DE1469525A1 - Method for treating textiles - Google Patents

Description

Case 9Ö27 / 52-P

THE DOW CHEMICAL COMPANY »Midland, Michigan / USA

Process for treating textiles

The present invention relates to coatings, finishes and impregnations for textile materials, in particular compositions dispersed in aqueous media, which on carpets and rugs, coarse woolen blankets and similar materials to improve their wash resistance to be brought.

The application of synthetic latices to textile fabrics is known. It is also known to tufted carpets and rugs by mechanical penetration (forcing) of Yarns and / or piping through loosely woven fabrics, such as, for example, coarse canvas, and subsequent fastening Gen the yarns and fibers by applying a prepared natural or synthetic latex to the back to manufacture such products and subsequent drying. The durability of such manufactured products against deterioration during washing and des

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Cleaning on the spot largely depends on the water resistance of the adhesive backing supplied by the dried latex preparation. Around Initially, vulcanized adhesives were used to provide the necessary water resistance Mixtures based on the known vulcanization technology Developed from rubber. However, such systems are complicated and relatively expensive. Besides that Because of the accuracy and details of the mixture, the vulcanization-type mixture is generally used by specialist companies manufactured for blends and sold to the textile companies and not manufactured in the carpet weaving mill itself. In many applications, the vulcanized systems have been replaced by non-vulcanized latices, the generally referred to as "self-curing" and with which a certain degree of water resistance with carboxyl group-containing latices through crosslinking di.rcl ·. use is achieved by heat. The water resistance imparted by the latter system is useful for many applications minimal and insufficient for other uses. It would be very useful to have a mix of that can be easily used in textile factories (i.e. does not require extensive preparation in the application); which is so stable that it can be stored for long periods of time, for example three months, and which is water-resistant that of vulcanized latices

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effected water resistance is equal to or better than this while the ease of use and ede Economics of the "self-curing" carboxylated Latices remain intact.

According to the present invention, improved adhesives and coatings for textile fabrics are now accessible by applying a coating layer of the aqueous mixture according to the invention to the fabric and drying the layer and then heat-curing it on the fabric. As essential wet names of the invention is an aqueous dispersion of Copolymerlsates of at least two polymerisAerbaren fe'.thylenisch unsaturated monomers from the group styrene and styrene eopolymerisierbare monomers, wherein 0.5 -. 10 wt% of the monomers have at least one carboxyl group as substituent, with a water-soluble adduct of epihalohydrins with ammonia, an alkylene amine, a polyalkylene polyamine or mixtures thereof are mixed, wherein the adduct has an inherent viscosity (inherent viscosity) of less than 0.1, determined at 25 ^e C and a solution of 1 g of the adduct, dissolved in 100 ml water with a content of 5 wt.% of hydrogen chloride, comprising the mixture, optionally with fillers, applied to the fabric, dried and then heat-cured.

It is particularly advantageous to use the äthy.leni sch ^; <? nge-

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saturated monomer mixture 1 to 4 dew. % Use monomers which have at least one carboxyl group as a substituent, such as acrylic acid, fumaric acid or a mixture thereof, which is preferably polymerized with styrene, 1,2-butadiene or a mixture thereof.

Good results are obtained when the water-soluble Adduct by condensing the epihalohydrine with a polyaain of the formula

where χ represents the number 2 or 3 and η represents the number 0, 1.2, 3 or 4, in proportions around 0.75 to 1.8 mol of epihalohydrin per mol of primary amine and 0.3 to 0.8 mol per mol to give secondary amine, or is prepared with ammonia in an amount of 0.5 to 2.8 moles of epihalohydrin for each mole of ammonia. The epihalohydrin used in the preparation of the water-soluble adduct is preferably epihalohydrin.

Oute results are obtained when the mixture is applied with or without fillers to the fabric is dried and ansohllessend heat cured at a temperature from 93 to 177 ⁰ C.

.. II "

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The polymer dispersions and the water-soluble adducts « as defined above, result in easily miscible, compatible mixtures with excellent storage stability, the strongly adherent coatings with unusually good Resistance to water and washing operations form.

Particular typical alkylene polyamines are ethylene diamine (i.e. an amine for which η in the above formula is the number 0 means) * Dläthylenetriamine, Trläthylenentetramin, Tetraäthylenpentamin, Pentaäthylenhexamin und Dipropylenetriamln.

While epichlorohydrin is the preferred epihalohydrin, epichlorohydrin can be used with similar results if desired. The amine-epihalohydrin adduct is usually prepared by dissolving the epihalohydrin in water and then mixing the alkylene polyamine with the resulting solution using gentle agitation. Adjustment of the temperature of the solution to about 0 ° C to about 40 ° C and a low percentage of contaminants in the aqueous medium result in the formation of an adduct having a molecular weight range and viscosity useful in the practice of the invention. However, elevated temperatures, for example up to 85 ^° C. or higher, can be used, as will be shown by a later example. A mineral acid, such as hydrochloric acid, can be used to stop or "cancel"

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be added to the reaction to cause the formation of an adduct

Avoid tes with too high a viscosity.

The amine-epihalohydrin adduct is suitably an aqueous solution containing from about 10 wt.% Of the adduct, calculated as free base, is prepared and used, but this is not a critical limitation, since compounds are used with higher or lower proportions of adduct , so long as the intrinsic viscosity of the adduct is less than about 0.1, determined at 25 ⁰ C in a solution of 1 g of adduct per 100 ml of water containing 5 wt.% contains hydrogen chloride. When water is used with a content of 5 wt.% Sodium chloride as a solvent, the intrinsic viscosity should be less than approximately 0,1.2.

The ammonia-epihalohydrin adduct is suitably an aqueous solution containing from about 10 wt.% Adduct, calculated as free base, is prepared and used, but this is not a critical limitation, since materials can be used with greater or lesser proportions of adduct , as long as the intrinsic viscosity of the adduct is less than about 0.1, determined at 25 ^° C. in a solution of 1 g of the adduct per 100 ml of water which contains 5% by weight of hydrogen chloride. When water is used with a content of 5 wt.% Sodium chloride as a solvent, the measured inherent viscosity should be less than about 0.13 · In the present specification, the term "calculated

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as a free base "that any salt-forming constituents, which may be associated with this are not included in the weight of the adduct in calculations.

The latex used with the ammonia-epihalohydrin adduct as defined earlier is characterized by the fact that it forms a film below about 100 ° C and is about 0.5 to about 10% by weight , preferably about 1 to about 4% by weight, as an essential component. £, based on the weight of the polymer in the latex, contains units derived from monomers with carboxyl groups. Latexes, the greater amount of play contained at from monomers containing carboxyl groups derived units up to about 30 wt.%, Can be prepared and used, but such materials require higher amounts of ammonia Epihalogenfoydrid adduct, in order to achieve the required water resistance, and it can SiOH result in undesirable rigidity. Hence, such masses are usually not preferred. To produce the latex which can be used for carrying out the invention, at least two polymerizable, ethylenically unsaturated monomers of the styrene class and monomers copolymerizable with styrene are used in an emulsion system to form a latex copolymer that forms a film below about 100 ° C or at this temperature by adding solvents or softening can be mowed to form a film, co-polymerized. At least one of the to form one

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Latex for use in the present invention polymerize monomers consists of those polymerizable, ethylenically unsaturated monomers that Carboxy! Side groups contain, or the substituent groups have, which can be converted into carboxyl groups after polymerization. Examples of such carboxyl-containing monomers are α, ß-ethylenically unsaturated monocarboxylic acids, α, 8-ethylenically unsaturated dicarboxylic acids and mixtures and salts thereof. Special examples for such ethylenically unsaturated monomers with carboxyl side groups are acrylic acid, methacrylic acid, itaconic acid, Fumaric acid, maleic acid, acidic ethyl maleate, acidic Butyl maleate and salts of such acids. Often there are mixtures of a monooarboxylic acid and an oicarboxylic acid, each Ethylenic unsaturation is used. Sometimes up to three or more different α, β-ethylenic become unsaturated carboxylic acids combined in the recipe.

The ethylenically unsaturated monomers of the styrene class and monomers copolymerizable with styrene include those above described monomers with carboxyl groups, the alkenyl aromatic compounds (the styrene compounds), the Derivatives of ethylenically unsaturated acids, such as acrylic esters, acrylic oils, maleic acid esters, fumaric acid esters and unsaturated alcohol esters, the unsaturated ketones, the conjugated diolefins and other compounds containing one or more ethylenic bonds leading to

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Addition polymerization are capable.

Particular examples of such ethylenically unsaturated compounds are styrene, ct-methylstyrene, ar-methylstyrene, Ar-ethylstyrene, «», Ar-dimethylstyrene, ΑΓ, ΑΓ-diinethylstyrene, Ar-tert-butylstyrene, vinylnaphthalene, methoxystyrene, Cyanoatyrene, Acetylstyrene, Monochlorostyrene, Diohlorstyrene, and other halostyrenes, methylraethaerylate, ethyl acrylate, Butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, phenyl aylate, acrylonitrile, methacrylonitrile, Ethyl-fi-chloroacrylate, diethyl maleate, polyglycol maleate » Vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, vinyl methyl ketone, methyl isopropenyl ketone, vinyl ethyl ether and 1,3-butadiene and isoprene.

The optimal amount of the monomers having carboxyl groups copolymerized in the latex will vary somewhat depending on the properties desired for a particular end use. The lower amounts are generally used if the reactive carboxyl side groups of the Latexpolymerlsat8 are in verhältnlsmässig greater concentration at the surface of the particles, rather than being homogeneously dispersed throughout the particles, and if an ^m inimales Auamass is desirable to cross-linking.

The monomers described above are in aqueous emulsion, the surface-active agents, catalysts, Modifi-

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^ΛΌ Η69525

and the like. Contains and under conditions of tent, temperature, pressure, moving and the like. According to the well-known principles of emulsion polymerization ^ polymerized. Because of the carboxyl-containing monomers However, the effects caused are the types of ingredients that are present in the aqueous phase of emulsion polymerization used are chosen so that they are compatible with such monomers. For example usually only anionisohe or nonionic emulsifiers are used. There are also the carboxyl substituents (especially in the salt form) the monomers and the resulting copolymer in the latex have surface-active properties can impart the amount of the usual surfactant in the step of emulsion polymerization often significantly reduced or even omitted. The latlces can be made by adding monomers that are selected as described above, or water dispersions can instead be used for such latices of preformed polymers that have been modified, for example by grafting or by others Measures to have carboxyl side groups, or polymers with the formation of water dispersions of Polymers with such carboxyl groups are hydrolyzable, can be used.

To the latex, the water-soluble adduct becomes in an amount added to about 0.1 part to about 5 parts, preferably

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se about 0.5 parts to about 2 parts adduct (calculated as free base) per 100 parts of polymer solids in the latex. As mentioned, the ratio depends a little on the Amount of carboxyl groups in the latex polymer from. For example, if the latex polymer has 1 part of copolymerized monomer containing carboxyl groups per 100 parts Contains total weight of polymer, the amount of adduct commonly used is in the range of about 0.10 parts to about 2 parts, while the range is from about 0.10 parts to about 5 parts of adduct when the polymer is 10 parts Contains acid calculated as above.

The mixture of a latex and a carboxyl group-containing Polymer contains., And the water-soluble adduct as described above is required for the practice of the present invention. With the usual known RUoke side glues, impregnation agents and coatings for textile fabrics, however, it is common to add thickeners and, in particular, to introduce fillers. " to achieve the greatest economic efficiency. Such thickeners and fillers can also be used in the practice of the present invention. Dooh are the vulcanizing agents that are usually required for the known materials containing latioes are, not necessary · The most commonly used filler is calcium carbonate, which can be undesirable also other mineral pigments, such as titanium dioxide,

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Mica, clay, lead carbonate, ocher, hangan silicate, lead chromate and other inorganic salts such as sulfates and arsenates can be used as part of the filler. Such fillers can be used in amounts between about 75 parts to about 600 parts per 100 parts of copolymer solids in the Hasse latex. The mixtures containing the earboxyl group-containing latex and the epihalohydrin adduct are advantageously applied to numerous textile fabrics. Such mixtures are applied with the most varied types of devices, for example roller application machines, streiohmaschlnen and spray application machines. The composite is then passed through a .material 'oven to remove volatile materials, in particular moisture, usually at a temperature of about 90 to 18O ° C (200 to 350 ⁰ F) to about 126 I6j ^e c (26O preferably to 325 ⁰ F At the same time as the volatile materials are removed in the oven, the heating accelerates, which facilitates the removal, also accelerates the reaction of the carboxyl groups of the polymer, which are provided by the latex, with the reactive groups of the ephalohydrogen adduct, so that the mass hardens or is networked. The masses result in coatings, impregnations and reverse side glues for textile fabrics, such as, for example, woven woolen blankets and rugs, rugs and carpets, tufted rugs, rugs and carpets, velor carpets, upholstery fabrics and unwoven products. Such textile fabrics can be made of natural or synthetic

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Pairs or mixtures thereof.

The test for wasoh-resistant shows the advantageous water resistance of the products in accordance with the invention.

Check for stability

The test is Waaohbeetttndigkeit (* 0 ⁹ P 16) and 30 g of a commercially built detergent the Usually, in a household type used carried out in an automatic Haushaltawaeohmasohlne with back and hergehendem agitator, using water of 71 ⁰ C. The carpet or blanket sample is washed in the normal wash cycle for 15 minutes and then subjected to the machine's normal rinse and dry sole oven cycle. The samples of the material are then examined for any visible effects resulting from such treatment and evaluated in the following manner:

Observable effect Numerical
valuation Literal
valuation no visible effect 1 excellent very, little fraying of the
edge Well holds in the middle of the material,
However, it tears at the edges 7th sufficient no protection 10 slows

The following examples illustrate the invention without it

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to restrict. All parts and percentages are on by weight unless otherwise stated.

example 1

To a 76 l (20 gallon) capacity reaction vessel, 55 kg (120 lbs.) Of water was placed, and then 2542 g (5.6 lbs.) Of ethylenediamine was placed and the reaction vessel was closed. The temperature of the resulting aqueous solution spontaneously rose from 235 ⁰ C to 28 ° C while the pressure was at slightly less than atmospheric pressure maintained "were over a period of 10 minutes, then 10.4 kg (23 lbs.) Of epichlorohydrin was added, while the Temperature was kept ^{at 45 0} C by circulating cooling water in the dumbbell of the reaction vessel. Stirring in the reaction vessel was continued from the beginning of the addition of the materials up to JK) minutes after the addition of the last Bpichlorhydrin. The product obtained, which had 13 * 2 % of an adduct (calculated as the free base), was filtered through glass wool. The Äthylendiamln-epichlorohydrin adduct 30 obtained had an inherent viscosity of 0.075 in hydrochloric acid, when it was measured at 25 ⁰ C in the concentrations given above. A portion of the solution of ethylenediamine-epichlorohydrin adduct (1 * 0 g, calculated as free base) carrying 7 ug '© was mixed with 200 parts of a latex, hi ?. using before ... gentle agitation. 50 % concentration of pesticides, which is a copolymer of 42 % styrene.

«14 9098Q4 / 1UA

56% 1,3-butadiene, 1.75% and 0.25 AcrylsKure 1 ° fumaric * based sates, containing on the weight of copolymer! Mixed * Then, 300 parts of calcium carbonate was as much Natriumpolyaorylatverdickungsmittel to reduce the viscosity to about 4000 oP (10 parts of a 10 # solution or 1 part solids) and enough water to adjust the solids concentration of the mixture to 70 % . The resulting preparation was then used in an amount of 678 g dry weight

ρ 2
per m (20 oz./yd) applied to a tufted wool carpet with pile soles , which is tufted by

2

1016 g per m of wool yarn in a coarse canvas of 338 g ^ n

(30 oz. Wool yarn tufted into 10 oz./yd coarse canvas) and cured in a forced ^{air oven for 12 minutes at UQ 0} C (300 ^{0 F).}

The resulting tufted carpet, glued on the back, was tested for washing resistance according to the following description Tested operation, whereby the rating excellent (1) was obtained.

Example 2

An ethylenediamine-epichlorohydrin adduct was prepared as described in Example 1 with the exception that no cooling water was used and the jacket was kept at the temperature of the reaction components, so

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that the temperature rose as determined by the exothermic reaction. The highest temperature reached was about 85 * C. The intrinsic viscosity was 0.095 in aqueous Sodium chloride and 0.075 in hydrochloric acid when measured 25 "C in the concentrations given above. A mixture the ethylene diamine epichlorohydrin adduct with another portion of the same latex as in Example 1 was used made of the same proportions. Carpet samples glued to the back were made from it and tested for their water resistance as in Example 1. They also received an excellent rating (1}.

example 3

Ethylenediamine-epichlorohydrin adducts were wise prepared from Example 1 with the exception that different amounts of epiehlorohydrin per mole of ethylendlamine were used. Mixtures were made with other parts of the latex from Example 1 in an amount of 1 part Adduct produced for every 100 parts of solids in the latex. Carpet samples glued to the rear were in the same Manufactured and tested as described in Example 1. The results are given in Table I.

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Eplchlorhydrin
Ethylenediamine Table I. Evaluation of the resistance to wasoh Mole
Mole 1 Ever bad (10) 2 sufficient (7) 3 excellent (1) 4th sufficient (7) ⁺

^{+ also} tends to induce instability in the aqueous dispersion

Example 4

Other amine-epichlorohydrin adducts were prepared in the manner of Example 1, but using different amines. Epiohlorhydrin was used in a proportion of 1 mole of epichlorohydrin every atom of nitrogen in the amine. Such adducts have been made from ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Each of these adducts was measured with a latex containing a Copolymerlsat of 39.4% styrene, 58.2% butadiene, 1,2 J6 fumaric acid and 1.2 $ acrylic acid in an amount of 1 part per 100 parts of adduct copolymer, on a solids basis , mixed to form aqueous dispersions that were stable for at least 90 days at temperatures between about 0 ^° C (32 ^° F) and about 38 ^° C (100 ^° F). If tufted carpet samples glued on the back are produced from the aqueous dispersions obtained as in Example 1

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and then tested for wash resistance, they showed effective for wash resistance Cure, i.e. they were given a rating of "I to 4.

Attempts to produce an adduct each with diethylenetriamine, Ethylenedlamine and dipropylenetriamine, but using glycide instead of epichlorohydrin were made in the same manner as the preparation of the adducts of Example 4 using the same Quantities, i.e. 1 mol of glycide per g-atom of nitrogen in the amine. The masses obtained are not examples of the invention were in the 'same Mc-ngen ~ antellen with the same latex as described for example 4 is mixed. Smalled on the back Carpet samples that are thus described in the previously described Ways were made received a rating; from 7 to 10 for the test for detergency. J-he "another Exams using the same / earthen each however, with varying proportions of glycide, the washbasin strength of the carpet samples progressively deteriorated with increasing proportion of glycid,

Example 5

Mixtures of the ethylene diamine-epichlorohydrin adduct of Example 4 and the latex of Example 1 were prepared in the manner of Example 1, but using

"-SS - BAD ORiGINAi-

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different proportions of adduct and latex. on Backside glued carpet samples were also made and tested in the manner shown in Example t. The results are given in Table II.

Table II

Stability of the aqueous evaluation of the parts Adduct (a) Dispersion (b) Resistance to washing

0.5 greater than 90 days .7 1.0 greater than 90 days 1 2.0 greater than 60 days 1 5.0 greater than 5 days 1

a 100 parts of copolymer in the latex b at temperatures between 0 ⁰ C (? 2 ^β Ρ) and 38 ⁰ C (100 ⁰ P)

Example 6

An ammonia solution was prepared by mixing 50 ml of 15% ammonium hydroxide with 823 ml of water. With gentle stirring, 177 ml (1.5 mol) of epichlorohydrin was dissolved therein. The temperature was not allowed to rise above 50 ° C. during the initial reaction time of about one hour. 10 parts of the 10 # solution obtained in this way (about 1 part of the adduct, calculated as the free base) were stirred gently with 200 parts of a latex, at 50% pesticide concentration, which is a copolymer of 40 # styrene, 58 % butadiene, 1 , 75 S ^ acrylic acid and $ 0.25

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■ 909804/1 144

Fumaric acid, based on the copolymer weight, contained, stirred. Then there was 300 parts of calcium carbonate and so much Sodium polyacrylate thickener to reduce the viscosity to about 4000 cP (10 parts of a 10 # solution or 1 part of solids) to bring, interfered. The preparation obtained was in an amount of 678 g dry weight per m (20 oz./ yd) applied to a tufted wool carpet with pile loops, obtained by tufting 1016 g of woolen yarn per m in

ρ Ο

(oz 30th wool yarn tufted per oz yd in rough fabric 10. per yd) a canvas of 338 g / m was prepared, and (300 ⁰ F) cured in a forced air oven for 12 minutes at 149 ⁰ C.

The carpet glued on the reverse side was tested for wash resistance according to the procedure described earlier tested and received the rating excellent (1)

Example 7

In a Reaktlonsgefäss of 76 1 (20 gallon) capacity 58.5 kg (I29 lbs.) Of water and 4 kg (8.8 lbs.) Of an aqueous solution containing 28 wt.% Ammonia mixed. To the resulting solution, 7 kg (15.6 lbs.) Of epichlorohydrin was added over about 10 minutes. The reaction vessel was closed and a slight overpressure was maintained * in order to prevent the ammonia from escaping. The temperature in the reaction vessel was ~

- ^20th

fl Π Q «η Λ / 1 1 A Λ

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de "held for 2 hours at 44 ⁰ C. Then the Reaktlonsgemisch was cooled, filtered through glass wool, and stored in polyethylene lined with canisters of 18.9 1 (5 gallon) capacity. The aqueous solution thus obtained contained 8.3 % product, calculated as the free base. The inherent viscosity of a 1 #igen solution of the product in an aqueous solution containing 5% sodium chloride, at 25 ⁰ C, was 0.068, while a 1 in 5 # #ige solution of hydrochloric acid having an inherent viscosity of 0.054.

If the ammonia-epiehlorohydrin adduct with the in example 6 was mixed together with the filler and thickener of this example and the mixture obtained is applied to tufted carpet and washing resistance was tested by the same method as in Example 1, the evaluation was made excellent (2) received.

When epibromohydrin on the basis of an equal molar amount is used in place of the epichlorohydrin in the adducts of the above examples, similar ones become advantageous Get results. Accordingly, similarly advantageous results are obtained if for the latlces in the above examples of the invention other carboxyl group-containing Latlces are used, like latlces, the follow-

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de copolymers contain:

(a) styrene, 1,3-Äitadlen and acrylic acid,

(b) ethyl aerylate, n-butyl acrylate and acrylic acid,

(c) styrene, 1, j5-bsitadiene, acrylic acid and methacrylic acid ^

(d) ethyl acrylate, methyl methacrylate and acrylic

(e) styrene, n-butyl acrylate, acrylonitrile and

Acrylic acid,

Contain Cf) other Latlces which are film-forming below about 100 ⁰ C, and the polymers having carboxyl groups, the earbcasylgruppenhaltige component in Copolymerlsat in an amount of about

': 0.5 to about 10% by weight of ₃ calculated as acrylic acid,

ι based on the total copolyraerisate weighted. "

\ j is present,

* i For further comparisons with the products according to the invention effect the epichlorohydrin adducts from Eaisp.tel 1

^: ί when mixed with common commercial latices containing copolymers of vcn / ityroi and H ^ ji-butadlene, with

j which, however, do not contain monomers containing arboxyl groups

are polymerized, a soicne instability of the latex,

? ! that no homogeneous mixture can be produced. By

I ^! ■ ■

I the addition of significant quantities of additional surfactant is a minimum amount of SfcaMLttalfc

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achieved that is barely enough to mix the latex and of the adduct and to allow immediate application to a tufted carpet. However, such coatings show no noticeable improvement over similar coatings made from the same latex, However, no epichlorohydrin adduct is mixed in.

Mixtures according to the invention are compiled below:

An aqueous dispersion characterized by a mixture of (A) a latex of a copolymer of at least 2 polymerizable ethylenically unsaturated monomers from the class of styrene and contains styrene copolyraerisierbare monomers, wherein 0.5 to 10 wt.% Of the monomers at least one carboxyl group as substituents and (B) a water-soluble adduct of an epihalohydrin and ammonia, an alkylene polyamine, a polyalkylene polyamine or mixtures thereof, the adduct having an intrinsic viscosity of less than 0.1, measured at 25 ^° C. in a solution of 1 g of the containing adduct per 100 ml of water containing 5 wt.% of hydrogen chloride, which has preferably

1 to 4 wt.% Of the ethylenically unsaturated monomers have at least 1 carboxyl group as a substituent, the monomers having a carboxyl group as a substituent

90980 k / 114 4

Acrylic acid, puinaric acid or a mixture thereof are " the ethylenically unsaturated monomer essentially styrene *. Contains 1,3-butadiene or a mixture thereof, the water-soluble adduct is an adduct of 0.5 to 2.8 moles Is epihalohydrin with 1 mole of ammonia, especially the adduct of 1 to 2 moles of epihalohydrin with 1 mol of ammonia «

especially the adduct of epichlorohydrin with ammonia, or the adduct of an epihalohydrin with an alkylene polyamine the formula

H ₂ Mf (CH ₂ ) _X NH J _n (CH ₂ ) _X WH ₂

where χ is the number 2 or 3 and η is the number 0 * 1,2,3 or 4 represent,

In particular the adduct of 0.75 to 1.8 moles of epihalohydrin per mole of primary amino groups and 0.15 to 0.8 moles of epihalohydrin per mole of secondary amino groups in the alky-xene polyamine,

especially the adduct of epichlorohydrin with the Alkylene polyamine and

the monomers with carboxyl groups as substituents monocarboxylic acids, Dicarboxylic acids, half esters of dicarboxylic acids or mixtures thereof.

BATH

ο η α ο η / «/ 1 λ ι, ι.

Claims (8)

Patetite claims 1. A method for treating textiles by applying an aqueous adhesive or a coating layer to the textile material, drying and heat curing the layer, characterized in that an aqueous dispersion of a copolymer of at least 2 polymerizable, ethylenically unsaturated monomers from the group of styrene and monomers that can be polymerized with styrene wherein 0.5 to 10 wt.% of monomers having at least one carboxyl group as a substituent, is mixed with a water-soluble adduct of epihalohydrins with ammonia, an alkylene polyamine, a polyalkylenepolyamine, or mixtures thereof, wherein the adduct has an inherent viscosity of at least 0.1 , determined at 25 ^e C in a solution of 1 g of adduct in 100 ml of water containing 5 wt.% hydrogen chloride, and in the mixture is applied as a coating layer to the textile material. - 25 909804/1144 . H6-9525 2 »The method of claim 1, characterized in that t to 4 wt.% At least of the ethylenically unsaturated monomers used a carboxyl group as the substituent .. 3. Process according to claim 1 or 2, characterized in that acrylic acid, fumaric acid or a mixture thereof is used as the ethylenically unsaturated monomer with a carboxyl group or with carboxy groups. 4. The method according to any one of claims 1 to J>, characterized in that the ethylenically unsaturated monomer having at least one carboxyl group is copolymerized with styrene, 1 _a , 3-butadiene or a mixture thereof. 5. The method according to claim 1, characterized in that the water-soluble adduct used by condensing an epihalohydrine with a polyamine of the formula H ₂ NC (CH ₂ ) _x NHJ _n (CH ₂ ) _X NH ₂ where χ is the number 2 or j3 and η is the number 0, 1, 2,? or 4 represent * in an amount of 0.75 fis' ^ 8 mol of epihalohydrin per mole of primary amine and 0.3 to 0.8 mol of epihalohydrin per mole of secondary amine is obtained * 6. The method according to claim -1, characterized in that that the water-soluble adduct used by Eondensie- - ²⁶ - 909804/1144 Η69525 ren an epihalohydrin with ammonia in a proportion from 0.5 to 2.8 moles of epihalohydrins per half of ammonia is preserved " 7. The method according to claim 5 or 6, characterized in »that the epihalohydrin used is epichlorohydrin. 8. The method according to any one of claims 1 to 7 * gekennzelchntt that the applied layer is dried and then at a temperature of 93 to 177 ° C is heat-cured. - 27 - 909804/1 UA