carboxylated latex additive on the performance of the asbestos felt. The KaIt tensile strength with the carboxylated styrene-butadiene-Latax was 6.86 kg / cm (33.4 pounds / inch) and the stiffness was 102. When the methacrylic acid content of the additive latex was increased, there was a significant increase of 50% in both observed in tensile strength as well as in stiffness. The other properties including drainage were not affected by this.

Example 16

The latices of Examples 4-14 contained 20% solids. These latices were made with a COD (60% styrene, 36% butadiene and 4% fumaric acid) latex with 40% solids mixed so that the total solids obtained contained &% of the highly carboxylated polymer. There were too

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three different commercial strength additives and one carboxylated styrene / butadiene latex tested without any additives. The results obtained are shown in the table below.

8Q9835 / Q8 & 9

Tabel

Schopper Tensile strength in kg / cm
(lbs / inch) warm Plasticizers Example no. Riegler ( ) cold 4.05 (22.6) 4.24 (23.7) 4th 17.5 8.75 (48.9) 4.12 (23.0) 3.83 (21.4) 5 17.3 8.77 (49.0) 4.49 (25.1) 3.94 (22.0) 6th 20.0 10.36 (57.9) 3.76 (21.0) 3.81 (21.3) 7th 15.0 9.59 (53.6) 3.67 (20.5) 3.88 (21.7) 8th 15.5 9.52 (53.2) 3.60 (20.1) 3.72 (20.8) 9 15.1 9.77 (54.6) 4.03 (22.5) 4.22 (23.6) 10 15.7 10.13 (56.6) 3.60 (20.1) 3.81 (21.3) 11 16.2- 9.52 (51.7) 4.17 (23.3) 4.12 (23.0) 12th 16.8 10.13 (56.6) 4.05 (22.6) 4.26 (23.8) 13th 16.0 9.09 (50.8) 3.7S (21.1) 4.05 (22.6) 14th 13.2 3.97 (50.1) 3.62 (20.2) 4.44 (24.8) Commercial
X addition ^x; ' 23.8 10.01 (55.9) 4.12 (23.0) 3.65 (20.4) Commercial
Y-Zu s at ζ ^xx) 23.4 9.42 (52.6) 3.94 (22.0) 3.97 (22.2) Commercial
Z-Zu s at ζ ^χχχ ) 20.9 9.24 (51.6) 3.79 (21.2) 3.04 (17.0) COD - no addition 22.0 7.98 (44.6)

The commercial additives are:

^x - Polyamide-JJpichlorhydrin-Harz - folr ^ cup resin, available from Hercules Incorporate., Wilmington,
Delaware, USA,

Acrylpolymeres - Accostrength 862 r; ^ sIn ₅ available from Firna Arcerican Gyanamid Co,

Accostrength 100 VKA resin.

All eleven mixtures according to the invention gave a higher one Cold tensile strength than the carboxylated styrene / butadiene latex without any addition. The average improvement in cold tensile strength was 18%. Three of the mixes (Examples 6, 10 and 12) gave greater than 25% improvement in cold tensile strength. Six of the eleven according to the invention Blends gave higher hot tensile strength than that carboxylated styrene / butadiene latex without the additive. All eleven blends of the invention gave higher plasticizer tensile strength than the carboxylated styrene / butadiene latex without any additive; the average improvement was 22%. Along with the increase in tensile strength, there was an average reduction in the Schopper-Riegler waiting time by 24%. Although the tensile strength improved with the commercial additives, no significant occurred Improvement in terms of drainage.

Although the invention has been explained in more detail above with reference to preferred embodiments, it is It goes without saying for the expert that it is by no means limited to it, but that it is in many respects can be altered and modified without departing from the scope of the present invention.

. $ 09835 / D 6

Claims (9)

ΡΑ ~ Γ ίΞMTANWALTS A. GRUNECKBR DiPl - ING H. KINKELDEY W. STOCKMAIR DR-IMa-AeE (CALTECH) 2806863 K SCHUMANN TT W ^ T DARERNAT-DiHL-PHYS P. H. JAKOB DlPL-ING. G. BEZOLD DR RERIMAT- DPU-CMOA 8 MUNICH MAXIMILIANSTRASSE P 12 361 claims 1. Binder preparation for asbast fibers, thereby indicated that it contains or consists from a latex mixture in which the dispersed phase contains or consists of 1) 80 to 99.5% by weight of a synthetic rubber and 2) 0.5 to 20% by weight of a highly carboxylated polymer which contains (a) 30 to 85 parts by weight of an unsaturated carboxylic acid of the formula CH ₂ - C - COOH in which R is methyl or ethyl, (b) 5 to 50 parts by weight of an unsaturated carboxylic acid ester of the formula CH ₀ - C-COOR ₁
I ^L
R ₂ 809835/0649 ORIGINAL! MSPECTED TELEPHONE (OSS) 22 28 62 TELEX O6-S9 3SO TELEGRAMS MONAPAT TELEKOPERER wherein R, alkyl of 1 to 8 carbon atoms and R ^ water substance, methyl or ethyl, and (c) 0 to 20 parts by weight of a termonomer of the formula H R ^ II ³ C = C where R »is hydrogen, methyl, ethyl or halogen, X ^ is hydrogen or C, -C.galkoxycarbonyl and X" is a representative from the group aryl, aminocarbonyl, cyano, C. - C, alkoxy, carboxy, C. - C. _fi Alkoxycarbonyl, halogen, acyl, aldehyde, keto, isocyanato, C ₀ - Cr heterocycle, C ₁ - C —alkylene, halo- ό y j. ή. genmethylene, acetomethylene, SuIfο, C .. - C / -alkoxysilane and mean hydrogen. 2. Preparation according to claim 1, characterized in that the synthetic rubber latex is selected from Group styrene / butadfen latex, acrylonitrile / butadiene latex and neoprene latex. 3. Preparation according to claim 1 and / or 2, characterized in that that the synthetic rubber latex is a carboxylated styrene / butadiene latex, the 30 to 85 wt.% Styrene, 25 to 70 wt.% Butadiene and 0 to 5% by weight of a carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid and itaconic acid. 4. Preparation according to at least one of claims 1 to 3, characterized in that it is the highly carboxylated Latex is a methacrylic acid / methyl acrylate copolymer. 809835/0649 5. Preparation according to at least one of claims 1 to 3, characterized in that it is the highly carboxylated Latex is a methacrylic acid / ethyl acrylate copolymer. 6. Preparation according to claim 4 and / or 5, characterized in that the highly carboxylated latex contains methacrylic acid in an amount within the range from 50 to 80% by weight and component (b) in an amount within the range from 20 to 50% by weight is _o 7. Preparation according to at least one of claims 4 to 6, characterized in that it is the highly carboxylated Latex is a terpolymer. 8. Preparation according to claim 7, characterized in that that in the terpolymer component (a) in an amount within the range of 50 to 70% by weight, component (b) in an amount within the range from 20 to 30% by weight and component (c) in an amount within the range from 3 to 8% by weight are present. 9. Asbestos film, characterized in that it contains or consists of asbestos fibers, which by a binder are connected together, which consists of a binder — latex which has a dispersed phase of (1) 80 to 99.5% by weight of a synthetic rubber and (2) 0.5 to 20% by weight of a highly carboxylated polymer, this contains (a) 30 to 85 parts by weight of an unsaturated carboxylic acid of the formula CH «= C - COOH wherein R is methyl or ethyl., (b) 5 to 50 parts by weight of an unsaturated carboxylic acid ester of the formula CH ₀ = C - COOR ₁ 2 ι R ₂ where R- alkyl with 1 to 8 carbon atoms and R_ hydrogen, Methyl or ethyl, and (c) 0 to 20 parts by weight of a termonomer of the formula TJ -p C = C I! X ₁ X ₂ wherein R "is hydrogen, methyl, ethyl or halogen, X, hydrogen or C ₁ -C ^ alkoxycarbonyl and X _{0 is} a representative J_ JLo i from the group aryl, aminocarbonyl, cyano, C. - C-ralkoxy, carboxy, C. - C. ^ alkoxycarbonyl, halogen, acyl, aldehyde, keto, isocyanato, C_ - C-heterocycle, C, -C-alkylene, halomethylene, acetomethylene , SuIfο, C ₁ - Cralkoxysilane and hydrogen mean. 80983S / 0649