CH367369A - Infinitely variable transmission, especially for passenger vehicles with high-speed engines - Google Patents

Description

  

  The present invention relates to a method for water- and solvent-resistant coating or impregnation of textile materials with polyurethane plastics using an aqueous dispersion of a polyurethane polyelectrolyte precondensate containing free methyl groups and isocyanate groups.



  The production of dispersed, crosslinkable polyurethanes is known from DAS 1 241 104 and French patent 1,483,587. Thereafter, compounds are used as cross-linking reagents which contain at least one reactive H atom and an N-alkoxymethyl group or an isocyanate group and an alkoxymethyl group. These patents give no information on the structure of high molecular weight polyurethanes by using isocyanate group-free, methylol group-containing precondensates with the in in this description.



  The published Dutch patent application 67.08653 and the German patent specification 1 244 410 describe ben u. a. the production of coatings based on polyurethane solutions, not dispersions. In addition, no precondensates containing methylol groups are used.



  In contrast, the inventive method for water- and solvent-resistant coating or impregnation of textile materials with polyurethane plastics is characterized in that an aqueous dispersion of a solid or liquid, isocyanate group-free, free reactive methylol group-containing polyurethane polyelectrolyte precondensate is used, the precondensate for the purpose Chain extension is subjected to a heat treatment at 25 to 200 C, which heat treatment is carried out before the application of the dispersion to the textile material and / or after the car rings during and / or after removal of the water.



  The dispersion of a polyurethane polyelectrolyte precondensate that can be used to carry out this process can be produced taking into account the following statements.



  According to one possible method of preparation, the polyurethane precondensates to be dispersed are provided at the end with reactive groups which are particularly reactive towards formaldehyde, and they are reacted with formaldehyde in the presence of water during or immediately before the dispersion. Another possibility is to use polyurethane precondensates which, for. B. be reacted with compounds containing reactive methylol groups via isocyanate groups, so that polyurethanes with terminal free methylol groups are formed.

   Contrary to expectations, there is no premature networking; rather, the dispersing process is made considerably easier by the addition of formaldehyde or the terminal methylol groups. During and after the dispersion there is thus a chain extension to the high molecular weight polyurethane.



  A polyurethane polyelectrolyte precondensate of this type is particularly suitable for the preparation of the dispersion which 1. has an average molecular weight of less than 25,000, preferably from 2000 to 10,000, 2. hydrophobic nonionic chain segments of at least 60 chain links.

    
EMI0001.0017
  
    3. <SEP> one <SEP> salary <SEP> from <SEP> 4 <SEP> to <SEP> 120 <SEP> milliequivalent,:, <SEP> preferred <B> u </B>
 <tb> I.
 <tb> Z ' <SEP> N <B> I #, </B> <SEP> I <SEP> <B>) p </B>
 <tb> Z
 <tb> Either 8 to 80 milliequivalent%, of salt groups or groups capable of salt formation, which are converted into salt groups in the course of the process, and 4. at 120 ° C. a viscosity of less than 1500, preferably 100 to 1000 poise , which are dispersed with water at 20 to 150 C, preferably 50 to 130 C, the amount of water being 0.5 to 4 times the amount of polyurethane polyelectrolyte. The reactive methylol groups containing compounds are specifically amine-formaldehyde resins or phenol -Formaldehyde resins with free methylol groups are suitable.



  It is also expedient to adjust the polyurethane dispersions to a pH value between 4 and 2 before, during or after a heat treatment.



  Another suitable method of production is that the polyurethane polyelectrolyte precondensate having methylol groups has been produced during or immediately before the dispersion by the action of an aqueous formaldehyde solution on a polyurethane polyelectrolyte with acylated amino groups that are reactive towards formaldehyde.



  One type of production consists in that the polyurethane polyelactrolyte containing methylol groups by the action of a formaldehyde-containing aqueous solution at temperatures above 50 C on a polyurethane polyelectrolyte obtained from compounds with reactive hydrogen atoms with a molecular weight of 50 to 20,000 and polyisocyanates and which has at least 4 milliequivalent% of salt groups or groups capable of salt formation, which are then converted into salt groups, as well as terminal acylated amino groups which are reactive towards formaldehyde, has proven to be particularly expedient.



  A type of production can also be considered which consists in that the methylol group-containing polyurethane polyelectrolyte is obtained from compounds with reactive hydrogen atoms with a molecular weight of 50 to 20 100, preferably 50 to 8,000, and polyisocyanates, (potential) polyurethane polyelectrolytes free of NCO groups, the 1. an average molecular weight of less than 25,000, preferably from 2000 to 10,000, 2. hydrophobic nonionic chain segments of at least 60 chain links, 3.

   a content of 4 to 120 milliequivalent%, preferably from 8 to 80 milliequivalent%, of salt groups or groups capable of salt formation, which are converted into salt groups in the course of the process, 4. a viscosity of less than 1500 P at 120.degree , preferably from 50 to <B> 1000 </B> P, and 5.

       terminal, formaldehyde-reactive amino groups of the formula -XN HR, where X is -CO-, -CS-, -S02-, -NR-CO-, -NR-CS-, -0-C0-, -S-CO -, -O-CS-, -0-S02-, -CN R-, -NR-CNR-, -CO-NR-CO-, -CS-NR-CS,
EMI0002.0001
    stands, where Z stands for -NHR,
EMI0002.0002
   or R is

   and R preferably hydrogen or an alkyl radical or alkenyl radical with 1 to 4 carbon atoms, which can also be part of a heterocyclic 5- or 6-ring with 1 to 3 heteroatoms and which is represented by -OH, -OCH3, -OC2H5, -CCI3, - COOH, -S03H can be substituted, or -CN, -CO-R ', -S02-R' (where R 'stands for an alkyl, alkenyl, alkoxy or carboxyalkyl radical with 1 to 4 carbon atoms) , has been produced by the action of formaldehyde-containing aqueous solutions at temperatures above 50 C, preferably 80 to 150 C, the equivalent ratio of -X-NHR to formaldehyde between 1: 0.3 and 1: 4 and the amount of water being 0, 5 to 4 times the amount of polyurethane.



  The aqueous solution containing formaldehyde should preferably take effect at pH values between 9 and 4.1. A preferred acylated amino group -X-NHR is an unsubstituted -CO-NH2 group or an unsubstituted urea or biuret group -NH-CO-NH2. Polyurethane electrolytes with groups that are reactive toward formaldehyde can also conveniently be produced by adding compounds with (potential) salt groups to polyurethanes with reactive unsaturated double bonds.



  Particularly suitable polyurethane polyelectrolyte precondensates are those which contain one of the following groups:
EMI0002.0008
   -C00 (-) -503 (-) -O-so 3 (-) -so 2 (-)
EMI0002.0009
      (R = alkyl, cycloalkyl, aralkyl, aryl) It is also possible to adjust the polyurethane dispersions to a pH value between 4.2 and 2 before, during or after the heat treatment or to add them to the dispersions Addition of at least half of the total amount of water, 0.5-20% by weight, of polyisocyanate with a molecular weight of 110-4000 can be emulsified.



  In this context, dispersions are generally understood to mean heterogeneous two-phase water-polyurethane systems, in particular those in which water forms the continuous phase. The term also includes sedimenting suspensions with particle diameters above approx. 5μ and colloid solutions or sols with particle diameters of approx. 10 to 100 μm. However, optically clear, homogeneous aqueous solutions are not to be understood here.



  The compounds with several reactive hydrogen atoms which are suitable for the preparation of the polyurethane polyelectrolytes in question according to the invention are linear or branched and have a molecular weight of 50-20,000, preferably 50-8,000. These compounds, known per se, have terminal hydroxyl, carboxyl, amino or mercapto groups: as far as they are higher molecular weight compounds, polyhydroxyl compounds vvie polyesters, polyacetates, polyethers, polythioethers, polyamides and polyesteramides or even vinyl polymers with more than one hydroxyl group.



  As polyethers z. B. the polymerization products of sterol oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrins and their mixed or graft polymerization products and those obtained by condensation of polyhydric alcohols or mixtures thereof and the polyhydric alcohols obtained by alkoxylation of polyhydric alcohols, amines, polyamines and amino alcohols . Isotactic polypropylene glycol can also be used. Products with a high alkylene oxide content are unsuitable if they lead to water-soluble polyurethanes.



  As polyacetates, for. B. the compounds which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde are possible. Suitable polyacetates can also be prepared by polymerizing cyclic acetates.



  The polyethioethers include, in particular, the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, amino carboxylic acids or amino alcohols. Depending on the co-components, the products are polythioethers, polythio mixed ethers, polythioether esters, polythioether ester amides. Such polyhydroxyl compounds can also be used in alkylated form or as a mixture with alkylating agents.



  The polyesters, polyesteramides and polyamides include those obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated alcohols, amino alcohols, diamines, polyamines and their mixtures, predominantly linear or branched condensates and z. B. polyterephthalates or polycarbonates. Also polyesters made from lactones, e.g. B. # -Caprolactone, or from hydroxycarboxylic acids can be used. The polyesters can have hydroxyl or carboxyl end groups.

   To their structure can NEN as alcohol component also higher molecular weight poly risate or condensates such. B. polyethers, polyacetates, polyoxymethylene (with) can be used. Unsaturated polyesters can be grafted with vinyl monomers.



  Particularly suitable structural components for polyesters are: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , 2,2-dimethyl-1,3-propanediol, cyclohexanedimethanol, quinitol, glycerol, trimethylolpropane, hexanetriol, pentaerythritol, butenediol, bis-hydroxyethyldiane, succinic acid, glutaric acid, adipic acid, suberic acid, phthalic acid, isophthalic acid, terephthalic acid, terephthalic acid , Terephthalic acid bis-glycol ester, maleic anhydride, fumaric acid, 6-hydroxycaproic acid, 4-hydroxybenzoic acid, trimellitic acid.



  Polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols such as castor oil and carbohydrates can also be used.



  In principle, polyhydroxyl compounds which have basic nitrogen atoms are also suitable, e.g. B. polyalkoxylated primary amines or polyesters or polythio ethers, which contain condensed alkyl diethanolamine. Compounds with reactive halogen atoms can also be condensed in, e.g. B. glycerol-u-chlorohydrin. Such compounds can also be used in alkylated, i.e. H. Onium form.

   Polyesters with built-in sulfonate or carboxylate groups, as described, for example, in French patent 1,496,584, can also be used. Among the polymers and copolymers of vinyl compounds which carry more than one hydroxyl group, those which have a molecular weight of 500-20,000 and which carry 2 to 10 hydroxyl groups are preferred. Examples include partially saponified vinyl acetate copolymers, low molecular weight polybutadienes with ON groups and, above all, oxidized polyethylene or polypropylene, the production of which is described, for example, in British patent specification 959,362.



  To vary the lyophilicity or the hydrophobicity and the mechanical properties, mixtures of different polyhydroxyl compounds can be used.



  Suitable higher molecular weight compounds with amino end groups are z. B. in French patents 1,361,810, 1,300,981, DAS 1,122,254 and US Pat. No. 2,888,439.



  All aromatic and aliphatic diisocyanates, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmctane diisocyanate, 4,4'-diphenyldimethylmctane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, are also suitable as starting material for the production of the polyurethane polyelectrolytes in question. 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of toluene diisocyanate, optionally in a mixture, 1-methyl-2,4-diisocyanato-cyclohexane, 1,6-diisocyanato-2, 2,4-trimethyl-hexane, 1,6-diisocyanato-2,4,

  4-trimethyl-hexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl-cyclohexane, chlorinated and bronzed diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatophenyl-perfluoroethane, tetramethyl-butane-1, 4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane-diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, p-xylylene diisocyanate,

   m-xylylene diisocyanate and the hydrogenation products of the aromatic diisocyanates listed. Urethane and biuret di- or triisocyanates can also be used, e.g. B. adducts of 1,6-hexane diisocyanate, 1,3-xylylene diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane with water or amines or polyalcohols, and also isocyanates with ionic groups, as they are, for example, by Addition of isocyanates with reactive halogen atoms to di- and polytertiary amines is obtained, phthalic acid bis-isocyanatoethyl ester, and also polyisocyanates with reactive halogen atoms,

   such as 1-chloromethylphenyl-2,4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate. Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 moles of hexamethylene diisocyanate with 1 mole of thiodiglycol or dihydroxydihexyl sulfide. Triisocyanates or crude technical mixtures of polyisocyanates can also be used. Partially masked polyisocyanates, e.g. B. dimeric toluene diisocyanate, or with, for example, phenol, tert.

      Butanol, phthalimide, caprolactam, methyl ethyl ketoxime, partially converted polyisocyanates. Aliphatic and araliphatic diisocyanates are particularly preferred.



  The low molecular weight compounds with reactive hydrogen atoms that can be used to produce usable polyurethane polyelectrolytes include: 1. the usual saturated and unsaturated glycols, such as ethylene glycol or condensates of ethylene glycol, 1,3-butanediol, 1,4-butanediol, Butenediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, hexanediol, bishydroxymethyl cyclohexane, dioxethoxyhydroquinone, dioxäthyldiane, terephthalic acid bis-glycol ester, succinic acid di-ss-hydroxyethyl amide,

          Succinic acid di- [N-methyl - (# - hydroxy-ethyl)] - amide, 1,4-di - (# - hydroxy-methyl-mercapto) - 2,3,5,6-tetrachlorobenzene, 2-methylene propane diol (1,3), 2-methylpropanediol- (1,3);

    2. aliphatic, cycloaliphatic and aromatic diamines such as ethylenediamine, hexamethylenediamine, 1,4-cyclohexylenediamine, benzidine, diamino-diphenylmethane, dichloro-di- amino-diphenylmethane, the isomers of phenylenediamine, hydrazine, ammonia, carbohydrazide, adipic acid dihydrazide, Sebacic acid dihydrazide, piperazine, N-methylpropylenediamine, diaminodiphenyl sulfone, diaminodiphenyl ether, diaminodiphenyldimethyl methane, 2,4-diamino-6-phenyltriazine;

       3. Amino alcohols such as ethanolamine, propanolamine, butanolamine, N-methyl-ethanolamine, N-methyl-isopropanolamine; 4. aliphatic, cycloaliphatic, aromatic and heterocyclic mono- and diaminocarboxylic acids such as glycine, α- and -alanine, 6-aminocaproic acid, 4-aminobutyric acid, the isomeric mono- and diaminobenzoic acids, the isomeric mono- and diaminonaphthoic acids; 5. water.



  There are also less common, z. B. hochschmel zende chain extenders with reactive What hydrogen atoms in the context of the present process, such. B. 4,4'-Di- (N-methyl - # - hydroxyäthylamino) -diphenyl- methane, ethyl-bis-3-hydroxy-cyclohexyl-phosphine oxide, N, N'-dimethyl-ethylene-diamine, oxalamidrazone, oxalic acid- bis-ethanolamide, 2,6-di- (hydroxymethyl) -tetrahydropyran, di- (hydroxy-neopentylidene) -penta-erythritol, dimethylol-tetrahydropyrimidine-thione, N, N'-bis- (2-aminoethyl) oxalic acid amide , N, N'-bis (2-aminopropyl) oxalic acid camide, diethyl sulfone,

   4-methylamino-butanol- (2), N, N'-carboxybutylurea, methylene-bis-benzoic acid, methylene-bis-benzyl-alcohol, hexane-his-semicarbazide, γ-hydroxybutyric acid hydrazide, 6-aminocaproic acid hydrazide, phenyl glycol , Dimethyloldihydropyran, dimethylol tetrahydrofuran, tetrachlorobutanediol, dithiooxamide, pentaerythritol monoacetone ketal, pentachlorophenylglycerol ether, 1,4-dipiperazino-butane-2,3-diol, sulfuryl disulfamide, 1,

  1- (di-hydroxymethyl) -d3-cyclohexene. Lauric acid di (hydroxyethyl) amide, isobutylidene diureide, also the compounds: HO (CH2) 2-NH-CO-CO-NH- (CH2) a-NH-CO-CO-NH (CH2) 2-OH
EMI0003.0100
    
EMI0004.0001
    HO- (CH2) 2-CO-NH- (CH2) e-NH-C0- (CH2) 2-0H Such strongly polar chain extenders capable of forming hydrogen bonds result in combination with ionic chain extenders, as they are e.g. B. formed by salt formation of basic chain extenders, particularly high strength and water resistance even with an effect of moisture and solvents.



  Special chain extenders with at least one basic nitrogen atom are e.g. B. mono-, bis- or poly-oxalkylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, such as N-methyldiethanolamine, N-ethyl-diethanolamine, N-propyl-diethanolamine, N-isopropyl-diethanolamine, N-butyl diethanolamine, N-isobutyl-diethanolamine, N-oley1-diethanolamine, N-stearyl-diethanolamine, oxethylated coconut fatty amine, N-allyl-di-ethanolamine, N-methyl-diisopropanolamine, N-ethyl-diisopropanolamine,

      N-propyl-diisopropanolamine, N-butyl-diisopropanolamine, N-cyclohexyl-diisopropanolamine, N, N-dioxäthylanifin, N, N-dioxätliyltoluidin, N, N-dioxätliyl-α;

  -amino- pyridine, N, N'-dioxäthyl-piperazine, dirnethyl-bis-oxäthyl- hydrazine, N, N'-bis - (# - hydroxy-ethyl) -N, N'-diethyl- hexahydro-p-phenylene- diamine, N - # - hydroxyethyl pipertzine, polyalkoxylated amines such as oxpropylated methyl diethanolamine, further compounds such as N-methyl-N, N-bis- γ-aminopropylamine, N - (γ;

  -Aminopropyl) -N, N'-dimethylethylenediamine, N- (γ-aminopropyl) -N-methyl-ethanolamine, N, N'-bis - (γ-aminopropyl) -N, N'-dimethylethylenediamine, N, N'-bis- (γ-aninopropyl) -piperazine, N - (# - amirioethyl) -piper-azine, N, N'-bisoxethyl-propylenediamine, 2,6-diaminopyridine, diethanolamino-acetamide, diethanolaminopropionamide, N, N -Bis-oxäthyl-phenyl-thiosemicarbazid, N, N-bis-oxäthyl-methylsemicarbazid, p, p'-bis-aminomethyl-dihenzyiniethyl-amine, 2,6-diamine pyridine.



  Chain extenders with halogen atoms or R-SO2O groups capable of quaternizing are, for example, glycerol-α-chlorohydrin, glycerol monotosylate, pentacrythritol bis-benzenesulfate, glycerol monomethanesulfonate, adducts of diethanolanine and chloromethylated aromatic isocyanates or aliphatic isocyanates such as N, N-bis-hydroxyithyl-N'-m-chloromethylphenylurea, N-hydroxyattiyl-N'-chlorohexylurea, glycine mono-chloroethyl urethane, bronacetyl dipropylenetriamine, chloroacetic acid diethanolamide.



  It is possible to use tri- or higher functional components, e.g. B. branched polyesters or polyethers, trifunctional or higher-functional isocyanates such as tris-isocyanatohexyl biuret or cyclic isocyanurate oligomers of diisocyanates. Higher-functional chain extenders such as glycerol, trimethylolpropane, pentaerythritol, dipropylenetriamine, hexane triamine can be used just as well.



  Monofunctional compounds with only one isocyanate-reactive group can also be used, e.g. B. (un) saturated fatty alcohols, fatty amines or fatty acids.

   Resin acids, N, N-dimethylethanolamine, N, N-diethylethanolamine, 1-dimethylaminopropanol- (2), N-oxethylmorpholine, N-methyl-N - # - hydroxyethylaniline, N-oxethylpiperidine, α-hydroxyethylpyridine, γ ; -Hydroxyethylquinoline, N, N-dimethylhydrazine, N, N-dimethylethylcinediamine, 1-diethylamino-4-aminopentane,?

  Amino pyridine, 3-amino-N-ethylcarbazole, N, N-dimethylpropylenediamine, N-aminopropylpiperidine, N-aminopropyl-morpholine, N-atninopropyl-ethylenimine, 1,3-bis-piperidino-2-amino - propane.



  As monofunctional alkylating agents for converting the hasish reaction components into the salt form for the purpose of producing the polyurethane polyelectrolyte, examples are given: methyl chloride, methyl bromide, methyl iodide, ethyl bromide, propyl bromide, butyl bronide, dimethyl sulfate, diethyl sulfate, methyl chloromethyl ether, methyl 1,2-dichloroethane Benzyl chloride, benzyl bromide, p-chlorobenzyl chloride, trichlorobenzyl chloride, p-nitrobenzyl chloride, ethylene chlorohydrin, ethyl bromohydrin, epichlorohydrin, ethylene oxide, propylene oxide,

          Styrene oxide. Benzene, toluene, naphthalenesulfonic acid esters, w-bromoacetoplenone, dinitrochlorobenzene, # -chloropentenamide, chloroacetic acid as well as their esters and amides, chloromethyldimethylethoxysilane, pentamethylchloromethyldisiloxane, pentamethylbromomethyldisiloxane, glycolcerol bromomethyl disiloxane, glycolcerol bromomethyl disiloxane, glycolcerol bromomethyldisiloxane -mono-chloroacetic ester, bromine-ethyl-isocyanate, chlorine-methyl-naphthalene, 3-methyl-3-hydroxymethyl-oxetane-methanesulfonate, phenylethyl bromide,

       p-2-Bromoethylbenzoic acid, 5-chloromethyl-furan-2-carboxylic acid, ethylphosphonite dichloroisopropyl ester, bromoethyl acetoacetate, propane sultone, butane sultone. Further examples can be found in DAS 1 205 087.



  Quaternization can also be carried out with cyanogen chloride or cyanogen bromide. Epoxides are used in combination with water and / or an acid as a quaternizing agent.



  Polyfunctional alkylating agents are also suitable, e.g. B. 1,4-dibromobutane, p-xylylene dichloride, 1,3-dinethyl-4,6-bis-chloromethyl-benzene, methylene-bis-chloroacetamide, hexamethylene-bis-bronithyl-urethane, adducts of 2-3 mol Chloracetamide to a di- or triisocyanate. Further suitable polyfunctional alkylating agents are contained, for example, in Dutch patent application 67/03743.



  Examples of tertiary amines suitable for quaternization are trimethylamine, triethylamine, triethanolamine, dimethylaminoethanol, N-methyldiethanolamine, pyridine, quinoline, and N-dimethylamino-propyldiethanolamine.



  Acids can also be used to form salts in this reaction stage. even those that simultaneously exercise a chain-building function, such as B. sulfurous acid, sulfuric acid, hypophosphorous acid, phosphinic acids, phosphonous and phosphonic acids, glycolic acid, lactic acid, succinic acid, tartaric acid, oxalic acid, phthalic acid, trimellitic acid.



  Further acids can be found in German Patent 1,178,586 and German Patent 1,179,363. Particularly preferred acids are those which greatly increase the hydrophilicity and in particular the dispersibility of the polyurethanes, such as hydrochloric acid, fluoric acid, sulfamic acid, phosphoric acid and their derivatives, tartaric acid, oxalic acid, lactic acid, acetic acid, acrylic acid. Various salt-forming agents can also be used in combination. As a result, a synergistic effect is achieved with regard to the dispersibility.



  The previously mentioned compounds with reactive hydrogen atoms, insofar as they contain basic N atoms or divalent S atoms, are used in combination with alkylating agents or acids to produce cationic polyurethane polyelectrolytes. Correspondingly, cationic polyurethane polyelectrolytes can be produced from compounds with reactive hydrogen atoms with reactive halogen atoms or ester groups of strong acids in combination with tertiary, secondary or primary amines, organic sulfides or phosphines.



  Correspondingly, the polyurethanes can also be modified anionically by incorporating suitable compounds. For this purpose, the starting materials for the production of the polyurethane polyelectrolytes are compounds which contain at least one hydrogen atom that reacts with isocyanate groups and at least one salt-like anionic group capable of anionic salt formation, possibly in a mixture: 1.

   Hydroxy and mercapto acids, such as glyceric acid, glycolic acid, thioglycolic acid, lactic acid, trichlorolactic acid, malic acid, dioxymaleic acid, dioxyfumaric acid, tartaric acid, dioxywcic acid, mucic acid, saccharic acid, citric acid, glyicceric acid-boric acid, manitol-benzoic acid, glyicceryl-boric acid , Protocatechuic acid, i-resorcylic acid, # -resorcylic acid, hydroquinone-2,5-dicarboxylic acid, 4-hydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, oxyterephthalic acid, 5,6,7,8-tetrahydro-naphthalic (2) -carboxylic acid- (3),

          1-hydroxynaphthoic acid (2), 2,8-dihydroxynaphthoic acid (3), # -oxypropionic acid, m-oxybenzoic acid, pyrazolonecarboxylic acid, uric acid, barbituric acid, 2,6-bis-hydroxymethyl-p-cresol;

       2. aliphatic, cycloaliphatic, aromatic and heterocyclic mono- and diaminocarboxylic acids, such as glycine, α- and # -alanine, 6-aminocaproic acid, 4-aminobutyric acid, sarcosine, methionine, leucine, isoleucine, serine, valine, ornithin, Histidine, lysine, proline, phenylalanine, threonine, cysteine, asparagine, glutamine, arginine, aspartic acid, glutamic acid, oxaluric acid, anilidoacetic acid, anthranilic acid, 2-ethylaminobenzoic acid, 3-aminobenzoic acid, 4-amino-benzoic acid, phenolic acid, 4-diaminobenzoic acid,

      5-aminobenzene dicarboxylic acid; 3. aliphatic, cycloaliphatic, aromatic and heterocyclic dicarboxylic and polycarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, schazinic acid.

   the isomeric phthalic acids, diphenic acids, the isomeric naphthalic acids, maleic acid, funaric acid, sulfodiacetic acid, diglycolic acid, thiodiglycolic acid, methylene-bis-thioglycolic acid, the isomeric pvridine-carboxylic acids, the isomeric pvridine-acetic acids, citric acid, quinoline-dicarboxylic-acetic acid, nitrilotetric acid, citricilotetric acid; 4th

   Hydroxy and carboxy sulfonic acids: 2-hydroxyethanesulfonic acid, phenolsulfonic acid (2), phenolsulfonic acid (3), phenolsulfonic acid (4), phenol disulfonic acid (2,4), sulfoacetic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, benzoic acid - (1) -disulfonic acid- (3,5), 2-chloro-benzoic acid- (1) -sulfonic acid- (4), 2-hydroxy-benzoic acid- (1) -sulfonic acid- (5), naphthol- ( 1) sulfonic acid, naphthol (1) disulfonic acid, 8-chloronaphthol (1) disulfonic acid, naphthol (1)

  - trisulphonic acid, naphthol- (2) -sulforic acid- (1), naphthol- (2) -trisulphonic acid, 1,7-dihydroxy-naphthalenesulphonic acid- (3), 1,8-dihydroxynaphthalenedisulphonic acid- (2,4). Chromotropic acid, 2-hydroxynaphthoic acid- (3) -sulfonic acid- (6), 2-hydroxycarbazole-sulfonic acid- (7): 5.

   Aminosulfonic acids: amidosulfonic acid, hydroxylamine monosulfonic acid. Hvdrazine disulphonic acid, sulphanilic acid, N-phenylamino-nethanesulphonic acid, 4,6-dichloroaniline-sulphonic acid- (2), phenylenediamine- (1,3) -disulphonic acid- (4,6), N-acetylnaphthytamine- (1) sulfonic acid (3), naphthylamine (1) sulfonic acid, naphthylamine (2) sulfonic acid, naphthylamine disulfonic acid, naphthylamine trisulfonic acid, 4,4'-di- (p-aminobenzoyl- amino)

  -diphenyl-urea- disulfonic acid- (3,3 '), phenylhydrazine-disulfonic acid- (2,5), 2,3-dimethyl-4-aminoazobenzene-disulfonic acid- (4', 5), 4'-aminostilbene disulfonic acid- (2 , 2 ') - # 4-azo-4 # -anisole, carbazole-disulfonic acid- (2.7), taurine, methyltaurine, butyl-taurine, 3-amino-benzoic acid- (1) -sulfonic acid- (5), 3 -Aninotoluene-N-methane-sulfonic acid, 6-nitro-1,3-dimethylbenzene-4-sulfamic acid, 4,6-diaminobenzene-disulfonic acid- (1,3), 2,4-diaminotoluene-sulfonic acid- (5) , 4,4'-diaminodiphenyl-disulfonic acid- (2,2 '),

          2-aminophenol sulfonic acid (4), 4,4'-diamino-diphenyl ether sulfonic acid (2), 2-amino anisole-N-methanesulfonic acid, 2-aminodiphenylamine sulfonic acid, ethylene glycol sulfonic acid, 2,4 -Diaminobenzenesulfonic acid;

       6. organic phosphorus compounds such as derivatives of phosphinic acid, phosphonous acids, phosphonic acids and phosphoric acids and esters of phosphorous and phosphoric acid and their thio analogs, eg.

   B. bis (a-hydroxyisopropyl) phosphinic acid, hydroxylalkanephosphonic acid, phosphorous acid bis-glycol ester, phosphorous acid bis-propylene glycol ester, phosphoric acid, phosphoric acid bis-glycol ester, phosphoric acid bis-propylene glycol ester;

    7. The hydroxy, mercapto and aminocarboxylic acids and sulfonic acids, polycarboxylic and sulfonic acids also include the (optionally saponified) addition products of unsaturated acids such as acrylic acid, methacrylic acid and unsaturated nitrites such as acrylonitrile, of cyclic dicarboxylic anhydrides such as maleic anhydride, phthalic anhydride, succinic anhydride, of sulfocarboxylic acid anhydrides such as sulfoacetic acid, o-sulfobenzoic anhydride, of lactones such as # -propiolactone,?

  -Butyrolactone, the addition products of the reaction products of olefins with sulfur trioxide such as carbyl sulfate, of epoxycarboxylic and sulfonic acids such as glycidic acid, 2,3-epoxypropanesulfonic acid, of sultones such as 1,3-propanesultone, 1,4-butanesultone, 1.8 -Naphthsultone, of disulfonic anhydrides such as benzenedisulfonic acid (1,2) anhydride to aliphatic and aromatic amines such as 1,2-ethylenediamine, 1,6-hexamethylenediamine, the isomeric phenylenediamines, diethylenetriamine, triethylenetetramine, ammonia, tetraethylenepentamine, pentaethylenepentamine, pentaethylene, hexrazine, if appropriate , Amino alcohols such as the hydroxalkylated amines and hydrazines such as ethanolamine, diethanolamine, triethanolamine, ethanolethylenediamine,

    Ethanol hydrazine, alcohols such as ethylene glycol. Propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, polyhydric alcohols such as trimethylolpropane, glycerol, hexanetriol, the (optionally hydrogenated) addition products of epoxy and ethyleneimine compounds such as ethylene oxide, propylene oxide, butylene oxide , Styrene oxide, ethylene imine and unsaturated nitrites such as acrylonitrile with aliphatic and aromatic aminocarboxylic acids and aminosulfonic acids, the reaction products of oxyalkanesulfonic acids, halocarboxylic acids and halocarboxylic acids with optionally alkylated hydrazines such as hydrazine acetic acid,

       Hydrazinethanesulphonic acid, hydrazinmethanesulphonic acid, the saponified addition products of cyanohydrins with hydrazines such as 1,2-hydrazine-bis-isobutyric acid; also the addition products of sodium hydrogen sulfite with olefinically unsaturated compounds such as allyl alcohol, maleic acid, maleic acid bis-ethylene and bis-propylene glycol esters; B. hydrazine carboxylic acids such as hydrazine dicarboxylic acids; 9. Higher molecular weight condensates, such as polyesters, which contain carboxyl groups.



  For conversion into the salt form for the purpose of producing anionic polyurethane polyelectrolytes suitable connec tions are, for. B .: 1. organic bases such as monofunctional primary, secondary and tertiary amines such as methylamine, diethylamine, triethylamine, trimethylamine, dimethylamine, ethylamine. Tributylamine, pyridine, aniline, toluidine, alkoxylated amines such as ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylaminoethanol, oleyldiethanolamine and polyfunctional polyamines, in which the individual amino groups may have different basicities, such as.

   B. the polyamines obtained by hydrogenation of addition products of acrylonitrile with primary and secondary amines, per- or partially alkylated polyamines such as N, N-dimethylethylene diamine, also compounds such as α-aminopyridine, N, N-dimethylhydrazine; 2. Inorganic bases, compounds with a basic reaction or compounds that split off, such as ammonia, monovalent metal hydroxides, carbonates and oxides such as sodium hydroxide and potassium hydroxide. Different salt formers can also be used in combination; carboxyl groups can also only be partially neutralized.



  Cationic and anionic polyurethane polyelectrolytes can also be produced by subsequently modifying nonionic polyurethanes by addition reactions cationically or anionically. For example, polyurethanes which have unsaturated C = C double bonds can be obtained by adding compounds which have at least one -OH, -SH, -NHR, -SCI group capable of addition reactions and a further group capable of salt formation, z. B.
EMI0006.0038
   (R = H or alkyl), -S, -P, -COOH, -SO, H,
EMI0006.0039
   or have a corresponding salt group, modify them to give polyelectrolytes.

    Such compounds capable of addition reactions are, for example: thioglycolic acid, glycolic acid, # - chlorosulfenylpropionic acid, # -alanine-Na, lysine, dimethylaminoethanol, diethylaminoethyl mercaptan, N, N-dimethylpropylenediamine, methyl-2-tydroxyethyl-2-ethylsulfide, Taurine, N-methyltaurine, 2-mercaptoäthylsulfonsaures Na trium, N, N-dimethylhydrazine, N, N-dimethylethylenediamine, sodium hydrogen sulfite.



  Another possibility of ionic modification of inherently nonionic polyurethanes is the action of monoisocyanates with tertiary amino, sulfide or reactive halogen groups. After the groups mentioned have been converted into the salt form by reaction with tertiary amines or quaternizing agents or acids, the polyurethane is modified by ionic side chains.



  Compounds suitable for modification are, for example: chloroethyl isocyanate, bromoethyl isocyanate, chlorohexyl isocyanate, the isomers of chloromethylphenyl isocyanate, chloromethyltolyl isocyanate, dimethylaminoethyl isocyanate, adducts of amino alcohols, diamines and thioether alcohols or. Thioether amines on mono- and polyisocyanates, methyl mercaptoethyl isocyanate.



  Another possibility for modification is the reaction of polyurethanes with cyclic compounds with 3-7 ring members which have salt-like groups or groups capable of forming salts after the ring has opened, e.g. B. Dicarhonsäureanhydrides, Disulfonsäureanhydridc, sulfocarboxylic anhydrides, sultones, lactones, epoxycarboxylic acids, epoxysulfonic acids, N-carboxyglycine anhydride, carbyl sulfate. This modification option is described in detail in DAS 1 237 306.

   Also those in the Belgian patent documents 636 <B> 799 </B> and 658 026 processes described are suitable for the production of cationic polyurethanes which can be used as starting material for the process according to the present invention.



  The order in which the components used to build up the polyurethane polyelectrolytes are added is fundamentally indifferent. You can, for example, combine all components, including those explained in more detail below, at least one acylated amino group-bearing Kom component or the di- or polymethylol compound at room temperature or elevated temperature and then allowed to react with one another, generally heated to about 100-160 must be, while in the presence of a basic component or a catalyst the reaction takes place spontaneously.

   It is also possible first to produce a prepolymer bearing NCO groups in a known manner and then to implement this further. Particularly preferred is a mode of operation in which the (potential) salt groups come as close as possible to the chain ends, so that the most pronounced possible block structure with a hydrophobic chain segment of 130-400 chain links is created. This is z.

   B. achieved by first preparing a higher molecular weight hydrophobic prepolymer from polyhydroxy compounds and polyisocyanates that are free of (potential) salt groups and then using chain extenders carrying (potential) salt groups, further polyisocyanate and the at least one acylated amino group carrying component or the at least one, preferably more than one methylol group carrying component further converts.



  According to a preferred mode of operation, the to
EMI0007.0003
    stands, where Z stands for -NHR,
EMI0007.0004
   or R is and R is hydrogen (preferred) or an alkyl or alkenyl radical having 1-4 carbon atoms which can be substituted by -OH, -OCH3, -OC2H5, -CCl3, -COOH, -SO3H. R can also stand for -CN, -COR ', - SO2R', where R 'denotes an alkyl, alkenyl, alkoxy or carboxyalkyl radical with 1-4 C' atoms. So it is acylated amino end groups or quasi acylated amino groups which are on a polarized C = N double bond.



  Furthermore, R can also be part of a 5-7-membered heterocyclic ring with 1-3 heteroatoms. O, S and N are to be mentioned as heteroatoms. The group -X-N H-R can be found inside or outside the ring.



  The easiest way to prepare the polyurethane polyelectrolytes in question is to first build up a polyurethane with terminal NCO groups on the basis of the compounds previously listed with reactive hydrogen atoms and a molar excess of polyisocyanates, which has an average molecular weight of less than 20,000 (preferably 1 (100 to 10 0). This corresponds to a content of free NCO groups of 0.3-20% (preferably 0.8-10%). The range is very particularly preferred between 1.5 and 6% NCO, whereby there are generally at least 2 NCO groups per polyurethane molecule.

   Such prepolymers are obtained in a known manner by maintaining an NCO / OH ratio between 1.1 and 2 when preparing the formulation.



  This prepolymer can then be allowed to react with compounds which have at least one of the groups -X-NH-R defined in more detail above and additionally a group Y which is reactive towards NCO groups. This group Y can e.g. B. one -OH, -NH2, -NH-R1, -SH, -COOH, -CONH2, -CSNH2, -CO-NH-NH2, -NH-CO-NH2, -NH-CS-NH2, -NH- Be an NH2 group.



  The compounds suitable for reaction with the prepolymers containing NCO groups are thus at least monofunctional both with respect to isocyanates and with respect to formaldehyde and have the general formula YX-NHR or Y-R2- (X-NHR) n, where X and Y are the above and R2 have an organic dispersing polyurethane electrolyte an average molecular weight of less than 25,000, preferably 2000 to 10,000, and have terminal groups of the general formula -XN HR which are reactive toward formaldehyde, where X is -CO-, -CS-, -SO2-, -NR-CO-, -NR-CS-, -O-CO-, -S-CO-, -O-CS-, -O-SO2-, -CN R-, - N R-CN R-, -CO-N RC O-, -CS-N RC S-,
EMI0007.0015
    is monovalent or polyvalent radical. n is 1-4.

   R2 is preferably an aliphatic, aromatic, cycloaliphatic or araliphatic radical with 1-18 carbon atoms, which can also be substituted by alkoxy groups or halogen atoms. As can be seen, X-NHR can be equal to Y, since e.g. B. the carbonamide or urea residue can react with both isocyanates and formaldehyde.



  Generally speaking, the compounds YX-NH-R or Y-R2- (X-NHR) n except for the connec tions that result directly from the definition of X and Y, generally so-called aminoplast-forming NH group-containing components, as they are, for . B. in Angewandte Chemie 76, 909-919 (1964) are defined and described in more detail (cf. also A. Bachmann and Th. Bertz: Aminoplaste, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig 1967). It is essential that the preformed polyurethanes, which carry 0.3-20k free NCO groups, with the compounds Y-X-NHR or

   Y-R2- (X-NHR) n essentially do not react with chain lengthening to give high molecular weight polyurethanes, but with chain termination, so that the average molecular weight does not exceed 25,000 and is preferably between 2000 and 10,000. By determining the end groups or by viscometric and osmometric molecular weight determination - to name a few examples, the average molecular weight can be estimated with sufficient accuracy.



  For the practical feasibility of the reaction it is particularly crucial that the z. B. solvent-free melt can be easily processed with conventional mixing units when the formaldehyde-containing solutions are then mixed in. Therefore, the polyurethane composition formed, which has terminal groups -X-NHR, should have a viscosity of less than 120 at 120 1500 </B> have poise. Preferably the viscosity is 50-1000 poise.



  Although the compounds YX-NHR or Y-R2- (X-NHR) ", with which the prepolymers are modified, react predominantly monofunctionally with respect to isocyanates, they can of course also proportionally be incorporated bifunctionally into the polyurethane molecule, provided that the molecular weight or the viscosity does not rise above the limits given above.



  If, after the water has been removed from the dispersion by evaporation, strongly crosslinked products are desired on the textile material, the compounds YX-NHR or Y-R2- (X-NHR) "can also be used in the preparation of the prepolymers containing NCO groups in bi- or polyfunctional form can be used.

        Compounds of the formula YX-NHR belong, for example, to the following prevention classes: ureas, sulfamides, semicarbazides, guanidines, oxamides, biurets, sulfonylureas, hydrazodicarbonamides, urethanes, cyanamides, acid amides, cyantiric acid amides, imidazolidones, heximidahydropyrimidone, , 3,5-tritizinone and the corresponding thio compounds.



  Individual representatives of these classes of compounds that are suitable for the preparation of the dispersion are, for example, urea, thiourea, sulfamide, semicarbazide, thiosemicarbazide, N-hydroxyurea, guanidine and its salts, methylurea, ethylurea, butylurea, methylthiourea, methylthiourea, allylthiourea , Methylsemicarbazide, methylthiosemicarbazide, methylguanidine, oxamide, thiooxamide, bitret, thiobiuret, iminooxamide, dithiooxamide, dithiobitret, iminothiooxamide, aminostulfonylurea, hydrazodicarbonanide, thiohydrazodicarbonamide.

       Guanyl urea, aminostifonyl thiourea. Dithiohydrazudicar- honamide, guanylthiourea, guanidinothiourea, N-aminooxamide, N-aminothiooxamide, hydrazocarboxylic acid, hydrazocarboxylic acid, iminooxanide hydrazide, guanidinocarbohydrazide, N-aminosulphamide, guanidino-uridine, N-aminosulfamide, guanoguananidine, Diithylurea, ethylene urea (imidazolidone), 4,5-dihydroxyimidazolidone,

       4,5-dimethoxy-imidazolidone, hexahydropyrimidone, melamine, 5-methyl-1,3,5-hexahydrotriazone, 5-ethyl-1,3,5-hexahydrotriazone, 1-oxa-3,5-diazinon, 4-ureido-6-methyl-hexahydropyrimidone, 4- and other condensation products of urea with formaldehyde, acetaldehyde or isohutyraldehyde, triacetone diurea, tetrahydropyrinidone, 4,6,6, -trimethyl-2-thiono-tetrahydropyrimidone,

      Allophanoic acid ethyl ester, trimethyl biuret, phenyl bitret, benzoyl bitret. Aninobiuret, cyanurea, biguanide, ammeline, thioammeline, carbonyldiurethane, ureadicarboxylic acid diamide, trimethylolnelamine, guanazole, guanazine, dieyandiamide, I-hydroxy-2,2,2-trichloroethylurea, N, N'-bis- (1- hydroxy-2,2,2-trichloroethyl urea, acetyl urea, trichloroacetyl urea, benzoyl urea, triuret, hexahydropyrimidone, acetylguanidine.

    Trichloroacetylguanidine, metlylsulfonylurea, ethylsulfonylurea, phenylurea, N, N'-diphenylurea, N, N'-ditolylurea, N, N'-o-phenyleneurea, peri-naphthyleneurea, diphenyl urea, 2,4-dimethyl urea, ethylene di urea, 2,4-dimethyl urea - methylsenicarbazide, o-hydroxyethylisourea, diphenylguanidine, N-methyl-N'-acetylguanidine, aminoguanidine, anilidoguanidine, N-amino-N-phenylguanidine, acetoguanamine, acetogtanide, oxamic acid, oxaluric acid,

       Thiooxamidic acid, methylolurea, N, N'-bis-methylolurea, hydroxyethylurea, N, N'-bis-hydroxyethylurea.



  Compounds of the formula Y-R2- (X-NII-R) n are for example: Glycolic acid amide, Glykolsätrethioamid, Hydroxymethylsulfonamid, Hydroxynethylurea, Hydroxymethylthiourea, Iminoglykolsäureamid, Hydroxymethylgtanidin, Glycinomamid, aminomethioamid, Aminomethylstioamid, aminomethylstioamid, Aminomethylstioamid Aminomethylguanidine, sarcosinamide, sarcosine thioamide, butylaminomethylsulfonamide, thioglycolic acid amide, thioglycolic acid thioamide, malonic acid diamide,

       Thio malonamide, Aminosulfonylacetamid, Ureidoacetamid, Thioureidoacetamid, carbamic acid glykolsäureamidester, carbamic acid thioglykolsäureamidester, Thiocarbamin- acid glykolsäureamidester, amidosulfonic-glykolsäureamidester, Guanylacetamid, guanidino acetamide malonic säuredithioamid, Aminosulfonylthioacetamid, acetamide Ureidothio-, Thioureidothioacetamid, Carbamic acid glycolic acid thioamide ester, Ureideomethylsulfonamid,

       Methylene-bis-urea, ureidomethyl-thiourea, ureidomethyl-guanidine, thioureidomethyl-stlfonamide, methylene-bis-thiourea, thioureidomethyl-tanidine, malonic acid camid hydrazide, aminosulphonyl-accthydric acid, glycidic acid, carbo-anhydride acid, carbo-anhydride-acid, carbo-acido-acido-acidrazide. acethydrazide, glycolic acid acid, glycine acid, sarcosine, thioglycolic acid, malonic acid,

       Malonsäurethioamid- treid, Ureidoacetureid, Malonsäureureid hydrazide, hydrazine zinoacetureid, urea Hydrazinoacetamid, Hydrazinothioacetamid, Aminosulfonylnethylhydrazid, Hydrazinomethylharnstoff, Hydrazinonethylthioharnstoff, Carbamoylmethylhydrazin, Glykolsäurethioureid, Glycinthioureid, Äthylaminonethyl-, N-methyl-N'-nethylaminomethylharnstoff, Malonsätremonoamid, carboxymethyl-urea, carbamyl - acetic acid, thiocarbamyl-O-acetic acid, thiocarbamyl-S-acetic acid, amidosulfonic acid glycolic acid ester,

       Carboxymethylguanidine, guanylacetic acid, malonic acid monoureide, 2-hydroxypropionic acid amide, 1-hydroxypropionic acid amide, 2-hydroxyethylthiopropionanide, 2-hydroxyethylsulfonamide, N-methyl-2-hydroxyethylsulfonanide, 2-hydroxyethyl urea. 4,4'-diureidomethyl-diphenyloxide, ethylene-bis-methanesulfonamide, hexamethylene-bis-p-toluenesulfonamide, 4,4'-diureidomethyl-benzene, N, N'-bis- (2-hydroxyethyl) -urea, N, N , N'-tris (2-hydroxyethyl urea), N, N-bis (2-hydroxyethyl) urea, 2-hydroxyethylthiourea, N,

  N-bis- (2-hydroxyä thvl) -thiourea, 2-hydroxyethyl urethane. Ethylene glycol bis-carbamic acid ester, 2-hydroxy-ethylguanidine, 2-hydroxypropionic acid acid, β-alanine amide,?

  Alanine dermide, sarcosine amide, taurine amide, N-methyl taurine amide, 2-aminoethylurea, 2-aminoethylthiourea, 2-aminoethyl urethane, S- (2-hydroxyethyl) thiourethane, O- (2-hydroxyethyl) thiourethane, 2-hydroxyethyl sulfuric acid amide, guanylethanol, guanylethylamine, 2-aminoethylguanidine, 2-mercaptopropioneamide, 2-mercaptoethylsulfonamide, succinic acid monoamide, maleic acid monoamide, 2-carhoxyethylsulfonamide.

   2-carboxyethyl urea, 2-carboxyattyl urethane, 2- (uanylpropionic acid, 2-carboxyethylguanidine, succinic acid onoureide sulfuric acid reagent, 2-guanyl propionamide, 2-carbonanidoethylguanidine, succinic acid amidureide, succinic acid dithioamide, succinic acid amide hydrazide, hydrazinocarbonylethyl urea,

       Hydrazinocarbonylethyl urethane, amidostlfonylethyl urea, ethylenebisurea, carbamylethylurea, guanylethylurea, guanidinoethylurea, urcidopropionic acid, ethylene bis-urea, 2-hydrazino urea, 2-hydrazino urea, 2-hydrazino urea, 2-hydrazino urea, 2-hydrazino-urea, 2-hydrazino-urea, 2-hydrazino urea. Guanylethylhydrazine, 2-hydrazinoethylguanidine, 2-hydrazinopropionic acid, 3-hydroxybutyramide, 3-hydroxypropyl urea, N, N'-bis (3-hydroxypropyl)

  - urea, N, N-bis- (3-hydroxypropyl) -urea, N, N-bis- (3-hydroxypropyl) -thiourea, 3-hydroxypropyl urea, 3-hydroxypropylguanidine, leucine amide, isoleucinamide, 3-aminopropylsulfonamide, 3 Aminopropylurea, 3-aminopropyl thiourea, 3-aminopropyl urethane, guanylpropylamine, 3-aminopropyl guanidine;

       3-carboxy propyl urea, glutaric diamide, 3-carbonamidopropyl urea, 3-guanyf-butyr <tinide, 3-carbonamidopropylguanidine, trimethylene-bis-urea, trimethylene-bis-thiourea, 3-hydrazinobutyramide, 3-hydrazinopropylurea, 4-amino-bitter acid amide, 5-amino-valeric acid amide, 6-amino-caproic acid camide ,

          11-Amino-undecanoic acid amide, 1,4-tetramethylene-bis-urea, 1,6-hexamethylene-bis-urea, 2,2-dimethyl-1,3-trimethylene-bis-urea, malic acid diamide, aspartic acid diamide, citric acid diamide, the isomeric amino-phthalic acid diamides and hydroxy-phthalic acid diamides, citric acid diureide, amino-phthalic acid ditride, aspartic acid diureide, carbamic acid 2-hydroxyethyl ester, hydroxymethyldicyandiamide, N, N'-bis-hydroxyä thyldicyandiamide,

       6-methylaminocaproic acid amide, 6-aminocaproic acid amide, 6-aminocaproic acid methylamide, 6-methylaminocaproic acid methylamide, 6-aminocaproic acid methylamide, 6-methylaminocaproic acid methylamide, 6-aminocaproic acid, 6-aminocaproic acid, phthalic acid bis-amoethanolamide, maleic acid bis-amoethanolamide, maleic acid bis-amethanolamide bis-amide, terephthalic acid-bis-amide, hydroxyethoxypropionic acid amide, hydroxyhexyloxypropionic acid amide,

       6-aminocaproic acid, 11-aminoundecanoic acid, p-aminobenzamide, p-aminobenzureide, glutaric acid amide.



  The compounds Y-X-NHR or Y-R2- (X-NHR) u mentioned can be used in equivalence to the NCO groups present, but also in excess. An equivalent ratio of 1.0-2.5 and in particular 1.0-1.5 is preferred. However, it can also be desirable, in particular with regard to a branched and therefore later crosslinked molecular structure, to work below the equivalence and in particular in the equivalent ratio of 0.6-1. In this procedure, the NCO / OH ratio in the synthesis of the prepolymer can also be over 2 and up to 3.



  End groups of the formula -X-NHR also arise from the fact that prepolymers with terminal NCO groups are reacted with ammonia or primary amines, for example with methylamine, ethylamine, ethanolamine. For this purpose, the amine component is expediently initially introduced and the prepolymer is added or the amine is converted into the carbonate to reduce the reactivity. The conversion can be carried out in the presence of water.



  Urea, thiourea, alkylene-bis-ureas, aminocarboxamides and acidides are very particularly preferred. Imidazolidone and amino derivatives of triazine.



  In general, R preferably represents hydrogen, i. H. Formally, they are acyl derivatives of ammonia. Such end groups -X-NH2 ensure particularly high reactivity with formaldehyde and reactive methylol compounds and their ethers, which is of particular importance for dispersions that crosslink at room temperature or only slightly elevated. Of the substituted ureas, imidazolidone (ethylene urea) and its derivatives are particularly reactive and therefore preferred.



  Some of the compounds listed under the anionic modification components are also suitable for reaction with prepolymers bearing NCO groups and for the formation of polyurethanes which have end groups which are reactive toward formaldehyde. These are above all compounds which at the same time have a group which is reactive towards NCO, an amide or ureide group and a carboxyl or sulfonic acid group, optionally in salt form.



  Examples are: dioxymaleic acid monoamide, tartaric acid monoureide, oxaluric acid, citric acid mono and diamide, citric acid mono and diureide, tartaric acid amide, asparagine, glutamine, aspartic acid monoureide, glutamic acid monoureide, ureidosulfinic acid, acetylsulfonic acid-C-acetamide Acetylguanidine-C-sulfonic acid, propionyl urea-α-sulfonic acid, propionamide-α-sulfonic acid, butyramide-α-sulfonic acid, isobutyramide-α

  sulfonic acid, acetogtanamine sulfonic acid, N-methyl-aspartic acid, N-methyl-aspartic acid acid, N-hydroxyethyl aspartic acid acid, N-hydroxy-ethylaspartic acid acid, addition products of amino amides or aminoureids with α, γ, ss-unsaturated carboxylic acids Aminocarboxylic or sulfonic acids on?

  , γ, ß-unsaturated carboxamides or ureides, N-carbonamidomethylglycine, N-carbonamidomethyl-6-aminohexanoic acid, N-carbonamidomethyl-anthranilic acid, carboxymethylaminoacetylurea, addition products of sultones and ß-lactones such as ss -Propiolactone on ureas and carbon amides such as 3-ureidopropanesulfonic acid, 3-ureidohutanesulfonic acid, 2-ureidcopropionic acid.



  It is also possible to use adducts which have arisen from an aminomethylation or sulfomethylation reaction on ureas or carbonamides. It is clear that the addition of sultones, lactones, carboxylic acid anhydrides and also the aminomethylation and sulfomethylation can also be carried out on the polyurethane having acylated amino end groups before the dispersion.



  Corresponding (potential) cationic compounds can also be used analogously, eg. B. α-dimethyl-amino-ss-hydroxypropionamide.



  Of course you can hzw the end groups -X-NHR. -X-NH2 can also be introduced in another way, for example by using poly (ester) amides with (partially) terminal carbonamide groups or ureide groups in the production of the polyurethane and in this case using less than the equivalent amount of diisocyanate.



  Another possibility is to use polyesters with terminal carboxyl groups or low molecular weight polycarboxylic acids as structural components. After reaction with insufficient amounts of polyisocyanate, a polyurethane with terminal carboxyl groups is obtained which is reacted with ammonia and heated, with acid amide groups (proportionally) being formed in a known manner.



  Furthermore, polyurethanes with terminal tertiary amino groups can be quaternized with an alkylating agent which contains an acylated amino group -X-NHR. Polyurethanes with terminal sulfide groups can also be ternated with alkylating agents accordingly. The preparation of polyurethanes with terminal tertiary amino groups is described, for example, in Belgian patent 636,799. To produce such polyurethanes with tert. Amino end groups are preferably reacted with corresponding NCO prepolymers with, for example, dimethylaminoethanol, dimethylaminopropanol, N, N-dimethylhydrazine, N, N-dimethylethylenediamine, N, N-dimethylaminopropylamine, N, N-dimethylaminohexylamine.

    



  Suitable alkylating agents are, for example, chloroacetamide, bromoacetamide, N-methylchloroacetamide, # -bromopropionic acid amide, α-chloropropionic acid amide, α-bromopropionic acid amide, α-bromo-isobutyric acid amide, m-chloromethylbenzamide, p-chloromethylbenzamide, 4 -Chloromethyl-phthalic acid diamide, α-bromosuccinic acid diamide, 2-chloro-4,6-di-amino-s-triazine, 2-chloro-4-methoxy-6-amino-s-triazine,?

  - methylsulfonyl-oxy-succinic acid diamide, ethylsulfonyloxy-acetamide, chloroacetylurea.



  Likewise, polyurethanes with terminal reactive halogen atoms whose production is described, for example, in Belgian patent 636 799, can be quaternized with tertiary amino amides, e.g.

   B. with dimethylaminoacetamide, 2-diethylaminepropionamide, dimethylamino succinic acid diamide, p-diethylaminomethylbenzamide, m-dimethylaminobenzamide, 2-dimethylamino-propionic acid camide, 2-dibrrtylaminopropionic acid camide.



  According to a further possibility, polyurethanes with terminal -OH, -SH, -NHz groups, for example, can be converted into polyurethanes with terminal amide groups by addition of acrylamide or acrylonitrile and subsequent partial hydrolysis. By adding z. B. maleamic acid or maleinuric acid is introduced at the same time the electrolyte-forming group.



  The addition of, for example, hydroxyalkylamides, hydroxyalkylureas, mercaptoalkylamides, aminoalkylamides, aminoalkylthioureas onto terminal double bonds capable of addition, such as those obtained by incorporating unsaturated dicarboxylic acids or glycols in the polyurethane, can also be used as a method for introducing acylated amino end groups.



  The total amount of acylated amino groups -X-NH-R can be greater than that of the end groups alone, since such groups can also be introduced by bifunctional chain extenders or by alkylating agents or by neutralizing agents (acids or bases).



  However, the total amount should not exceed 400 milliequivalent-% and is preferably 20-120 milliequivalent-%. An end group is to be understood as a group which, according to the definition of -X-NH-R, is only linked to a longer residue on one side, while R should not contain more than 4 carbon atoms. -X-NH-R can therefore also be side branches of a main chain or end group of such a side branch. On average, a polyurethane molecule should have about 1.5-10 such end groups, but preferably 2-S.



  The end groups which are reactive towards formaldehyde are introduced into the polyurethane at temperatures between room temperature and approx. Temperatures between 80 and 160 are preferred. At higher reaction temperatures there is a risk of the polyurethane polyelectrolytes beginning to decompose, while at lower temperature the stirrability is impaired. In addition, the chosen reaction temperature depends on the reactivity of the compound which is added to the prepolymer and provides the end groups.



  The reaction of a prepolymer containing free NCO groups with, for example, 6-aminocaproamide takes place sufficiently quickly at 80 and below, while the reaction with urea requires temperatures above 120. In general, it is advisable to work above the melting point of the additional component if there is insufficient solubility.



  In addition, prepolymers which carry free NCO groups and have a content of 0.3-20%, preferably 0.8-10e NCO, can be reacted with compounds which carry at least one, but preferably at least two, free reactive methylol groups. Prepolymers with 1.5-6% r free NCO are very particularly preferred.



  These compounds bearing free methylol groups are, for example, the mono-, di- and oligomethylol compounds of the compounds YX-NHR and Y-R2 - (X-NHR) n defined in more detail above, and methylol compounds of aliphatic and araliphatic ketones and nitriles are also suitable , # -Ketone carboxylic acid esters, generally of compounds with CH-acidic hydrogen atoms and of phenols, di- and polycarboxamides, di- and oligourethanes. A restriction is that the compounds suitable for reaction with NCO prepolymers must still have at least one free methylol group after they have reacted with the isocyanate groups present.



  Suitable methylol compounds are e.g. B. dimethylol urea, tetramethylol urea, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, tetramethylol hydrazodicarbonamide, dimethyloldicyandiamide, pentamethylol-4-ureido-6-methyl-hexahydropyrimidone, tetramethylol-tetra-methyl-acetone, tetramethylamethyl-acetone, hexahydropyrimidone, hexahydropyrimidone, hexahydro-ethyl-acetone, hexahydropyrimidone, hexahydro-ethyl-ketone, hexahydropyrimidone, hexahydropyrimidone, dimethylamethylamethyl-acetone, hexahydropyrimidone, hexahydropyrimidone, hexahydropyrimidone, hexahydropyrimidone, hexahydropyrimidone, tetramethylol-acetone, tetramethylolmelamine, Tetramethylol hexanone, dimethylol thiourea.



  In addition, methylol compounds of the compounds already listed with end groups reactive toward formaldehyde are suitable.



  Furthermore, condensation products containing methylol groups from urea-formaldehyde, urea-acetaldehyde-formaldehyde, urea-furfural-formaldehyde, urea-crotonaldehyde-formaldehyde, melamine-formaldehyde are suitable. In general, the most varied of phenol-formaldehyde or amine-formaldehyde condensation products containing methylol groups can be used, as have been widely described and industrially produced as phenol or amine resins. Xylene-formaldehyde resins containing methylol groups can also be used.



  High molecular weight, low molecular weight polymers and copolymers based on acrylamide or methacrylamide and formaldehyde can also be used.



  In general, the methylol compounds of di- and oligourethanes, such as those generally formed from polyisocyanates and alcohols or from polyisocyanates and polyalcohols or from monoisocyanates and polyalcohols, can be used.



  Examples are methylol compounds of the adducts of: 1,6-hexane diisocyanate and methanol, ethanol, propanol, 2,4-tolylene diisocyanate and trimethylolpropane and methanol, triphenylmethane triisocyanate and methanol. Pentacrythritol and methyl isocyanate, trimethylol propane and methoxymethyl isocyanate.



  In general, the methylol group-containing substance which can be used is nonionic, electroneutral in character. It is then reacted with an NCO prepolymer, which itself (potentially) has electrolyte character, e.g. B. by virtue of built-in cationic or anionic salt groups or precursors thereof, such as basic amino groups, sulfide groups or carboxyl groups.



  However, one can also start from prepolymers which are free from ionic groups or their precursors and react these prepolymers with methylol compounds (potentially) containing ionic groups; in particular with those which carry basic amino, quaternary ammonium, carboxyl or sulfonic acid groups or their salts.



  Such products are, for example: methylol compounds of dioxymaleic acid monoamide, tartaric acid monoureide, citric acid mono and diamide, citric acid mono and diureide, tartaric acid amide, asparagine, glutamine, ureidosuccinic acid, succinic acid, acetic acid, acetyluronic acid, maleic acid, maleic acid -Hydroxyäthylasparagin, N-Hydroxyäthyl- aspartic acid acid, N-Carbonamidomethylglycine,

       Sodium sulfomethyldicykindiamide and aminoplast and pltenolplast precondensates containing methylol groups, which have electrolyte character due to the use of (potentially) ionic components. Such ionic components, which are generally used together with the usual compo th such as urea, melamine, cyanamide, dicyandiamide, phenol, cresol, aldehydes, ketones are, for.

   B. glycine, taurine, N, N-dimethylethylenediamine, chloroacetamide.



  The methylol compounds mentioned can be used in equivalence to the NCO groups present; H. one mole of methylol compound to one NCO equivalent. But they can also be used in excess.

    An equivalent ratio of 1.0-2.5 and in particular of is preferred <B> 1.0-1.5. Of course, methylol end groups can also be introduced in other ways, for example by reacting polyurethanes with terminal double bonds, epoxides, carboxyl or anhydride groups with the methylol compounds.



  In addition, polyurethanes with reactive halogen atoms which are capable of quaternizing can be reacted with methylol compounds containing tertiary amino groups. Conversely, polyurethanes with terminal tertiary amino groups, as described, for example, in Belgian patent 636 799, can be made to react with methylol compounds p bearing reactive halogen atoms with quaternization.



  Suitable compounds with reactive halogen atoms are, for example, the methylol compounds of the haloalkylamides listed above. Suitable compounds with tertiary amino groups are, for example, the methylol compounds of the aminoamides listed above.



  Of course, the polyurethane electrolytes can also have only a proportion of methylol groups in addition to acylated amino groups -X-NHR which are reactive towards formaldehyde. For example, an average of around one reactive methylol group per molecule is often sufficient for a later chain extension. If dispersion with the addition of formaldehyde is planned, the content can be even lower.



  The conversion of the starting components to the (potential) polyurethane electrolytes, in particular their last stage (reaction of the NCO prepolymer with compounds YX-NH-R or Y-R2-X-NHR or their methylol compounds) can also be reduced by adding Quantities of solvents such as dimethylformamide, diethylformamide, ethylene glycol, diethylene glycol and their ethers and esters are favored. The amount of solvent introduced in this way should, however, be a maximum of about 6% of the total ge polyurethane dispersion. However, their amount is preferably only 0.2-2%.

   The use of solvents with hydroxyl groups, which are later incorporated into the polyurethane under the action of the added formaldehyde, is particularly advantageous.



  In the quaternization reaction of a potential polyurethane electrolyte, which contains basic nitrogen atoms ent, with chloroacetamide z. B. by adding 1 to 3% Glykolmonomethylätheracetat avoided the sublimation of the amide to the cool parts of the reaction vessel.



  It should be emphasized, however, that the preparation of the dispersion can be carried out in the absence of organic solvents.



  The abovementioned absence of organic solvents is possible because polyurethanes free of NCO groups are dispersed by mixing with water. Only during or at any point in time after the dispersion does a heat treatment and, if necessary, lowering of the pH value lead to a further kettenauf building reaction which, depending on the request, leads to a thermoplastic or more or less crosslinked high molecular weight plastic. This chain-building reaction to the high polymer takes place in the aqueous two-phase system without any appreciable increase in viscosity and / or only after application to the textile material.



  When building potentially cationic polyurethanes with built-in tertiary amino groups, the use of compounds that catalyze the reaction with isocyanates can usually be dispensed with. When building sulfonium polyurethanes or polyurethanes with anionic groups, the use of a catalyst can be advantageous. In particular, tertiary amines and organometallic compounds such. B. tributylamine, diazabicyclooctane, pyridine, tin octoate, dibutyltin dilaurate, zinc octoate, cobalt naphthenate, iron acetylacetonate.



  Polyurethane polyelectrolytes with groups reactive towards formaldehyde, which are converted into polyurethane polyelectrolytes containing methylol groups with formaldehyde-containing solutions during or immediately before the dispersion, should have an average molecular weight of less than 25,000, preferably between 2,000 and 10,000. The range between 3000 and 8000 is very particularly preferred. Furthermore, they no longer contain any free NCO groups. The average molecular weight is difficult to determine exactly, but it can be estimated with sufficient accuracy. End group determination and osmometric measurements are useful.

    In many cases, the approximate average molecular weight results from the stoichiometry of the reactants in the construction of the polyurethane.



  If, for example, 2 moles of a dihydroxy compound with a molecular weight of 2000, 1 mole of a basic chain extender with a molecular weight of 119, 4.75 moles of diisocyanate (molecular weight 168) and 3.5 moles of urea (molecular weight 60) are converted into a polyurethane with 2 terminal biuret groups, so the molecular weight is calculated to
EMI0011.0021
    The molecular weight calculated in this way is in practically all cases below 10,100 and mostly below 8,000.



  Another important criterion for practical use is that at 120 the viscosity is lower than 1500 poise. The viscosity is preferably between 50 and 1000 poise. At higher viscosities, mixing in aqueous formaldehyde-containing solutions is difficult and requires special units, e.g. B. Internal mixers or screw machines or slow-running spiral stirrers. There is also the risk of premature molecule enlargement up to crosslinking before the dispersion is complete.

    If no suitable measuring device is available, it can be used as a guide that the reaction mass in a 3-1 glass beaker should be easily stirrable at 120 with a normal anchor stirrer at 50-200 rpm.



  Products with viscosities below 50 and especially below 10 poise are practically of little interest, since the properties of the end products are then less favorable.



  It should be emphasized that in the case of the polyurethane electrolytes normally used with end groups reactive toward formaldehyde, there is no fixed relationship between viscosity and molecular weight.



       Polyurethane electrolytes with terminal groups that are reactive towards formaldehyde expediently have a salt group content of 4 to 120 milliequivalents. This means that with an average molecular weight of 2500 at least every tenth molecule bears a salt group. These parts of the polyurethanes which carry salt groups then act as emulsifiers for the nonionic parts. Salt groups of different chemical constitution come into consideration.



  The most common groups are:
EMI0011.0037
   -C00 @ "'), -S @ 3 t) @ -Q-Sa3 i) -S02) @
EMI0012.0001
    The same applies to polyurethane electrolytes bearing methylol groups.



  It is not necessary for the polyurethanes to be already ready in salt form before the aqueous formaldehyde-containing solutions are added. Instead, these groups can potentially, i. H. in a form capable of forming salts. This is particularly advantageous then. if the salt formation takes place through a simple neutralization process in the presence of water.



  Groups capable of salt formation (potential electrolyte groups) are z. B.
EMI0012.0004
   -COOHr -S03H-S02H,
EMI0012.0005
      Since salt formation in anhydrous medium is usually associated with a sharp increase in viscosity, it can be advantageous, especially in the case of already highly viscous polyurethanes, to make the salt formation by acids or bases only during the addition of water.



  Of course, salt groups and groups capable of forming salt can also be present next to one another. To achieve good dispersion, it is also advantageous if the (potential) polyurethane electrolytes have hydrophobic chain segments of at least 60 chain links. Hydrophobic chain segments are to be understood as meaning those segments which contain neither salt groups nor groups capable of salt formation or which change into salt groups. They are preferably polyether, polyester, polythioether, polyacetal segments, which can also be interrupted by longer hydrocarbon radicals or urethane or urea groups.

   Polyurethanes in which these hydrophobic segments consist of 250-400 chain links and have only a few (z. B. 4-10) urethane or urea groups are particularly preferred.



  After a further possibility of preparing the dispersion, water together with formaldehyde and optionally with acids or bases to neutralize potential salt groups is stirred into the (potential) polyurethane electrolytes with terminal reactive acylated amino groups at elevated temperature.



  Appropriately enough water is first added to the polyurethane mass until it starts to cloud. This amount of water may contain the amounts of bases or acids necessary to neutralize acidic or basic groups. This first amount of water is approx.
EMI0012.0013
   until the
EMI0012.0014
    Weight of the polyurethane mass. The temperature is preferably between 5i and 100. Aqueous formaldehyde solution and finally water are then added within the same temperature range, the temperature being 150 during the addition of water. If desired, you can also work under pressure.



  You can also dissolve the necessary amount of formaldehyde in the total amount of water necessary for dispersion and gradually stir in this very dilute formaldehyde solution.



  It is also possible to first add a concentrated formaldehyde-containing solution or suspension to a polyurethane melt (for example a suspension of paraformaldehyde in a little water) and then to disperse the polyurethane composition formed by mixing in water. Paraformaldehyde or formaldehyde-releasing compounds and water can also be added in succession to the reaction mass, an aqueous solution containing formaldehyde being formed in situ.



  However, it is also possible to first predisperse polyurethane electrolytes with terminal reactive acylated amino groups with water and only then to add formaldehyde in free or dissolved or chemically bound form. This is particularly indicated if during the dispersion at pH values below 4 or above 9 work is being carried out and there is a risk of premature polycondensation during the dispersion. It is only essential that at least some of the added water contain formaldehyde.



  Instead of free formaldehyde, it is also possible to use aqueous solutions of formaldehyde-releasing substances, in particular of paraformaldehyde, trioxane, methylal, hexamethylene tetramine, oligo-methylol compounds such as di- and oligomethylolureas, -hexahydropyrimidinones, -urons. -nelamine and other triazine derivatives are used. Methylol ethers can also be used, provided they are used together with acidic catalysts and are therefore partly present as free methylol compounds or free formaldehyde.



  The following methylol compounds come into consideration, for example: dimethylolurea, hexamethylolmelamine, hexamethylolmelamine methyl ether, tetramethylol acetone, hexamethylol acetone, methylol compounds and methylol ethers of urea, ethylene urea, methylenediurea, biuret, carbonyl diurea, hydrofluoric acid, tetrorahydrofuran, 1,3-tetrahydrofuran, hexamethylenediurea -oxdiazinon- (4), dicyandiamide, acrylamide and metlacrylamide polymers, formogtuanamine, acetoguanamine, benzoguanamine.



  In addition to formaldehyde, higher aldehydes such as acetaldehyde, chloral, crotonaldehyde, aerolein, furfural, glyoxal, glutaric acid dialdehyde, ketones such as acetone, methyl ethyl ketone, cyclohexanone and their condensates with compounds forming aminoplast or mixed condensates with compounds forming formaldehyde and aminoplast can be used .



  In any case, the aqueous solutions of such formaldehyde derivatives should contain free formaldehyde in equilibrium under the reaction conditions in order to guarantee a reaction with the active groups -X-NHR. However, in this reaction it is not necessary for groups bearing exclusively methylol groups
EMI0012.0034
    arise.

   Rather, it is entirely within the meaning of the invention that by reaction of the reactive groups -X-NHR with oligomethylol compounds HO-CH_-Z- (CH2-OH) ", where Z is, for example, a radical that is di- to hexafunctional towards formaldehyde and n is a whole Number from 1-5 is new methylol compounds
EMI0012.0045
    arise. On the other hand, further condensation, in which the methylol groups largely react, must absolutely be avoided before the dispersion is formed.

   This is achieved by mixing the polyurethane composition with the formaldehyde-containing aqueous solutions, preferably at pH values between 9 and 4.1 and in particular between 7.5 and 5.5. Furthermore, the mixing process should generally not take longer than about two hours to form the dispersion.



  The amount of formaldehyde required in free or bound form depends on the amount of reactive groups -X-NHR present. In this context, reactive groups -X-NHR located within the chain must also be taken into account, for example if tertiary nitrogen has been quaternized with chloroacetamide. The equivalent ratio -X-NHR to formaldehyde (based on free formaldehyde) is between 1: 0.3 and 1: 4, in particular between 1: 2 and 1: 0.6. Lower amounts of formaldehyde are unfavorable because of the insufficient chain extension, even if there is sufficient dispersibility. Higher amounts of formaldehyde are generally useless, but cause the dispersion to have a strong odor and high levels of formaldehyde release during drying.



  To accelerate the reaction between the acylated amino end groups with the dissolved formaldehyde. Catalysts such as sodium carbonate, potassium carbonate, ammonia or urotropine can be added. However, their amount should be kept low, especially in the case of cationic products. so as not to impair the stability of the dispersions formed.



  The amount of water required depends above all on the concentration at which the initially formed paste of water in polytrethane changes into a polyurethane / water dispersion. This can be the case with a polyurethane concentration of approx. 68%, but also only with 20%. Accordingly, the total amount of water required is 0.5-4 times and preferably 0.8-3 times the amount of polyurethane.



  The rate at which the water is added must be such that the water is evenly absorbed by the polyurethane compound. The mixing process can generally be carried out without further ado in customary stirring apparatus or stirred kettles with slowly rotating anchor stirrers. All that is required is to ensure that the stirring power is adequate for the high viscosities that occur. Particularly suitable are agitators that also ensure good mixing of the reaction material in the vertical direction, such. B. spiral stirrer. High speed stirrers are generally less suitable.



  If the polyurethane composition already contains terminal methylol groups, for example as a result of the reaction of a prepolymer bearing NCO terminal groups with oligomethylol compounds, the presence of formaldehyde is eliminated during the dispersing process. The procedure then is to stir water into the (potential) polyurethane electrolytes with terminal reactive methylol groups at an elevated temperature, optionally together with the amounts of acids or bases necessary for neutralizing potential salt groups.



  The self-dispersion of the polyurethane that takes place in this process is due to the combined effect of the built-in ionic groups and the terminal methylol groups.



  In general, the water is initially absorbed with the formation of an almost clear solution. As the addition of water progresses, a milky-white paste is created, which contains the water partly dissolved and partly dispersed in the polyurethane (dispersion water in oil type). When more water is added, the paste changes into a polyurethane-in-water dispersion. In some cases this transition does not take place until the dispersion cools down.



  The temperature during the addition of water is between room temperature and 150 and preferably between 50 and 130. You can z. B. stir in about the first half of the amount of water at temperatures between 80 and 130 and add more water while cooling. According to a particularly preferred procedure, the entire amount of water is added at temperatures around 100 until the polyurethane-in-water dispersion is formed. At temperatures above 130, it is expedient to work under excess pressure.



  If the entire production of the polyurethane mass, or even just the dispersing process, is to be carried out continuously, screw machines are particularly suitable for this.



  If the dispersions formed are cooled immediately after preparation and used at room temperature, the properties of the coatings or impregnations obtained are unsatisfactory. Strength and water resistance are poor. Heat treatment is also necessary to achieve satisfactory properties. This can take place before and / or during and / or after applying the dispersions.



  The heat treatment prior to the removal of the water from the dispersion can be carried out so that the dispersion obtained for some time, e.g. B. 10 minutes to 48 hours, an elevated temperature above 50 is exposed. The length of time depends on the temperature and the pH. At pH values of 5-7 and tem peratures around 5t-80 C, more than 10 to 48 hours are generally necessary, while at 140 and a pH of 2 already <B> 10 Minutes can be sufficient.



  At temperatures above 120 it is preferred to work in a pressure vessel.



  The dispersion obtained is preferably subsequently stirred for 1-4 hours at an internal temperature of 90-110 immediately after preparation. The subsequent reaction that takes place can be increased by lowering the pH <B> 5-2 </B> (preferably 4-3), for example by adding tartaric acid or phosphoric acid, are greatly accelerated.



  This aftertreatment is particularly necessary when the process is carried out with drying of the applied dispersion <B> 25 ' </B> C provided and a sewing hciz..n is not possible.



  In addition to or instead of this measure, the dispersions applied can also be dried at elevated temperature. Because of the risk of bubble formation, temperatures below 100 are preferred for this. The dispersions are usually brought to pH values of 2-5 (preferably 4-3) beforehand, unless a post-heating process at a higher temperature is planned. This way of working is mainly used for continuous coatings and their applications, e.g. B. lamination, gluing and painting, into consideration, where the drying is carried out relatively quickly sig in the drying tunnel.



  In addition to or instead of these measures, the dried or dried products, eg. B. after Formge environment, coatings or impregnations, are also exposed to a reheating process. For this purpose, for example, heated to temperatures between 50-200 (preferably 70 to 150) and let be at this temperature for some time. The drying temperature of the environment can also be higher in the case of short-term drying, but the temperature of the polyurethane must not exceed 200. At this temperature, a dwell time of 30 seconds can be sufficient, while at 1t10 the heating time can be 1-4 hours.

   The aqueous dispersions to be used can have a liquid or paste-like consistency and are generally stable without the addition of emulsifiers, but corresponding cationic, anionic or neutral emulsifiers and protective colloids can be added, such as acidic or ammoniacal casein, soaps, inert soaps, alkylsulfonates , Polyvinyl alcohol, oxethylated phenols, oleyl alcohol polyglycol ethers, oxethylated phenols, oleyl alcohol polyglycol ethers, oxethylated polypropylene glycol or natural products such as gelatin, gum arabic, tragacanth, isinglass.

   Such additives are mainly used to reduce the relatively high surface tension of the polyurethane dispersions. They also influence the chemical stability of the dispersions and their coagulability.



  The dispersions can be blended with equally charged dispersions such. B. with polyvinyl acetate, polyethylene, polystyrene, polybutadiene, polyvinyl chloride and copolymer plastic dispersions.



  Finally, fillers, plasticizers, pig ments, carbon black and silica sols, aluminum, clay and asbestos dispersions can also be incorporated into the dispersions.



  In many cases it is more beneficial to use such fillers, plasticizers, pigments, stabilizers such. B. against the influence of light or hydrolyzing influences, crosslinking agents, optical brighteners, thixotropic agents. To incorporate means for improving the surface properties and the handle in substance in dissolved, pasted or dispersed form before the addition of water to the melt of the polyurethane or to the concentrated aqueous solution of the polyurethane polyelectrolyte present before the dispersion.



  The already mentioned acylating amines Y-X-NH-R or # -R2- (X-NH-R) n can be added as additional components to the dispersion. which act as crosslinkers for the existing methylol compounds are used. Such acylated amines can be added at any point during the build-up of the polyurethane composition or the dispersion or shortly before application. Polyisocyanates in free form, which have a molecular weight between 1 lt) and approx. 4000, can be added immediately before the dispersion at the earliest, but before added after the dispersion or the finished dispersion.



  The dispersions that can be produced are used according to the invention for coating or for covering and impregnating textile materials, in particular woven and non-woven textiles. Using the process, antistatic and wrinkle-free finishes, bonded fleeces, bonds, hydrophobic treatments and softening can be obtained.



  Solvent-free, bonded nonwovens can be obtained, whereby the fibers can be of natural (tree-filled, wool) or synthetic origin (rayon, polyamide, polyacrylonitrile, polyester).



  It is advantageous that the method according to the invention can be carried out on conventional machines according to application methods that have already been practiced technically. The dispersions to be used can be applied particularly easily as 30-70 percent pastes by pouring or knife coating. The conversion into paste form, if necessary using commercially available thickeners, which are expediently used in amounts of 1-10% e to set the desired viscosities, reduces the sedimentation speed depending on the concentration and causes the mass to flow smoothly and evenly. Highly concentrated pastes with a solids content of approx. 50 to 70% can be kept for days without phase separation.



  The dispersions, in particular suspensions or pastes, are applied to a textile material, e.g. B. woven or non-woven textile structures or fiber mats, felts or nonwovens, which by virtue of their suction effect cause a continuous solidification of the coating consisting of microgel particles. This is then followed by drying and, if necessary, pressing at a preferably elevated temperature, the caviar structure of the coating being solidified.



  The dispersion applied can be dried at room temperature or at an elevated temperature, although no melting should occur with the material flowing together.



  If drying is carried out at temperatures between 10 and 40 ° C., the material generally does not solidify. The layers obtained can usually be crumbled up by hand and in many cases can even be redispersed in water.



  Solidification normally takes place through the action of elevated temperature, preferably between 50 and 180, with sintering of the particles with mechanical interlocking or partial interfacial fusion and a chemical crosslinking reaction between the particle interfaces. The interlinking of the edge zones prevents further excessive sintering or complete melting, so that the entire material remains penetrated by the finest channels.



  Drying and solidification can be carried out simultaneously or one after the other. The hardening temperature of pre-dried layers is approx. 10-30 higher than that of moist layers. As the water content decreases, the solidification temperature must be increased in order to achieve comparable results. The time of the tempera ture effect and the layer thickness and possibly the application of pressure, z. B. by hot rollers when solidifying, are other important factors that influence the micro porosity, water vapor permeability and the physical properties of the coatings available.



  Coatings of 100-400 thickness can be sintered by temperature shock, a few seconds being sufficient for largely anhydrous to a few minutes for coatings that are still slightly moist. The temperature here can be considerably higher than the hardening stone permeation otherwise necessary for longer drying times.



  The finished coatings are milky opaque or mostly completely opaque, have a pleasant warm feel, good tensile strength and low abrasion and are insoluble in solvents, often even in hot dimethylformamide. The water vapor permeability is significantly increased compared to corresponding homogeneous materials and in most cases corresponds to natural leather. A clear morphological structure can be seen under the light microscope. The coatings can then be given a finish to increase the resistance of their surface.

   Aqueous dispersions or solutions are preferably used for this purpose.



  The process products can be used in many ways. So z. B. produce tarpaulins, raincoats, bags, belts, shoes, upholstery materials, car linings, etc.



  The preparation of usable dispersions and their use according to the invention are described in the following examples.
EMI0014.0032
  
    Approach: <SEP> example <SEP> 1
 <tb> 500 <SEP> g <SEP> (0.303 <SEP> mole) <SEP> phthalic acid-adipic acid-ethylene glycol-polyester <SEP> (1 <SEP>: <SEP> I <SEP> <B>: 2.3); </B> <SEP> molecular weight
 <tb> 1650 <SEP> (PEP)
EMI0015.0001
  
    50 <SEP> g <SEP> (0.420 <SEP> mole) <SEP> N-methyl diethanolamine <SEP> (MDA)
 <tb> 52 <SEP> g <SEP> (0.870 <SEP> mole) <SEP> urea <SEP> (HS)
 <tb> 205 <SEP> g <SEP> (1, <SEP> 158 <SEP> mole) <SEP> toluene diisocyanate, <SEP> isomer mix <SEP> 65:

    <SEP> 35 <SEP> (T <SEP> 65)
 <tb> 39 <SEP> g <SEP> (0.420 <SEP> mole) <SEP> chloroacetamide
 <tb> 258 <SEP> ml <SEP> (2.5 <SEP> mole) <SEP> 30 percent <SEP> watery <SEP> formaldehyde
 <tb> 30 <SEP> ml <SEP> glycol monomethyl ether acetate <SEP> (GMA)
 <tb> 1150 <SEP> ml <SEP> water Procedure: PEP, MDA and HS are introduced at 60 and T 65 is added within 1 '. The temperature rises to 111 with a sharp increase in viscosity. After heating to 120, the temperature rises spontaneously to 133 (urea reaction). The chloroacetamide is added and rinsed with GMA. It is held at 130 for 10 minutes, allowed to cool to 100 and 1000 ml of water are added dropwise to 45 ', a temperature of 100-110 being maintained. An opaque, thick sol is obtained which, after 20 minutes, gives a thin, liquid, pale yellow, 41.5 percent latex on cooling.

    



  The particles are predominantly spherical with a diameter between 50-120 m.



  Part of the dispersion is adjusted to pH 2-3 with tartaric acid.



  At intervals of several days, samples of the original dispersion (pH 5-6) and the acidified dispersion each containing 10 g of solid substance are dissolved in 25 ml of tetrahydrofuran and the viscosity is measured in seconds from a 2 ml pipette that is detached from the bottom.
EMI0015.0004
  
    to <SEP> 3 <SEP> days <SEP> 10 <SEP> days <SEP> 21 <SEP> days <SEP> 45 <SEP> days
 <tb> pH <SEP> 5-6 <SEP> 0.6 " <SEP> 0.8 " <SEP> 1.2 " <SEP> 1.2 " <SEP> 1.0 "
 <tb> pH <SEP> 2-3 <SEP> 0.6 " <SEP> 1.0 " <SEP> 2.5 " <SEP> 5.0 " <SEP> 5.0 "To produce a lamination resistant to trichlorethylene between a cotton fabric and a polyurethane foam film, the dispersion is applied to the cotton fabric to form an adhesive layer.



       Example 2
EMI0015.0006
  
    Approach:
 <tb> 500 <SEP> g <SEP> (0.303 <SEP> mole) <SEP> phthalic acid-adipic acid-ethylene glycol-polyester <SEP> (1 <SEP>: <SEP> 1 <SEP>: <SEP> 2,3); <SEP> molecular weight
 <tb> 1650 <SEP> (PEP)
 <tb> 50 <SEP> g <SEP> (0.420 <SEP> mole) <SEP> N-methyl diethanolamine <SEP> (MDA)
 <tb> 52 <SEP> g <SEP> (t, 870 <SEP> mole) <SEP> urea
 <tb> 194.5 <SEP> g <SEP> (1.158 <SEP> mole) <SEP> 1,6-hexane diisocyanate
 <tb> 19.6 <SEP> g <SEP> (0.21 <SEP> mole) <SEP> chloroacetamide
EMI0015.0007
  
    12.6 <SEP> g <SEP> (0.21 <SEP> mole) <SEP> acetic acid
 <tb> 129 <SEP> ml <SEP> (1.25 <SEP> mole) <SEP> 30 percent <SEP> watery <SEP> formaldehyde
 <tb> 30 <SEP> ml <SEP> glycol monomethyl ether acetate
 <tb> 1400 <SEP> ml <SEP> water implementation:

    as in Example 1, with acetic acid being added together with the first portion of water.



  An opaque 32 percent sol was obtained. pH = 5. Samples of the original dispersion and a dispersion adjusted to pH 2-3 with tartaric acid were dried for 24 hours at room temperature and 2 hours at 80 and then loaded with distilled water. See table for results.
EMI0015.0008
  
    to <SEP> 1 <SEP> hour <SEP> after <SEP> 24 <SEP> hours
 <tb> water pollution <SEP> water pollution
 <tb> pH <SEP> 5, <SEP> 24 <SEP> hours <SEP> room temperature <SEP> resolved <SEP> resolved
 <tb> pH <SEP> l <SEP> 2-3, <SEP> 24 <SEP> hours <SEP> room temperature <SEP> unchanged <SEP> clear, <SEP> swollen
 <tb> pH <SEP> 5, <SEP> 30 ' <SEP> 80 <SEP> white <SEP> started <SEP> strong <SEP> white <SEP> started
 <tb> pH <SEP> 2-3, <SEP> 30 ' <SEP> H0 <SEP> unchanged <SEP> clear,

    <SEP> something <SEP> swollen The dispersion applied to a fabric, dried at room temperature, gives a soft, clear coating with good water resistance. Reheating at 80 C greatly improves these properties.



  Example 3
EMI0015.0009
  
    Approach:
 <tb> 500 <SEP> g <SEP> (0.303 <SEP> mole) <SEP> Phthalic Acid-Adipic Acid-Ethylene Glycol Polycster <SEP> (1 <SEP>: <SEP> 1 <SEP>: 2.3); <SEP> molecular weight
 <tb> 1650 <SEP> (PEP)
 <tb> 15 <SEP> g <SEP> (0, <SEP> 126 <SEP> mole) <SEP> MDA
 <tb> 26 <SEP> g <SEP> (t), 428 <SEP> mole) <SEP> urea
 <tb> 1l8 <SEP> g <SEP> (0.643 <SEP> mole) <SEP> 1,6-hexane diisocyanate
 <tb> 7 <SEP> g <SEP> (0.075 <SEP> mole) <SEP> chloroacetamide
 <tb> 3 <SEP> g <SEP> (0.061 <SEP> mole) <SEP> acetic acid
 <tb> 129 <SEP> ml <SEP> (1.25 <SEP> mole) <SEP> 30 percent <SEP> watery <SEP> formaldehyde
 <tb> 30 <SEP> ml <SEP> glycol monomethyl ether acetate
 <tb> 830 <SEP> ml <SEP> water Procedure: as in Example 2. After the addition of water at 130, a coarse-grained, thin latex is obtained which becomes thicker and rheopex on cooling.

   Yield 1.7 kg, solids 40%, pH 5-6. The coatings obtained on fabrics from the dispersion acidified to pH 2-3 by drying at room temperature are clear, glossy and soft and have good water resistance. Reheating at 120 significantly improves the properties.



  Example 4
EMI0015.0010
  
    Approach:
 <tb> 500 <SEP> g <SEP> (0.37 <SEP> mole) <SEP> Phthalic acid-ethylene glycol polyester
 <tb> (molecular weight <SEP> 1350)
 <tb> 30 <SEP> g <SEP> (0.252 <SEP> mole) <SEP> MDA
 <tb> 60 <SEP> g <SEP> (1.00 <SEP> mole) <SEP> urea
 <tb> 188 <SEP> g <SEP> (1.122 <SEP> mole) <SEP> 1,6-hexane diisocyanate
 <tb> 21 <SEP> g <SEP> (0.224 <SEP> mole) <SEP> chloroacetamide
 <tb> 1.7 <SEP> g <SEP> (0.028 <SEP> mole) <SEP> acetic acid
 <tb> <B> 129 </B> <SEP> ml <SEP> (1.25 <SEP> mole) <SEP> 30 percent <SEP> watery <SEP> formaldehyde
 <tb> 680 <SEP> ml <SEP> glycol monomethyl ether acetate <SEP> (GMA) polyester, MDA and urea are introduced at 85 and the 1,6-hexodiisocyanate is quickly added. The reaction begins after 2 minutes.

   Temperature rise above 150 is avoided by cooling. Solid chloroacetamide is added to the very viscous mass at 130 and it is rinsed with GMA. The mixture is stirred at 130 for 30 minutes and a solution of acetic acid in 80 ml of water is added dropwise to the highly viscous clear melt in the course of 13 minutes, the melt remaining clear. The formaldehyde solution is then added dropwise at 90 in 20 minutes and the remaining water in 50 minutes at 130. A relatively coarsely dispersed, viscous latex is obtained, the viscosity of which decreases on cooling. It is 52%. pH 5-6.



  The acidified latex is spread on textile fabric; one obtains high-gloss, clear and colorless layers. After a heat treatment at 80 these are waterproof.



  Example s
EMI0016.0001
  
    500 <SEP> g <SEP> (t0.281 <SEP> mole) <SEP> Phthalic acid-ethylene glycol polyester
 <tb> (molecular weight <SEP> l350), <SEP> Desmophen
 <tb> 52 <SEP> g <SEP> (0.870 <SEP> mole) <SEP> skin fabric
 <tb> 190.5 <SEP> g <SEP> (1.136 <SEP> mole) <SEP> 1,6-hexane diisocyanate
 <tb> 53.5 <SEP> g <SEP> (0.278 <SEP> mole) <SEP> citric acid
 <tb> 29.2 <SEP> g <SEP> (0.278 <SEP> mole) <SEP> diet ltanolamine
 <tb> 64.5 <SEP> ml <SEP> (0.63 <SEP> mole) <SEP> 30 percent <SEP> watery <SEP> formaldehyde
 <tb> 080 <SEP> ml <SEP> water Desmophene and urea are mixed with diisocyanate at 75 and heated up. At 130 ', an exothermic reaction sets in and the temperature rises to 151. After the reaction has subsided and cooled to 120, citric acid is added.

   A strong reaction sets in immediately with yellow coloration and foaming, the temperature first falling to 90 ° and then rising again to 120. A solution of diethanolamine in 80 ml of H2O in 3 minutes, 64.5 ntl of aqueous formaldehyde in 4 minutes and 750 ml of water in 15 minutes are then added one after the other at 100. Then a further 250 ml of water were added in 23 minutes at 13 °. After cooling, a white, viscous, slightly rheopex latex resulted with good spreadability.



  The latex is spread on a textile carrier material and dried. After heat treatment at 100 to 120, the coating is resistant to water and organic solvents. Example 6 The procedure was as in Example 2, but using only 32.25 ml of 30% aqueous formaldehyde. The latex obtained is very finely divided, viscous and shows slight thixotropy. After acidification to pH = 3, soft, somewhat sticky and thermoplastic coatings are obtained on application to tissue and subsequent drying at 80.



  * Example 7 The procedure was as in Example 2, but using 4 1 g of thiourea instead of urea and 64.5 ml of 30% aqueous (formaldehyde. A thin-liquid, yellow-colored latex without Tyndall effect was obtained.



  The dispersion, adjusted to pH 2-3 with tartaric acid, is brushed onto fabric; on drying at 80 pale yellow, transparent, soft, somewhat elastic and slightly sticky coatings are obtained. Example 8 The procedure was as in Example 2, but using 40 g of methylurea instead of urea and 64.5 ml of 30% aqueous formaldehyde.



  A 38 percent opaque sol was obtained, which dries onto fabrics at elevated temperature to form clear, soft and elastic layers. Previously acidifying the latex and drying it at an elevated temperature improves the water resistance.



  Example 9 The procedure was as in Example 2, but using 48 g of methylthiourea instead of urea and 64.5 ml of 30% aqueous formaldehyde.



  A 41% opaque sol was obtained which, applied to textile material, dries at 100 to form soft thermoplastic layers.



  Example 10
EMI0016.0012
  
    Approach:
 <tb> 5t) 0 <SEP> g <SEP> Phthalic Acid-Adipic Acid-Ethylene Glycol Polycster, <SEP> molecular weight <SEP> 1650 <SEP> (PEP)
 <tb> 50 <SEP> g <SEP> N-methyl diethanolamine
 <tb> 52 <SEP> g <SEP> urea
 <tb> 194.5 <SEP> g <SEP> 1,6-hexane diisocyanate
 <tb> 25 <SEP> g <SEP> acetic acid
 <tb> 129 <SEP> ml <SEP> 30 percent <SEP> watery <SEP> formaldehyde
 <tb> 1500 <SEP> ml <SEP> water Procedure: as in Example 2, with the addition of monochloroacetamide and glycol monomethyl ether acetate not required.



  1000 g of the dispersion obtained are diluted with 1000 ml of water. The 20% suspension obtained is coarsely dispersed and sediments within 12 hours, but can be redispersed again at any time by simply shaking it. By pouring off the excess water, an approximately 60-70% concentrated polyurethane paste is obtained, which can be diluted again with water at any time.



  The paste-like dispersion, acidified to pH 2-3, is applied to a textile fabric and dried at 80, giving a matt, soft and elastic coating with good water resistance. Example 11 1 kg (0.6 mol) of an adipic acid-hexanediol-neopentyl glycol polyester are reacted with 201 g of 1,6-hexanediisocyanate at 130 for 1 hour and then at 80 with 107 g of dimethylaminoethanol. The reaction is strongly exothermic. It is held at 130 for a further 30 minutes and a pale, viscous polyurethane resin with an average molecular weight of 2200 with terminal tertiary amino groups is obtained.



  218 g of the above resin are reacted with 20.6 g of monochloroacetamide for 1 hour at 120 ° C., a polyurethane resin with quaternary ammonium groups and terminal carbonamide groups being formed.



  For this purpose, at 100 ', first 30 ml of water, then 80 ml of 30 percent aqueous formaldehyde and finally 300 ml of water are added. A 42 percent latex is obtained which, after acidifying to pH 3, is applied to a fabric and dries at 12-4 to form a soft, elastic coating. Example 12 To build up the polyurethane resin with terminal tertiary amino groups, the procedure is as in Example 13, but using 151 g of 1,6-hexane diisocyanate and 53 g of dimethylaminoethanol. The resin formed has an average molecular weight of 4,000.



       200.5 g of this resin are reacted with 10.3 g of monochloroacetamide at 120 for 1 hour. To this end, 10 ml of water, 40 ml of 30 percent aqueous formaldehyde and 530 ml of water are added to 100. A 28 percent latex is obtained which, after acidification on p13, is spread on fabric and dries at 12 (1u to form a soft, elastic coating.



  Example 13
EMI0016.0034
  
    Approach:
 <tb> 500 <SEP> g <SEP> (0.281 <SEP> mole) <SEP> PEf ' <SEP> (like <SEP> example <SEP> 1)
EMI0017.0001
  
    30th <SEP> g <SEP> (0.252 <SEP> mole) <SEP> MDA
 <tb> 32 <SEP> g <SEP> (0.534 <SEP> mole) <SEP> urea
 <tb> 134.5 <SEP> g <SEP> (0.800 <SEP> mole) <SEP> 1,6-hexamethylene diisocyanate
 <tb> 14 <SEP> g <SEP> (0.150 <SEP> mole) <SEP> chloroacetamide
 <tb> 6 <SEP> g <SEP> acetic acid
 <tb> 112 <SEP> g <SEP> tartaric acid
 <tb> 64.5 <SEP> ml <SEP> 30 percent <SEP> watery <SEP> formaldehyde
 <tb> 1050 <SEP> ml <SEP> water Procedure: as in Example 2. The above-mentioned amount of tartaric acid is added to the cold latex, which sets a pH of 2-3. For crosslinking, the acidified latex is heated to boiling for 50 minutes.

   A sample taken after this time is no longer soluble in tetrahydrofuran, but forms a gelatinous mass.



  After cooling, a 32 percent low viscosity, very finely divided latex is obtained, which is applied to textile material and dries at room temperature to form non-tacky, matt-gloss, tensile coatings.



  Example 14 500 g of PEP (cf. Example 13) are reacted with 71 g of 1,6-hexamethylene diisocyanate at 130 for 1 hour. At 80, 18 g of N-methyldiethanolamine and 5 minutes later a further 25.5 g of 1,6-hexamethylene diisocyanate and 17 g of urea are added. The mixture is stirred for 25 minutes at 130, 5 g of chloroacetamide in 10 ml of glycol monomethyl ether are added and the mixture is stirred for a further 15 minutes at 130.



  The following are now added in succession: 7 g of glacial acetic acid in 120 ml of water at 90 in 10 minutes, 80 ml of 30%. aqueous formaldehyde at 90 in 6 minutes, 250 ml of water at 130 in 15 minutes, 500 ml of water at 110 'in 25 minutes. The dispersion formed is adjusted to pH 4 with 20 ml of 30% tartaric acid, with thickening occurring, and then stirred for 1 hour at 110 until a 10 g sample with 50 ml of tetrahydrofuran forms a gelatinous mass. A relatively coarse-grained latex is obtained, which over time separates the serum on top and then forms a thick, easily spreadable paste. The paste can be easily diluted with water at any time.

   Using the process, this dispersion can be applied as a laminating adhesive layer, which is characterized by very good adhesion values even after storage in trichlorethylene. The wash resistance is good.



  Textile material is coated with the dispersion, which is a one-component system that is stable in storage, by drying the coating at room temperature after application by knife coating and condensing at 120 ° C. for 15 minutes.



  A soft, elastic and abrasion-resistant coating is obtained which, after 110 hours of Fade-O-MeteC exposure or 12 days of oxygen aging, shows no yellowing and no reduction in mechanical properties. After 12 days of aging at 70 C and 95% air humidity, the tensile strength is still 75 kp / cm2. The material is therefore resistant to hydrolysis. Example 15 500 g of a phthalic acid-ethylene glycol polyester with an OH number of 48, 25.4 g of N-methyldiethanolamine and 26 g of urea are mixed at 85 with 108 g of 1,6-hexamethylene diisocyanate. As a result of the polyaddition that starts immediately, the temperature rises to 122.

   The temperature is increased to 130 and 20 g of chloroacetamide in 20 ml of glycol monomethyl ether are added. After stirring at 100-120 for 30 minutes, 130 ml of 30N aqueous formaldehyde are added dropwise over the course of 20 minutes. 1050 ml of water are stirred into the viscous, almost clear mass in 50 minutes, a finely divided dispersion being formed. This is adjusted to pH 4 with 20 ml of 30% tartaric acid and stirred for a further 30 minutes at 120. One sample is clearly soluble in tetrahydrofuran.



  The 37% latex is used to coat textile material. It dries at room temperature in a short time to give completely tack-free, high-gloss coatings that are easy to grip and that become scratch-resistant, well-adhering and resistant to water and organic solvents when heated at 80.



  EXAMPLE 16 500 g (0.298 mol) of an adipic acid-hexanediol neopentylglycol polyester, 50 g of N-methyldiethanolamine and 53 g of urea are mixed with 193.5 g of 1,6-hexanediisocyanate at 70. It is heated until between 120 and 130 exothermic reaction sets in. The temperature should not exceed 150. Then 20 g of monochloroacetamide are added and, after 30 minutes, first 12.6 g of glacial acetic acid in 150 ml of water, then 50 ml of 30% aqueous formaldehyde solution. The mixture is stirred for 75 minutes at 100, after which the formaldehyde odor has practically disappeared. 1.2 l of water are stirred into the clear, viscous solution over the course of one hour. A very finely divided, opaque, thick liquid latex is created.

   This is adjusted to a pH of 4 with 20 ml of 30% tartaric acid solution, mixed with 30 ml of 30% aqueous formaldehyde solution and stirred at 100 for 2 hours. The dispersion is painted onto fabric. After drying, highly elastic, non-tacky and lightfast fabric coatings are obtained. Example 17 a) Prepolymer 2000 g (0.760 mol) of adipic acid diethylene glycol polyester and 254 g (1.51 mol) of 1,6-hexamethylene diisocyanate are heated to 130 for 2 hours. b) Dispersion 304 g of the above prepolymer are mixed at 80 with a solution of 31.6 g of maleic acid and 14 g of potassium hydroxide in 144 g of 20% sodium taurine solution in water (90).

   60 cm3 of 30% formaldehyde solution are added in 3 minutes and then 600 cm3 of water in 8 minutes and a thin, white latex is obtained, which is then adjusted to pH 4 with 30 cm3 of 30% tartaric acid solution. After application to tissue, soft, elastic, solvent-resistant coatings are obtained when the latex dries and heats off at 130. Example 18 250 g (0.162 mol) of phthalic acid-ethylene glycol polyester and 12.7 g (0.107 mol) of N-methyldiethanolamine are reacted for 30 minutes at 130 with 110 g (0.635 mol) of 1,6-hexamethylene diisocyanate (NCO / OH- Ratio 2.44).

   The mixture is then stirred with 33 g of urea at 130 for a further 30 minutes (NCO / urea ratio 1.4). Quaternization takes place with 10 g of chloroacetamide in 30 minutes at 130. It is allowed to cool to 110, 100 cm 'of 30% aqueous formaldehyde solution is added, the mixture is stirred for 30 minutes at 110 and then 500 cm' of water at 90 ° is added. The thin, relatively coarsely dispersed latex is acidified with 10 cm '30% strength tartaric acid solution, cooled and mixed with 30 g of hexamethylmelamine pentamethyl ether.



  When used, the latex dries at room temperature to form shiny fabric coatings that are heated to 120-130.

 

Claims (1)

PATENT CLAIM 1 A method for water- and solvent-resistant coating or impregnation of textile materials with polyurethane plastics, characterized in that an aqueous dispersion of a solid or liquid polyurethane polyelectrolyte precondensate which is free of isocyanate groups and has free reactive methylol groups is used, wherein the precondensate is subjected to a heat treatment at 25 to 200 C for the purpose of chain extension, which heat treatment takes place before the application of the dispersion to the textile material and / or after its application during and / or after removal of the water. SUBCLAIMS 1. Process according to claim 1, characterized in that a polyurethane polyelectrolyte precondensate is used which has methylol groups attached to optionally acylated amino groups. 2. The method according to claim I or sub-claim 1, characterized in that a polyurethane polyelectrolyte precondensate is used, which a) an average molecular weight of less than 25,000, preferably from 2000 to 10,000, b) hydrophobic nonionic chain segments of at least 60 chain links, c) a content of 4 to 120 milliequivalent%, preferably 8 to 80 meq%, of salt groups or groups which can be salted in the process, and d) has a viscosity of below 1500 P, preferably 100 to 100 P, at 120 C. , that the water content of the dispersion is 0.5 to 4 times the amount of precondensate and that the heat treatment is preferably carried out at 70 to 150.degree. 3. The method according to claim 1, characterized in that a polyurethane polyelectrolyte precondensate is used whose free, reactive methylol groups are part of an amine-formaldehyde resin or phenol-formaldehyde resin, which is built into the molecule of the precondensate. 4. The method according to claim, dependent claim 2 and dependent claim 3, characterized in that the dispersion is adjusted to a pH between 4.2 and 2 before, during or after the heat treatment. 5. Method according to dependent claim 2, characterized in that said polyurethane polyelectrolyte pre-condensate, which preferably has a viscosity of 50 to 1000 P at 120 C, the free, reactive methylol groups on terminal amino groups of the formula EMI0018.0009 contains bound, where X stands for -CO-, -CS-, -S02-, -NR-CO-, -NR-CS-, -0-C0-, -S-CO-, -O-CS-, -0 -S02-, -CNR-, -N R-CNR-, -CO-NR-CO-, -CS-N R-CS-, EMI0018.0010 stands and EMI0018.0011 or R denotes, and R denotes hydrogen, -CN-, -COR ', -SO2-R', where R 'denotes an alkyl, alkenyl, alkoxy or carboxylalkyl radical having 1 to 4 carbon atoms, or an alkyl radical or Alkenyl radical with 1 to 4 carbon atoms means which is optionally substituted by -OH, -OCH3, -OC2H5, -CC13, -COOH or -S03H or can be part of a heterocyclic 5- or 6-ring with 1 to 3 heteroatoms, but is given before hydrogen. 6. The method according to dependent claim 5, characterized in that the amino group -X-N-R is derived from an unsubstituted group -CO-NH2 or from an unsubstituted urea or biuret group. 7th Method according to claim 1, characterized in that the polyurethane polyelectrolyte precondensate contains at least one of the following ionic groups: EMI0018.0018 -C00 (-), S03 -0-S03 (-), S02 (-) and EMI0018.0019 where R 1 is alkyl, cycloalkyl, aralkyl or aryl. B. The method according to claim I, characterized in that the dispersion used contains 0.5 to 20% by weight of emulsified polyisocyanates with a molecular weight of <B> 110 </B> to 4000. PATENT CLAIM II Textile material coated or impregnated by the method according to claim 1.