DE3507467A1 - Coating pastes containing PU plastics, and process for the production of water vapour-permeable polyurethane coatings - Google Patents

Abstract

The coating pastes are multiphase, stable mixtures of A) 5-50 % by weight of polyurethanes and/or polyurethane-ureas which are hydrophobic per se and contain 1-30 % by weight of incorporated formative components from the group consisting of silicone resins, polyethers or polyesters containing aromatic molecular segments, and/or perfluorocarbon resins, B) 0-30 % by weight of polyurethanes and/or polyurethane-ureas which are hydrophobic per se and are built up without the specific formative components mentioned under A), C) 4.5-50 % by weight of organic solvents for A) and B), D) 0-40 % by weight of organic non-solvents for A) and B), E) 0.5-10 % by weight of polymers which are free from urethane and urea groups and carry carboxyl groups, all or some of which have been neutralised by means of bases, F) 10-70 % by weight of water, and G) 0-5 % by weight of crosslinking agents, hydrophobicising agents, discoloration and degradation stabilisers and/or further coating assistants. y

Description

Coating pastes and processes containing PU plastics

for the production of water vapor permeable polyurethane coatings The invention relates to coating pastes containing PU plastics, as well as a new one Process for the production of water vapor permeable coatings on textile or Leather substrates in direct or transfer processes based on the principle of evaporation coagulation using these coating pastes containing polyurethane plastics.

The spreadable pastes are multiphase, stable mixtures of A) 5 - 50 Wt .-, c per se hydrophobic polyurethanes and / or polyurethane ureas, the 1 - 30 wt. -, c structural components from the group of silicone resins, the aromatic Polyether or polyester containing molecular segments and / or perfluorocarbon resins, included built-in, B) 0 - 30 wt. T per se hydrophobic polyurethane (ureas), which are built up without the special structural components mentioned under A), C) 4.5 - 50 6ev. -, c of organic solvents for A) and B), D) o - 40 6ev. -, c of organic non-solvents for A) and B), E) 0.5-10% by weight, c of polymers, which are free of urethane and urea groups and with bases in whole or in part Carrying neutralized carboxyl groups, F) 10 - 70 wt. t of water and G) O - 5 6ev. -, c of crosslinking agents, water repellants, stabilizers against discoloration and degradation and / or other coating aids.

Textile or leather coatings that have high permeability for Have water vapor and at the same time have a high level of water resistance especially in the clothing and footwear sector, of increasing interest. The advantage Such coated materials is that the clothing made from them on the one hand optimally protects, on the other hand the body moisture in the form of Allows water vapor to escape. These properties have both in health and hygienic as well as in terms of comfort Status.

An important process, microporous and therefore water vapor permeable To produce coatings is that of the so-called bath coagulation, as it is e.g. in DE-AS 1 270 276 and DE-AS 1 769 277 is described.

This involves using a substrate with an organic solvent dissolved polyurethane or polyurethane urea coated and the coated product in a bath of a non-solvent miscible with the solvent (e.g. Wassar). The polyurethane is coagulated by extraction of the solvent by the nonsolvent.

The disadvantages of this method are that it is required Complete removal of the solvent requires very large amounts of non-solvent and that the process takes a long time. Also are to carry out this process as well as for the work-up of the resulting solvent / nonsolvent mixtures special, relatively complex equipment is required.

There has therefore been no lack of attempts to create coatings that are permeable to water vapor like a simple direct or transfer coating on conventional textile coating machines to manufacture. Most of these attempts are based on what is known as evaporation coagulation. This process is carried out in principle so that one in a volatile Solvent-dissolved polymers contain some amount of a less volatile nonsolvent is added and the resulting solution, dispersion or suspension on a Substrate is painted. The coating is through gentle Heating, dried, the volatile solvent initially preferably evaporating. The consequence is that the polymer coagulates in the layer and after final drying has a microporous structure.

This procedure is described, for example, in DE-PS 1 694 059; included Polyurethanes are used that are in volatile organic solvents, such as E.g. tetrahydrofuran or methyl ethyl ketone are colloidally dissolved and with organic Non-solvents with a higher evaporation rate, such as petroleum ether, are mixed. A similar procedure is described in Swiss patent specification 481 971, with the addition that there among the nonsolvents to be added to the polymer solutions is also called water. Another example of this type is the procedure according to DE-PS 2 004 276. Here, hydrophilic polyurethanes are based on aromatic Diisocyanates used. the certain proportions of polyoxyethylene compounds as Build-up components included. Solutions of these polyurethanes in certain organic Solvents such as methyl ethyl ketone are used with water as a nonsolvent mixed and applied to a substrate, whereupon the coating by selective Evaporation is coagulated and then dried.

Those mentioned work on the principle of evaporation coagulation However, procedures still have serious shortcomings. A major disadvantage consists in the selective evaporation of the volatile solvent components needed a lot of time and one extremely precise temperature control requirement. The handling of the corresponding products on the coating machines is therefore complicated and, above all, only possible at slow driving speeds. Another serious disadvantage, which in particular the aforementioned method according to DE-PS 2 004 276 relates to the difficult processability of those described there Polyurethane solutions or suspensions justified. Although the solids content is low is, these products are even before the only at the time of application taking place water addition, highly viscous. They are called "muddy suspensions" described, have a strong tendency to premature drying with the formation of gel particles and specks and are therefore difficult to handle by the coater. Furthermore the coatings according to the latter patent have the disadvantage of inadequate Lightfastness.

The object of the present invention was therefore to provide a method for To provide the production of water vapor permeable coatings, this is carried out on conventional coating machines in the direct or transfer process and which does not have the disadvantages detailed above.

This task could be detailed by providing the below described, multiphase, stable coating pastes according to the invention and their Use in the coating process according to the direct or transfer process the principle of evaporation coagulation.

The invention is based on the surprising observation that from per se hydrophobic polyurethanes or polyurethane ureas, the specific below more precisely defined silicone, polyether, polyester or perfluorocarbon resin sigments incorporated and which are dissolved in organic solvents, by addition of certain non-polyurethane resins defined in more detail below with side or terminal carboxylate groups and, from certain amounts of water, multiphase, stable Streifhpasten are available that can be used in a particularly simple and quick manner Process into microporous coatings on conventional coating machines permit. The base polymers according to the invention are preferably Polyurethane ureas based on aliphatic polyisocyanates, which is advantageous The result is lightfast, water-vapor-permeable coatings.

The inventive method has the advantage that the polyurethane solutions are of low viscosity before the addition of water and, in this respect, from the coater who produces the ready-to-use spreading pastes shortly before use, easily and safely are to be handled. In addition, they are distinguished by the process according to the invention Spreading pastes produced by the addition of resin containing carboxylate groups and water characterized by particularly good storage stability and processing reliability.

The present invention is therefore a method for Production of water vapor permeable coatings on textile or leather substrates im direct or Transfer process based on the principle of evaporation coagulation using polyurethane plastics containing, optionally pigmented Spreadable pastes, characterized in that the spreadable pastes are multiphase mixtures from A) at least 5% by weight, preferably 5-50% by weight, of inherently hydrophobic polyurethanes undior polyurethane ureas, which contain 1 to 30 wt., c, preferably 1 to 20 wt. in particular 1.5-15% by weight, c special structural components from the group of silicone resins, the polyether containing aromatic molecular segments, the aromatic molecular segments containing polyester andtor the perfluorocarbon resins, incorporated, B) O - 30 6 wt .-, c per se hydrophobic polyurethanes and / or polyurethane ureas, which are manufactured without the special structural components mentioned under A), C) 4.5 - 50 wt., C organic solvents for A) and B), D) O - 40 wt., C organic Nonsolvents for A) and B), E) 0.5-10% by weight of polymers, which are free of urethane and urea groups and are laterally and / or terminally with Bases carry completely or partially neutralized carboxyl groups, F) 10 - 70% by weight Water and G) O - 5 Gev .-, c crosslinking agents, water repellants, stabilizers against discoloration and degradation, and / or other coating aids, used will. (The sum of the percentages A) to G) should add up to 100 each.) The spreadable pastes can also contain any customary amounts of dyes and pigments or powders for coloring, and optionally fillers.

The above-mentioned spreading pastes are another subject matter of the invention in the form of multiphase, stable mixtures of A) - G), as described above.

Those used to carry out the method according to the invention Spreadable pastes are preferably produced in such a way that solutions of the polyurethanes or polyurethane ureas A) and optionally B) in the organic solvents C), optionally with the addition of the organic nonsolvents D) and the coating auxiliaries G), which is completely or partially neutralized with aqueous solutions or dispersions Carboxyl groups bearing polymers E) are mixed and then if necessary, the remaining proportion of the water F) is also mixed in.

Components A) and B) are particularly preferably around polyurethane ureas based on aliphatic polyisocyanates.

The polyurethanes or polyurethane ureas A) are known per se Way obtainable polyadducts from polyisocyanates and compounds with active hydrogen atoms. An essential characteristic of these polymers is that they are hydrophobic, i.e. no stable dispersions or Solutions with water result, and that they contain certain structural components from the group the silicone resins, the polyether containing aromatic molecular segments, the aromatic Molecular segment-containing polyester and / or the perfluorocarbon resins incorporated contain.

Starting materials for the production of the polyurethanes or polyurethane ureas A) are 1.) any organic polyisocyanates, preferably diisocyanates of the formula Q (NCO) 2, where Q is in particular an aliphatic hydrocarbon radical with 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical with 6 to 15 Carbon atoms, an aromatic hydrocarbon radical containing 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms means.

A detailed list of suitable diisocyanates can e.g. DE-OS 3 134 112, DE-OS 2 854 384 and DE-OS 2 920 501 can be found.

Examples of such diisocyanates to be used with preference are tetramethylene diisocyanate, Hexamethylene diisocyanant, 1-methyl-1,5-diisocyanatopentane, 2-methylpentane-diisocyanate-2,5, 2-ethyl-butane-1,4-diisocyanate, dodecamethylene-diisocyanate, 1,3- and 1,4-diisocyanatocyclohexane, 1-methyl-2,4- and -2,6-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (Isophorone diisocyanate), 4,4'-diisocyanatodicyclohexylmethane, 4,4'-diisocyanatodicyclohexylpropane- (2.2), Mono-, bis-, tris- or tetraalkyl-dicyclohexylmethane-4,4'-diisocyanate, lysine-alkyl ester diisocyanate, ate, Oligomers or homopolymers of m- or plsopropenyl - «,« - dibenzyl diisocyanates according to EP-A 130 313, 1-alkyl-2-isocyanatomethyl-isocyanato-cyclohexane, 1-alkyl-4-isocyanatomethyl-isocyanato-cyclohexane according to EP-A 128 382, 1,4-diisocyanatobenzene, 2,4- or 2,6-diisocyanatotoluene, or Mixtures of these isomers, 4,4'-and / or 2,4'- and / or 2,2'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodiphenylpropane- (2,2), p-xylylene diisocyanate and ",", "',"' - tetramethyl-m- or -p-xylylene diisocyanate and mixtures consisting of these compounds.

The (cyclo) aliphatic diisocyanates mentioned are particularly preferred used.

It is of course also possible in the process according to the invention those in polyurethane chemistry per se known higher functional Polyisocyanates or modified ones known per se, for example carbodiimide groups, Allophanate groups, isocyanurate groups, urethane groups and / or biuret groups Use polyisocyanates (also).

2.) Water-insoluble polyhydroxyl compounds in polyurethane chemistry known species with molecular weights above 400, for example 400 - 10,000, preferably from 500-5000 and melting points below 60C, preferably below 45vC. The corresponding dihydroxy compounds are preferably used. The co-use of compounds having a functionality of three or more in the sense of the isocyanate polyaddition reaction in small proportions to achieve a certain degree of branching is also possible as the already mentioned, possible use of tri- or higher-functional ones Polyisocyanates for the same purpose. Furthermore, it is preferred that the corresponding Polyhydroxyl compounds mainly made from aliphatic structural components are.

Hydroxyl compounds to be used with preference are those in polyurethane chemistry known hydroxypolyesters, hydroxypolyethers, hydroxypolythiostherr hydroxypolycarbonates and / or hydroxy polyester amides. The hydroxyl groups in question Polyesters are, for example, reaction products of polyvalent, preferably divalent and optionally additionally trihydric alcohols with polyhydric, preferably dibasic carboxylic acids.

Are trihydric or higher alcohols for the production of the polyester used, the (con) use of monovalent carboxylic acids is also possible. Vice versa monohydric alcohols can be (co-) used when using higher-value carboxylic acids.

Instead of the free polycarboxylic acids, the corresponding Polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures of these can be used to produce the polyesters. The polycarboxylic acids are preferably of an aliphatic and / or cycloaliphatic nature and can optionally e.g., by halogen atoms, substituted and / or unsaturated. As examples of this may be mentioned: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, Fumaric acid, dimeric and trimeric fatty acids.

Monobasic carboxylic acids which may or may not be used are preferred saturated or unsaturated fatty acids, such as 2-ethylhexanoic acid, palmitic acid, Stearic acid) oleic acid, ricinoleic acid, linoleic acid, ricinic acid, linolenic acid as well technical fatty acid mixtures, as e.g. from natural raw materials (e.g.

Coconut fat, linseed oil, soybean oil, castor oil).

The polyhydric alcohols include, for example, ethylene glycol, propanediol (1,2) and - (1,3), butanediol- <1,4), - (2,4) andl or - (2,3), hexanediol- (1,6), octanediol- (1,8>, Neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, Glycerine, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), trimethylolethane, Pentaerythritol, quinitol, mannitol and sorbitol, methyl glycoside, also diethylene glycol, Dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in Question. The polyesters can have a proportion of terminal carboxyl groups. Even Polyesters from lactones, e.g. e-caprolactone or hydroxycarboxylic acids, e.g. $ -hydroxycaproic acid, can be used.

Also the, preferably two, hydroxyl groups that come into consideration according to the invention containing polyethers are of the type known per se and are e.g. Polymerization of tetrahydrofuran or epoxides such as ethylene oxide, propylene oxide, Butylene oxide, styrene oxide or epichlorohydrin with itself, e.g. in the presence of BF3 or through the addition of these epoxides, yellow also in a mixture or one after the other, of starting components with reactive hydrogen atoms such as alcohols and amines, e.g. water, ethylene glycol or propylene glycol- (1.2t.

To the essential characteristic of the hydrophobicity of the invention Polyurethane (urea) may be used as structural components Polyethers only contain a maximum of as many ethylene oxide units as the resulting Polyurethane <-ureas) less than 2 6ew. -, c on oxyethylene segments -CH2-CH2-0- included. Ethylene oxide-free polyethers are preferably used for the production of the polyurethane (ureas) according to the invention are used.

Polyethers modified by vinyl polymers, such as those used e.g. arise through polymerization of styrene, acrylonitrile in the presence of polyethers (US-PS 3,383,351, 3,304,273, 3,523,093, 3,110,695, DE-PS 1,152,536) are suitable. The higher-functionality polyethers, which may also be used proportionally, are formed in an analogous manner by known alkoxylation of higher functional starter molecules e.g. ammonia, ethanolamine, ethylenediamine, trimethylolpropane, glycerine or sucrose.

Among the polythioethers are in particular the condensation products of thiodiglycol with itself and! or with other glycols, dicarboxylic acids, Formaldehyde, aminocarboxylic acids or amino alcohols are listed.

Polycarbonates containing hydroxyl groups are those of the known type, e.g.

by reacting diols such as propanediol (1,3), butanediol (1,4) and / or Hexanediol- (1,6), made with diaryl carbonates, e.g. diphenyl carbonate or phosgene can be.

The polyester amides and polyamides include, for example, those made of polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent ones saturated and unsaturated amino alcohols, diamines, poly- amines and their mixtures, predominantly linear condensates. Also urethane or polyhydroxyl compounds containing urea groups are usable.

Representatives of the named to be used in the process according to the invention Polyisocyanate and hydroxyl compounds are, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology ", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume 1, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, Pages 5 - 6 and 198 - 199, as well as in the Plastics Handbook, Volume VII, Vieveg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

3,) According to the invention, in the production of the hydrophobic polyurethane (urea) e compounds which are at least difunctional in the sense of the isocyanate addition reaction from the group of the silicone resins (3a) containing aromatic molecule segments Polyether (3b), the polyester (3c) containing aromatic molecular segments and! or to use the perfluorocarbon resins (3d).

Specifically, these are 3a) containing polysiloxane segments Compounds with at least two terminal and / or pendent, opposite isocyanates reactive groups, with molecular weights of 194-10,000, preferably from 300 to 3000, Preference is given to difunctional polysiloxanes with organofunctional ones End groups used. These connections have structural units of the formula -O-Si- (R) 2-, where R is a C1-C4-alkyl or a phenyl radical, but preferably represents a methyl radical.

Organofunctional, linear polysiloxanes suitable as starting material according to the invention are for example in DE-AS 1 114 632, 1 190 176, 1 248 287, 2 543 638 or in DE-OS 2 356 692, 2 445 648, 2 363 452> 2 427 273 or 2,558,523. The organofunctional end groups are preferably aliphatic, optionally heteroatoms such as, in particular, oxygen-containing hydrocarbon radicals which have a hydroxyl, carboxyl, mercapto or primary or secondary amino group or carboxylic acid hydrazide groups. The preferred carbofunctional groups include primary and secondary hydroxyl groups, as well as secondary amino groups. Those starting compounds which have terminal primary hydroxyl groups are particularly preferred. The organofunctional groups can be present in the starting materials, for example, in the form of the following carbofunctional radicals: -CH2SH, -CH2-S-CH2-CH2-SH, -CH2-CH2-COOHJ -CH2-NH21 - (CH2) 4NH2, -CH2-NH-C4Hg or -CH2-NH-C6H11.

The organofunctional polysiloxanes have at least 1, preferably 3 to 30 structural units of the formula -O-Si (R) 2- (R is preferably methyl) a molecular weight of 194 to 20,000, particularly preferably between 300 and 3Q00 on.

Particularly preferred starting compounds according to the invention are hydroxymethyl-poly-dimethylsiloxanes of the general formula n = 3 to 30, as they are produced in a manner known per se, for example by the process of DE-AS 1,236,505.

3b) According to the invention, di- or higher-functional, preferably difunctional, hydroxy-functional polyethers, which are less than 10% by weight of oxyethylene segments -CH2-CH2-, are also used in component A by oxyalkylating aromatic compounds with at least two phenolic hydroxyl groups. 0 and have molecular weights from 226 to 3000, preferably from 300 to 2000, are used. Compounds with at least two phenolic hydroxyl groups for preparing the aromatic polyethers suitable according to the invention are, for example, hydroquinone, the isomeric naphthalenediols, but preferably diols of the general formula to use.

In the last-mentioned formula, X stands for one of the divalent radicals -S-, -O-, -SO2-, -CO- or -C (R1R2) - where R1 and R2 are identical or different and represent hydrogen or C1-C4-alkyl radicals, or where R1 and R2 form one close cycloaliphatic ring with 5 or 6 carbon atoms. Particularly preferred are those diols in which X is -C (R) 2-, very particularly preferably those in which X is -C (CH3) 2-.

The aromatic hydroxypolyethers suitable according to the invention are in a manner known per se by polyaddition of cyclic ethers to the abovementioned aromatic polyols. Cyclic ethers include, for example, ethylene oxide, propylene oxide, Butylene oxide, styrene oxide or mixtures of these compounds are possible. In the event of the (co-) use of ethylene oxide may only be such proportions of these compounds are used that according to the above condition, the resulting aromatic Polyethers contain less than 10% by weight of oxyethylene segments -CH2-CH2-0-. Preferably only propylene oxide is used.

The aromatic hydroxyl polyethers are adducts of bisphenol A and Propylene oxide is very particularly preferred.

According to the invention, in the hydrophobic polyurethanes A can also be aromatic Polyesters containing molecular segments, e.g.

3c) Polyesters of isomeric phthalic acids with at least two terminal and / or pendant hydroxyl groups and molecular weights of 250 to 5000, preferably from 250 to 2000 can be used. Preference is given to difunctional polyesters of these Kind of used. These are condensation products known per se from polyhydric, preferably dihydric alcohols with phthalic acid, isophthalic acid and / or terephthalic acid, these aromatic acids optionally also, e.g. may be substituted by halogen atoms.

Instead of the free dicarboxylic acids, it goes without saying that the corresponding carboxylic acid esters of lower alcohols or (in the case of phthalic acid) also their anhydride for the preparation of the aromatic compounds suitable according to the invention Polyester are used.

Furthermore, according to the invention, in A also 3d) perfluoroalkyl groups can be used containing compounds with at least two terminal and / or pendent, opposite Isocyanate-reactive groups and molecular weights of 250-5000, preferably can be used from 300 to 2000. Preference is given to using diols of the type mentioned, the at least three perfluorinated carbon atoms in the form of in the main chain of the diol incorporated and / or pendent to this arranged perfluoroalkyl groups contain, with "perfluoroalkyl groups" saturated, perfluorinated, aliphatic Radicals are to be understood, which have a linear, branched or also may have a cyclic structure. Diols of the above are particularly preferred Type used with pendant perfluoroalkyl groups, such as those in DE-OS 3,319,368.

Examples of such particularly suitable structural components are the N-sulfonylperfluoroalkyl-aminoalkanol derivatives of the general formula: CnF2n + 1-so2-N (-X-oH) 2 wherein X is a linear or branched, saturated alkylene radical with 2 to 4 Carbon atoms and n for an integer greater than 2, preferably 5 to 12 stands.

4.) Chain extenders from the group of polyhydroxyl and / or the polyamino compounds and / or the hydroxyamino compounds with molecular weights up to 399.

In detail, these are: 4a) Low molecular weight, monomeric and / or oligomeric polyhydroxyl compounds. The monomeric polyols preferably have Molecular weights from 62-399 and include compounds such as ethanediol, 1,2-propanediol and -1,3, butanediol-1,4 -2,3 and -1,3, neopentyl glycol, hexanediol-1,6, 1,4,3,6-dianhydrohexite, Trimethylol propane, glycerine and pentaerythritol. Examples of oligomers Chain extender are on average difunctional condensation products from the aforementioned tri- or tetrafunctional alcohols and monofunctional carboxylic acids with medium Molecular weights of 200-399. The carboxylic acids mentioned above are used for this purpose mentioned as possible structural components of the higher molecular weight hydroxyl polyesters saturated andtoder unsaturated fatty acids into consideration.

4b) Polyamines and / or hydrazine and / or hydrazine derivatives of molecular weight 32 and 60 to 399, preferably 32 and 60 to 300. The polyamines are they are preferably aliphatic or cycloaliphatic diamines, although optionally also proportionally tri- or higher-functional polyamines to achieve a certain level Degree of branching can also be used. Examples of suitable aliphatic Polyamines are ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, Propylenediamine-1,2, the mixture of isomers of 2,2,4- and 2,4,4-trimethylhexamethylenediamine and bis (2-aminoethyl) amine <diethylenetriamine).

Examples of suitable cycloaliphatic polyamines which can be used as individual stereoisomers or as any mixtures of stereoisomers are: (Isophoronediamine) *) instead of the methyl groups, there can also be C2-C4 straight-chain or branched alkyl groups, Araliphatic polyamines, such as, for example, m- and p-xylylenediamine and m- or p- «,«, «', a'-tetramethyl-xylylenediamine, can also be used as chain extenders for the polyurethane ureas according to the invention.

Examples of suitable hydrazine chain extenders are: Hydrazine, which is preferably to be used in the form of its hydrate, and hydrazine derivatives with at least two free hydrazine amino groups, such as carbodihydrazide, Adipic acid dihydrazide, terephthalic acid dihydrazide or ß-semicarbazido-propionic acid hydrazide.

5v) Monofunctional chain terminators that can be incorporated are e.g. oximes such as alkanone or cycloalkanone oximes, monofunctional alcohols such as n- or iso-butanol, Stearyl alcohol, monofunctional, primary or secondary monoamines such as butylamine, Di-n-butylamine or stearylamine or hydrazine derivatives such as N, N-dimethylhydrazine, Acethydrazide, stearic acid semicarbazide or the like. N, N-dimethyl-N'-hydroxyethylhydrazine, 4-amino-2,2,6,6-tetramethylpiperidine, bis-N, N- (3'-aminopropyl) -4-amino-1,2,2,6, 6-pentamethylpiperidine or 4- (2'-hydroxyethyl) -2,5-di-tert-butyl-hydroquinone.

Buildable crosslinkers, lubricants, antiblocking agents, agents for improved Dyeable are e.g. N, N-bis- (2'-hydroxyethyl) -stearylamine, tertiary amino groups containing diols such as N, N-bis- (2'-hydroxypropyl) -N-methylamine.

The polyurethanes or polyurethane ureas A) are preferred prepared so that initially from the polyisocyanates described under 1), the higher molecular weight polyhydroxyl compounds described under 2) and those under 3) described, rsactive towards isocyanates Connections off the group of silicone resins and / or aromatic polyethers and S or aromatic Polyester and / or the perfluorocarbon resins NCO prepolymers with at least two terminal ones Isocyanate groups are produced and then with them in a manner known per se the chain extenders described under 4) are implemented. Preferably the chain extension is carried out in organic solution, the organic Solvent taken from the group of solvents described below under C) Need to become. It is equally possible and often even advantageous to use mixtures from solvents and nonsolvents for the resulting polyurethanes or To use polyurethane ureas A) as a reaction medium for chain lengthening, it must be ensured that the polyurethanes or polyurethane ureas A)> at least in colloidal form, dissolve in these mixtures. In this case the solvents from the group of solvents described below under C) and the nonsolvents from the group described below under D) Nonsolvents selected.

In the case of chain extension in organic solution, one generally works with solids contents of 10-50, preferably 20-40% by weight, c. The viscosities of the chain-extended polyurethane urea) solutions, measured at room temperature, are set to 10,000 - 100,000, preferably 20,000 - 60,000 mPas / 250C. To ensure good viscosity stability, lacks monofunctional chain terminators are used once the desired solution viscosity has been reached 5.), such as the oximes described in DE-OS 3 142 706, in the required add small amounts.

In principle, it is also possible to use the polyurethanes or

Polyurethane ureas A) in a manner known per se with the aid of suitable mixing units, such as reaction screws, in the melt and the solids obtained after cooling, for example in the form of granules, for production of the spreadable pastes according to the invention in the solvents or solvent / nonsolvent mixtures mentioned dissolve.

Type and proportions of those used in the production of A) Starting materials are chosen so that the resulting polyurethanes respectively.

Polyurethane ureas A) 1 to 30, preferably 1 to 20 wt., C contain on polymer segments, by the incorporation of one or more of the above under 3a - d) described structural components from the group of silicone resins, the aromatic polyethers, aromatic polyesters and / or perfluorocarbon resins have arisen.

Both component A) are particularly preferably polyurethane ureas, from 1) 10-40 wt .-, c, preferably 15-35 wt .- L, the above under 1.) described aliphatic polyisocyanates and 2) at least 40 6ev. % By weight, preferably 45 to 80% by weight, c, of that described above under 2.) higher molecular weight polyhydroxyl compounds and 3a) 0-15 wt, -4 of the above under 3a) described silicone resins and / or 3b) 0-15% by weight of the above under 3b) aromatic polyether described and / or 3c) 0-15 wt .-, c the above under 3c) described aromatic polyester and / or 3d) 0-15 wt .- * of the above perfluorocarbon resins described under 3d), the sum of the percentages of the structural components 3a) - 3d) is 1-20% by weight, c, and 4a) 0-20% by weight of low molecular weight polyhydroxyl compounds of Molecular weight 62-399 and 1 or 4b) 2 - 20% by weight, preferably 3 to 20% by weight, c, the above under 4b) described polyamines andl or hydrazines, and 5.) 0 - 5 wt. Of other PU body components, e.g. installable stoppers, installable Crosslinkers or built-in stabilizers are produced.

In addition to component A), a second polyurethane (urea) component B) is also used in the formulation of the spreadable pastes according to the invention will. B) is a hydrophobic polyurethane with a completely analogous structure to A) or polyurethane ureas, which, however, do not include the special polymer segments 3a) - 3d) contain the connections described under 3a) - 3d) develop.

For the production of component B) can therefore from the same range starting materials are assumed as above for the preparation of the Component A) described, with the exception of the special ones mentioned there under 3a) to 3d) Superstructure components.

The organic solvents C) suitable according to the invention are organic Compounds, preferably of the boiling point range 50 to 150in, with which produce stable solutions of the polyurethanes or polyurethane ureas A) and B) permit. In this context, the term "solutions" does not only include real, visual clear polymer solutions, but also sedimentation-stable, colloid or microgel fractions containing organic solution systems, These are, for example, tetrahydrofuran, Diisopropyl ether, dioxane, glycol monomethyl ether, but preferably alcohols and / or Ketones each having 4 to 6 carbon atoms, particularly preferably isobutanol and / or Methyl ethyl ketone.

The organic nonsolvents D) which are suitable according to the invention are organic compounds, preferably des Boiling point range 50 up to 150lC, with which no stable solutions of the polyurethanes can be formed without further additives or polyurethane ureas A) d B) can be produced.

In the case of these nonsolvents, they are preferably aromatic and / or aliphatic hydrocarbons having 6 to 12 carbon atoms and / or Fatty acid esters with 3 to 7 carbon atoms. Toluene is particularly preferred, the isomeric xylenes and S or the commercial mixtures known as "Solvenaphtha" higher-emitting hydrocarbons are used.

In combination with the previously mentioned components for manufacture the polymers E) to be used in the coating pastes according to the invention are non-polyurethanes, i.e.

Polymers without urethane and urea groups that are on the side / or at the end Carboxylate groups completely or partially neutralized with bases. Preferably one starts with homo- or copolymeric polyacrylic and / or polymethacrylic acids and / or cellulose derivatives containing carboxyl groups, such as, for example, carboxymethyl cellulose Completely or partially neutralized poly (methacrylic acids) are particularly preferred or (meth) acrylic acid copolymers inserted. These are resins, that by polymerization of acrylic acid and / or methacrylic acid with itself or with other vinyl or. Vinylidene monomers such as styrene, styrene derivatives, (Meth) acrylic acid esters with 1 to 8 carbon atoms in the alcohol component andfor acrylonitrile These polyacrylic resins generally have medium molecular weights from more than 100,000 up to the microgel range.

Any organic ones can be used to neutralize the carboxyl groups or inorganic bases are used, preference is given to ammonia or organic Amines such as triethylamine, tributylamine, N, N-dimethylbenzylamine, N-methylmorpholine or organic amino alcohols, such as ethanolamine, N, N-dimethylethanolamine, diethanolamine, N-methyldiethanolamine or triethanolamine are used.

The polymers E) suitable according to the invention are advantageously used Form of their aqueous solutions or dispersions for use, whereby already the introduced water F) necessary for the production of the spreadable pastes according to the invention can be. But it is also just as possible to use only one polymer E) Introduce part of the water F) and add the remaining amount afterwards.

If the polymer E), which is less preferred, as a solid or used in the form of an organic solution must of course be the entire Amount of water F) can be added subsequently.

In addition to the main components A) - F) mentioned above, the inventive Coating pastes, where appropriate, customary coating auxiliaries G) such as crosslinking agents andIor contain water repellants. As a crosslinker, in particular to improve the fastness properties of the coatings produced from the coating pastes to cleaning processes Melamine-formaldehyde resins, blocked, for example, are suitable or free polyisocyanates, polyaziridines, epoxy resins and lots Epoxy resin-polyamine combinations or mixtures of such crosslinkers. As a water repellent For example, commercially available silicones and / or fluorocarbon resins can be added.

The spreadable pastes suitable according to the invention contain the above components described in the proportions mentioned above, preferably but in the following amounts: 5 - 30 wt .-, c A)> 0 wt .- t B), at least 5 wt .-, c> preferably 5-40% by weight, c> in particular 5-30% by weight C), 4.5-40% by weight, c D), 0.5-5% by weight, c E), 20-60% by weight, c F), and 0-5% by weight, c G).

The spreading pastes are produced by mixing an organic, hydrophobic polyurethane phase with an aqueous phase Formation of a stable, multi-phase, emulsion-like mixture. As above described, it is preferred that the organic phase is the polyurethane-ureas) A) and optionally B), the organic solvents C), optionally the organic Contains nonsolvents D) and optionally the coating auxiliaries G).

The carboxylate group-containing polymer E) is preferably in the Contain the total amount or a partial amount of the water F). It follows that the Production of the spreadable pastes in both a one-step and multi-step process can be done. A multi-stage process is present, for example, if initially the organic polyurethane phase with a solution or dis- persion of the carboxylate polymer E) is mixed in a portion of the water F) and then the remainder of the water F) was added to the resulting mixture will. In a similar way, partial amounts of the organic solvents C) or the organic nonsolvents D) subsequently to the already water-containing one Mixture are added.

The mixing of the organic with the aqueous phases for production the spreadable pastes suitable according to the invention are similar to those used in coating technology common agitators, such as dissolvers or dispersers. the Spreadable pastes can therefore consist of the organic and aqueous ones described above Primary products can be easily produced by the user of these coating systems. The ready-to-use pastes are characterized by high homogeneity and good storage stability and thus offer a high level of processing reliability.

If necessary, the spreadable pastes can also be used in pigmented form will. The pigmentation is then preferably carried out at the coating paste stage himself; but it is also possible to use the preliminary products, such as

to pigment the organic polyurethane solutions.

Organic or inorganic ones customary in textile coating can be used Pigments and powders, but also soluble dyes, can be used.

To carry out the method according to the invention, the above spreading pastes described in the textile coating known methods either doctored or directly onto textile or leather substrates processed according to the transfer process, i.e. first painted on release paper. The coatings are then subjected to temperatures in the drying tunnel of the textile coating machine of about 40-120in, preferably 50-80C, the temperature optionally can be increased successively. This occurs as a result of selective evaporation Solvent the coagulation.

The direct coating process usually uses two lines worked. On the dried first line (base line) is used as the second line a top coat is applied with a doctor blade and dried under the conditions described above. The coating pastes suitable for the top coat are also those of the invention, type described above; Their base polyurethanes can match those of the base coat pastes be identical or different.

In the simplest case, in the case of the transfer (or reverse) method, after the drying of the first line applied to the release paper, which in this case The process represents the top coat, an adhesive coat is applied with a doctor blade, to which the lamination takes place of the textile substrate, drying and peeling off the release paper. This adhesive coating can either consist of coating pastes according to the invention, above described type or from conventional dispersion or solution adhesive coating products, which are optionally foamed mechanically or with the aid of blowing agents will.

In principle, it is also possible using the method according to the invention Produce coatings in three or more layers, with the top coat possibly a compact, non-coagulated layer with a small amount of e.g. 3-15 g / m2, preferably 4 - 6 g / m2.

The coagulation and drying times are about 1 - 3 min, which is compared to other evaporation coagulation methods enables high working speeds on the coating machines. If the Coating pastes thermosetting crosslinking agents are mixed in, can then the drying process after crosslinking at temperatures of around 120 - 200C, preferably 140-160 ° C.

The coatings obtained by the method described above have a high water vapor permeability with good water tightness at the same time and high resistance to aging and cleaning processes. The accordingly Coated textiles or leather are suitable e.g. for the production of high quality Sports and rainwear, of sports and leisure equipment and of shoe materials.

The following examples serve to further illustrate the invention. Unless otherwise stated, all percentages relate to percentages by weight.

The coating tests listed in the examples were carried out according to carried out using the following methods: - Water tightness according to DIN 53 886, measured in mm water column (mm WS) - water vapor permeability according to IUP 15 (DIN 53 333), measured in mglcm2 h - scrubbing test according to SNV 198 498 (Swiss Association of Standards) Examples Example 1 I) Preparation of a polyurethane urea solution 2193 g of a polyester from diethylene glycol and adipic acid with an OH number of 44 and 79 g of a «, @ - bishydroxymethyl-polydimethylsiloxane the OH number 200 are dehydrated and then with 710 g of isophorone diisocyanate implemented. After 2 hours of reaction at 100-100 ° C. the NCO value is 5.9% (theory: 6.2, c) achieved. The prepolymer obtained in this way is diluted with 3916 g of toluene and cooled to 25iC. A solution is added to this solution with thorough stirring of 374 g of isophoronediamine in 3916 g of isobutanol are added dropwise. When a viscosity of 30,000 - 40,000 mPas is reached, the chain is extended by adding 40 g of butanone oxime stopped.

The mixture is subsequently stirred at 50 ° C. for 2 hours and a polyurethane urea solution is obtained with a viscosity t25eC) of approx.

40,000 mPas. The polyurethane A) contains the components 1-5 in parts by weight, c-parts (based on PU solids) of 20.9 / 64.6 / 2.3 / 11.0 / 1.2.

II) Production of the base coat paste 815 g of the one described under 1lI) Solution are diluted with 160 g of toluene. Then 13 g of a 75% solution are added of a blocked polyisocyanate with a block Cated NCO content of about 10% (described in DE-OS 3,313,236, Example 4) and 12 g of a 50 show aqueous melamine resin solution (hexamethoxymethylmelamine) added. A homogeneous, stable solution with a viscosity (25 ° C) of approx. 10,000 mPas.

100 g of that described below are stirred into this organic solution aqueous dispersion of a neutralized polyacrylic acid. Under high speed Stirring, 750 g of water are finally added. A white, two-phase one is obtained Spreadable paste with a solids content of approx. $ 15 and a viscosity (25vC) of approx. 12,000 mPas.

This paste contains components A - G in the following proportions by weight and c: A: B: C: D: E: F: G = 13.2 / 0 / 15.4 / 24.1 / 1.0 / 44.911.4.

Preparation of the neutralized polyacrylic acid dispersion: 250 g of one 25 show aqueous dispersion of a copolymer of 55% ethyl acrylate and 45 % Methacrylic acid are diluted with 625 g of water and neutralized with 125 g of triethanolamine. The neutralized copolymer consists of approx. 40, c of a water-soluble component the average molecular weight 250,000 and about 60 3 from a higher molecular weight Microgel portion.

III) Production of the top coat paste 810 g of the one described under 1 / I) Solution are diluted with 165 toluene. Then add 20 g of that described under 1 / II) 50 show an aqueous melamine resin solution and 5 g of a 40 show solution of a fluorocarbon resin (Scotchgard FC-326, from 3M). A homogeneous, stable solution is created with a viscosity (25 ° C) of approx.

10,000 mPas.

100 g of the neutralized solution described under III) are stirred into this solution aqueous polyacrylic acid dispersion and finally gives with high-speed stirring 750 g of water to it. A white, two-phase spreading paste with a solids content is obtained of approx. 15% and a viscosity of approx. 10,000 mPas. This paste contains the components A - G in the following percentages by weight: A: B: C: D: E: F: G = 13.1 / 0 / 15.3 / 24.3 / 1.0 / 44.9 / 1, 4th

IV) Direct coating a) Substrate polyamide: A polyamide fabric from Approx. 100 g / m2 product weight is coated with the base coat paste 1lII) using an air knife. The driving conditions are: Drying temperature: 70eCl80-Cl80iC Speed: 6 mlmin Surface (dry): 5 glm2 The top coat paste is used on the second coating unit 1! III) the top coat is applied using a roller doctor blade.

Squeegee gap: 0.23 mm Drying temperature: 70 ° C / 70 ° C / 70 ° C, followed by crosslinking at: 140 - 160 ° C circulation (dry): 20g / m² The article is characterized by a total circulation of 25 glm2 is characterized by high watertightness and high water vapor permeability.

Water resistance: - Original 1200 - 1300 mm WS - 30'C wash 1 x 950 - 1050 mm WS 300C wash 3 x 800 - 900 mm WS - dry cleaning 1 x 850 - 900 mm WS dry cleaning 3 x 600 - 700 mm WS water vapor permeability: 7 mglcm2 h Scrubbing test, 1000 strokes, wet: no damage b) Cotton substrate: A cotton fabric of approx. 140 g / m2 fabric weight is made water repellent using customary methods (with PERLIT SE (20 gll) and PERLIT SIISW (20 g / l), Bayer AG, D-5090 Leverkusen), and after Squeezing in the moist state with the base coat paste 11II) coated with an air knife.

Drying temperature: 70 0C! 80 0C! 100 0C speed: 6 mlmin edition (dry) 7 g / m² On the second coating unit, the Top coat paste 1! III).

Squeegee gap: 0.35 mm Drying temperature: 70aC / 700Ci70'C subsequent crosslinking at 140 - 1600C (dry): 28 g! m2 Water resistance: - Original 1400 - 1500 mm WS - 30'C wash 1 x 1000 - 1100 mm WS 30 "C wash 3 x 800 - 900 mm WS - Dry cleaning 1 x 950 - 1050 mm WS Dry cleaning 3 x 650 - 750 mm WS Water vapor permeability: 10 mglcm2 h scrubbing test, 1000 strokes, wet: without damage c) Substrate mixed fabric made of cotton and polyester or

Polyamide: Mixture of cotton and polyester or polyamide (approx. 130 glma goods weight) are after the water repellent treatment according to b) in the moist state coated with the base coat paste 1lII), as described under b). Afterward the top coat paste is applied to the second coating unit, as also described under b) 1! III) doctored.

Polyamide / polyester cotton cotton total weight 28 g! M2 28 g! m2 water resistance - original 1200 1500 mm WS - 300C wash 1 x 900 1000 mm WS 30 "C wash 3 x 750 850 mm WS - dry cleaning 1 x 750 900 mm WS dry cleaning 3 x 600 700 mm WS water vapor permeability 7 9 mnlcm2h scrubbing test, 1000 strokes, wet without damage without damage V) transfer coating a) spreading paste for the production of the water vapor permeable top coat: 1000 g of the under 1! III) described, water-containing top coat paste with 25 g of ACRAMIN brown FRL (Bayer AG, D-5090 Leverkusen) pigmented.

b) Spreading paste for the production of a thin undercoat (not according to the invention): 1000 g of the polyurethane urea solution described under 1 / I) are diluted with 150 g of toluene and 150 g of isobutanol and with 40 g of ACRAMIN brown FRL pigmented.

c) Spreading paste for the production of a water vapor permeable adhesive coat: 1000 g of the water-containing base line elements described under 1 / II) pigmented with 25 g ACRAMINS Brown FRL.

d) Dispersion whipped foam for the production of a foamed adhesive coat (not according to the invention): A mixture of 500 g of the aqueous compounds described below Polyurethane dispersion and 500 g of the aqueous polyacrylate dispersion described below, 6 g of a 50% aqueous ammonium stearate solution, 10 g of that described under 1lII) 25 show aqueous polyacrylic acid dispersion and 20 g of a 50 show aqueous melamine resin solution (Hexamethoxymethylmelamine) with concentrated aqueous ammonia solution adjusted to a pH of 9 and with a high speed stirrer to a foam (500 g / l) beaten.

Composition of the polyurethane dispersion: 82> 4% polyester 1,6-hexanediol, neopentyl glycol and adipic acid with an OH number of 66 (weight ratio Hexanediol: neopentyl glycol = 65:35), 14.6 $ hexamethylene diisocyanate, 2.4% Na salt of 2-aminoethyl-2-aminoethanesulfonic acid and 0.6% ethylenediamine; Solid 40 Vig dispersed in water.

Composition of the polyacrylate dispersion: 96% butyl acrylate, 1% Itaconic acid: 2.5% acrylamide and 0> 5% N-methylolacrylamide; Solid 40, cig dispersed in water.

e) Article made up of two lines: On the 1st coating unit of a tandem coating system the coating paste a) is knife-coated onto a commercially available release paper.

Doctor blade gap: if 18 mm Drying temperature: 70 ° C / 70 ° C / 70 ° C dwell time in the drying tunnel: 2> 5 min application (dry): 15 g / m² the paste c) is applied with a doctor blade gap of 0> 25 mm, and then is a roughened cotton fabric with a weight of approx. 140 g! m2 is laminated.

Drying temperature: 60 ° C / 70 ° C / 90 ° C then crosslinking at: 150 - 1600C The result is a soft, supple article with a total print run of approx. 35 g / m² and a water vapor permeability of 9 mg / cm2 h> which is suitable for production light outerwear is suitable.

f) Article from two lines: On the dried one described under e) The top coat is the dispersion whipped foam paste d) on the second coating unit applied to a doctor blade gap of 0.3 mm. Then the one described under e) Laminated cotton substrate. The drying of the adhesive coat takes place with increasing 80 ° C / 120iC / 160vC. A soft, full-bodied article is obtained with a total coverage of approx. 60 g! m2 and a water vapor permeability of 10 mg / cm2.

g) Article made up of three lines: On the 1st line of a three-line system the coating paste b) is knife-coated onto a commercially available release paper and passed through Drying at 60 - 120'C a thin, compact undercoat of 6 g / m² solid layer generated.

Then on the 2nd coating with the paste a) the water vapor permeable Squeegee coating; Driving conditions: as described under e); Edition (dry): 15 g / m2, on the 3rd coating unit, the dispersion whipped foam paste is used as an adhesive coat d) applied with a doctor blade gap of 0.3 mm. Then the one described under e) Laminated cotton substrate. The drying of the adhesive coat takes place with increasing 80-C1120iC1160-C. A soft, very voluminous article is obtained with a total circulation from approx.

65 glm2 and a water vapor permeability of 7 mg / cm² h.

Example 2 I) Primary coat: polyurethane urea solution and coat ---------------- paste from it.

2193 g of a polyester made from diethylene glycol and adipic acid with an OH number 44 and 79 g of a «> -Bishydroxymethylpolydimethylsiloxans with OH number 200 are reacted as described in Example 1 / I) with 577 g of isophorone diisocyanate; NCO content: 4.5, c.

The prepolymer obtained in this way is diluted by adding 2420 g of toluene and cooled to 20iC. Immediately before the beginning of the chain extension that now follows it is diluted even further with 1470 g of isobutanol.

Chain Extension: A separately prepared solution of 272 g of IPDA in a mixture of 1224 g of toluene and 1224 g of isobutanol is quickly under good Stirring added dropwise to the cooled prepolymer solution. With increasing viscosity gradually added 950 g of isobutanol. When a viscosity of 30,000 to 40 000 mPas is reached, is stopped by adding 30 g of butanone oxime.

The mixture is stirred for 1 h at 50 ° C. and a clear solution with a is obtained Viscosity (25-C) of 40,000 mPas.

815 g of the polyurethane urea solution described above are mixed with 165 g of toluene diluted. This dilute solution is added 15 g of the in Example 1 / II) blocked polyisocyanate described and 5 g of an epoxy resin (LEKUTHERMBX 50, Bayer AG). 100 g of the neutralized products described under 1 / II) are also stirred aqueous polyacrylic acid dispersion and then dispersed therein 750 g of water. The spreadable paste has a solids content of approx. 15% and a> viscosity (250C) of 10,000 mPas.

II) Top coat: Polyurethane urea solution and coating paste from it: 1913 g of a polyester made from 1> 4 butanediol and adipic acid (OHZ 50) and 85 g of one oc, -Bishydroxymethyl-polydi- methylsiloxane of OHZ 200 in a reaction screw with 644 g of isophorone diisocyanate and 323 g of isophorone diamine implemented at temperatures between 80 - 180iC. The extruded melt strand becomes granulated after cooling. 300 g of polyurethane urea granules are in 350 g of toluene and 350 g of isobutanol dissolved, the 30% solution has a viscosity (250C) of 30 000 mPas.

810 g of this solution are diluted with 165 g of toluene.

20 g of a 50% aqueous melamine resin are added to this solution according to Example 1JII) and 5 g of a silicone resin (SILOPREN # E 50, Bayer AG). Afterward 100 g of the neutralized aqueous polyacrylic acid dispersion described under 1 / II) and 750 g of water mixed in. The approx. 15 bed spreading paste has a viscosity of approx. 15,000 mPas.

111) Direct coating A polyamide fabric weighing approx. 90 gEm2 is coated with the base coat paste 2tI) using an air knife. The driving conditions in a 15 m long drying tunnel are: Drying temperature: 70 ° C / 80 ° C / 100 ° C / 150 ° C Speed: 8 mlmin Edition (dry): 5 gm2 On the second coating unit, the Top coat paste 21II) applied using a roller doctor blade: Drying temperature: 70-C over the entire channel. Squeegee gap: 0.30 mm Application (dry): 27 glmP Crosslinking (1 minS160 ° C), the article is made hydrophobic as described in Example 1 / IVb).

Water resistance: - Original 1500 mm WS - 30-C wash 1 x 1000 mm WS 30-C wash 3 x 900 mm WS - dry cleaning 1 x 800 mm WS dry cleaning 3 x 700 mm water vapor permeability: 5 mg! Cm2 h scrubbing test, 1000 strokes, wet: without damage Example 3 I) Base 1913 g of a polyester made from diethylene glycol and adipic acid of OH number 44 and 138 g of a polyether of bisphenol A and propylene oxide the OH number 205 is after dehydration with 348 g of toluene diisocyanate 2.4 / 2.6 (65:35) implemented. After 1 hour of reaction at 100 etc. the NCO value is 3.5 % achieved.

The NCO prepolymer is dissolved in 2997 g of toluene and before the start of Chain extension diluted with 1997 g of isobutanol. A solution is added dropwise at 25 ° C of 170 g of isophoronediamine in 1000 g of isobutanol are added. After reaching one The addition reaction becomes viscosity of 50,000 mPas by adding 20 g of butanone oxime stopped. The solution is 30 ig.

815 g of the polyurethane urea solution described above are mixed with 165 g of toluene diluted. This dilute solution is added 15 g of the in Example 1lII) described polyisocyanate and 5 g of a polyaziridine, as e.g.

in P 3 415 920 is added. 100 g of the are also stirred neutralized, aqueous polyacrylic acid dispersion described below and then mixes in 750 g of water. A white, two-phase spreadable paste is obtained of approx. 15% solids content with a viscosity (25-C) of approx. 15,000 mPas.

Preparation of the polyacrylate dispersion: 250 g of that described under 11II) 25 show polyacrylic acid dispersions are diluted with 662 g of water and with 88 g of N-methylmorpholine neutralized.

II) Top coat 2040 g of a polyester made from diethylene glycol and adipic acid with an OH number of 44 and 110 g of a polyether made from bisphenol A and propylene oxide from OHZ 205 are according to a known method at 100-110es with 666 g of isophorone diisocyanate implemented. After 2 hours of reaction, an NCO value of 5.9 is reached.

The prepolymer is dissolved in 3722 g of toluene and 1000 g of isobutanol. at 25-C one extends with a solution of 375 grams of isophoronediamine in 2722 g of isobutanol. After a viscosity of 40,000 mPas has been reached, 20 g butanone oxime stopped the pole addition reaction. The answer is 30 cig, 810 g the solution shown is diluted with 160 g of ethyl acetate. Adds to this solution 25 g of the 50% aqueous melamine resin described under 1 / II) and 5 g a silicone resin (BAYSILONBOFIOH 502, Bayer AG). 100 g of the are also stirred a neutralized, aqueous polyacrylic acid dispersion described under 31I) and then mixes in 750 g of water. The two-phase spreadable paste has approx. 15% solids content and a viscosity (250C) of 10,000 mPas.

III) Direct coating A polyester fabric weighing 80 g! M2 is used analogous to 21III) with the base coat paste 31I) using an air knife and the top coat paste 31II) coated with a roller doctor blade.

Total circulation: 25 g Im2 Water resistance: Original 1100 mm WS - 30'C wash 1 x 900 mm WS 30 "C wash 3 x 800 mm WS - dry cleaning 1 x 700 mm WS dry cleaning 3 x 600 mm WS water vapor permeability: 5 mglcm2 h scrubbing test, 1000 strokes, wet: without damage EXAMPLE 4 I) Primer coating paste according to Example 21I) II) top coat 1913 g of a polyester made from diethylene glycol and 0HZ 44 adipic acid and 102 g of a polyester made from ethylene glycol and phthalic acid the 0HZ 275 are reacted with 666 g of isophorone diisocyanate at 100-110in. To An NCO value of 6.0 is reached after a 2-hour reaction.

The prepolymer melt is dissolved in 5063 g of toluene. At 250C it will a solution of 340 g of isophoronediamine in 4000 g of isobutanol to extend the chain added dropwise. To end the polyaddition reaction, after reaching a Viscosity of 40,000 mPas 20 g of butanone oxime added. The answer is 25, cig.

25 g of the melamine resin solution described under 1SII) are added to 965 g of this solution and stir in 10 g of the silicone resin described under 3SII). Before dispersing with 750 g of water, 100 g of the neutralized aqueous solution described under 3tI) Incorporated polyacrylic acid dispersion. The spreading paste has a viscosity (25 "C) of 12,000 mPas.

III) Direct coating A polyester fabric is used analogously to Example BIIII) primed with paste 2/1) and further coated with paste 4SII).

Total circulation 30 glm2 Water resistance: - Original 1200 mm WS - 30 C wash 1 x 900 mm WS - dry cleaning 1 x 700 mm WS Water vapor permeability: 4 mgJcm2 h scrubbing test, 1000 strokes, wet: without damage. Example 5 I) Base line 1720 g of a polyester made from hexanediol-l, S, neopentyl glycol (glycol ratio = 65:35) and adipic acid with OH number 56.79 g of an α, # - bishydroxymethyl-polydimethylsiloxane the OHZ 200 are analogously to 1JI) with 555 g of isophorone diisocyanate to an NCO prepolymer implemented; NCO value: 5.1 L.

After dissolving the prepolymer in 3050 g of toluene and 1050 g of isobutanol the polyurethane urea is made with a solution of 255 g of isophoronediamine in 2000 g of isobutanol built up. The polyaddition reaction is stopped using 20 g of butanone oxime. The 30th goat solution has a viscosity (250C) of 39,000 mPas.

815 g of this solution are diluted with 165 g of xylene.

This dilute solution is added to 20 g of that described under 1 / II) blocked polyisocyanate. 100 g of the are added to the solution thus obtained neutralized polyacrylic acid dispersion described below and then 750 g water. The two-phase spreading paste has a viscosity (25'C) of approx. 15,000 mPas.

Preparation of the polyacrylate dispersion: 250 g of that described under 1lII) 25 show polyacrylic acid dispersions are neutralized with 105 g of N-methyldiethanolamine, after having previously been diluted with 645 g of water.

II) Top coat 1720 g of the polyester used in 5 / I) and 79 g of the dimethylpolysiloxane used in 5 / I) are mixed with 710 g of isophorone diisocyanate converted to an NCO prepolymer; NCO value: 7.1, c. The prepolymer is in 3350 g of toluene and 1350 g of isobutanol dissolved and analogous to 51I) with 375 g of isophoronediamine implemented in 2000 g of isobutanol.

The goat solution has a viscosity (25-C) of 42,000 mPas.

815 g of this solution are diluted with 165 g of butyl acetate and mixed with 20 g of the block described under 11II) Cated polyisocyanate, 100 g of the neutralized polyacrylic acid dispersion described under 5 / I) and 750 g of water stirred well; Viscosity of the coating paste: approx. 15,000 mPas (25-C).

III) Direct coating A polyester fabric is used analogously to Example 31III) primed with paste 51I) and further coated with paste 51II).

Total circulation: 30 g! M2 Water resistance: - Original 1500 mm WS - 300C laundry 1 x 1200 mm WS - dry cleaning 1 x 900 mm WS water vapor permeability: 8 mglcm2 h scrubbing test, 1000 strokes, wet: without damage. Example 6 I) Base line 1720 g of a polypropylene glycol polyether of OHN 56 and 79 g of an α, # - bishydroxymethyl-polydimethylsiloxane the OHZ 200 are analogously 1lI) with 577 g of isophorone diisocyanate to an NCO prepolymer implemented; NCO value: 5.6, c.

The NCO prepolymer melt is dissolved in 3090 g of toluene at 200C diluted with 1090 g of isobutanol and treated with a solution of 272 g of isophoronediamine in 2000 g isobutanol implemented. The goat solution has a viscosity (250C) of 42,000 mPas.

815 g of this solution are diluted with 165 g of toluene, then one adds 15 g of the blocked polyisocyanate described under 1lII), 10 g of the under 11II) aqueous melamine resin solution described, 100 g of the neutralized described under 11Il) Polyacrylic acid dispersion and 750 g of water are added. The two-phase spreadable paste has a viscosity (25-C) of approx. 17,000 mPas.

II) Top coat 2376 g of the prepolymer melt described under 6! I) are dissolved in 3160 g of toluene and diluted at 25 ° C. with 1160 g of isobutanol The prepolymer solution is mixed with a solution of 336 g of 4,4'-diaminodicyclohexylmethane at 25 ° C. while cooling converted to polyurethane urea in 2000 g of isobutanol. The 30 goat solution has a viscosity (25in) of 42,000 mPas.

810 g of this solution are diluted with 165 g of toluene and with 25 g of the under 11II) described aqueous melamine resin solution and 5 g of utner 31II) described Silicone resin added. 100 g of that described under 31I) are then used aqueous, neutralized polyacrylic acid dispersion and 750 g of water are added. the approx.

15 goat spread has a viscosity (25 ° C) of approx.

11,000 mPas.

Medium base coat paste 6JI) and top coat paste 6 / II) can be used on fabrics made of natural and synthetic fibers, coatings that are permeable to water vapor produce.

Water vapor permeability: 4 - 8 mglcm2 h Water resistance:> 1000 mm WS Example 7 I) Baseline Analog 61) 1720 g of a polytetramethylene glycol polyether are used the OHZ 56 instead of the polypropylene glycol ether used there with the rest, components mentioned there implemented. The 30 goat has polyurethane urea solution a viscosity (250C) of approx. 35,000 mPas.

The base coat paste prepared therefrom analogously to 61) has a solids content of approx. 15% and a viscosity <25'C) of 15,000 mPas.

II) top coat 1440 g of a polytetramethylene glycol polyether of OHZ 56 and 158 g of an α, # - bishydroxymethyl-polydimethylsiloxane with OHN 200 are analogous to 1 / I) with 710 g isopho- rondiisocyanate to an NCO prepolymer implemented; the NCO value is determined to be 7.8%. The prepolymer melt is in 3120 g of toluene dissolved, diluted at 25 ° C. with 1120 g of isobutanol and with cooling reacted with a solution of 375 g of isophoronediamine in 2000 g of amyl alcohol.

The 30 dough polyurethane urea solution has a viscosity (25'C) of approx. 42,000 mPas. The top coat paste prepared from it analogously to 61II) has one Solids content of approx. 15% and a viscosity (25-C) of 15,000 mPas.

Fabrics made from natural and synthetic fibers can be mixed with the base coat paste 7lI) and the top coat paste 71II). The articles are characterized by soft handle, little blocking surface, good adhesion to the substrate, good water vapor permeability and high water resistance (> 1200 mm WS).

Example 8 I) Basecoat coating paste according to Example 21I).

II) Top coat 2193 g of a polyether made from diethylene glycol and adipic acid the 0HZ 44 and 79 g of a «, -Bishydroxymethylpolydimethylsiloxans the 0HZ 200 are with 760 g 4,4'- Diisocyanato-dicyclohexyl-methane at 110 ° C in the Melt implemented. After 2 hours of reaction, the NCO content is determined to be 5.0%.

The melt is dissolved in 3900 g of toluene and 1900 g of n-butanol diluted at 25 ° C. A solution of 323 g of isophoronediamine is left with cooling flow in 2000 g of n-butanol. The 30 goat solution has a viscosity (25 ° C) of 32,000 mPas. The top coat paste prepared therefrom analogously to 61II) has a solids content of 15% and a viscosity (259C) of 15,000 mPas.

III) Direct coating A polyamide fabric with a weight of 100 glm2 is used with the base coat paste 2fI) primed (air knife) and then with a roller doctor blade the top coat 81II) applied; Driving conditions: analogous to 21III).

Total circulation: 35 g / m² Water resistance: -Original 1800 mm WS -30eC wash 1500 "chemical cleaning 1000" water vapor permeability: 8 mglcm2h srubb test, 1000 strokes, wet: without damage Example 9 I) Base coating paste according to Example 2 / I) II) top coat 1190 g of a polyester made from 1,6-hexanediol> Neopentyl glycol (glycol ratio = 65:35) and adipic acid with OHN 66 and 176 g Perfluorooctanesulfonic acid N, N-bis (2-hydroxyethyl) amide are mixed with 490 g of isophorone diisocyanate converted to an NCO prepolymer at 100-110'C. After 2 hours of reaction it is reached an NCO value of 5.2%. The prepolymer melt is dissolved in 2400 g of toluene, cooled to 25 ° C. and diluted with 1200 g of isobutanol. Under cooling, a Solution of 205 g of isophoronediamine in 1200 g of isobutanol was added dropwise. You get one 30 dough solution with a viscosity (25 <C) of approx.

45,000 mPas. The top coat paste prepared therefrom analogously to 6 / II) has a solids content of approx. 15% and a viscosity (25'C) of 17,000 mPas.

III) Direct coating A polyamide fabric with a weight of 100 gSm2 is used primed with base coat paste 21I) (air knife) and then with a roller doctor blade the top coat 91I) applied; Driving conditions: analogous to 2 / III).

Total circulation: 35 gIms Water resistance: -Original 1600 mm WS -30 ° C wash 1300 - chemical cleaning 1100 water vapor permeability: 7 mg / cm2h scrubbing test, 1000 strokes, wet: without damage Example 10 I) Base coat of coating paste according to Example 2SI) II) Top coat 1785 g of a polyester made from diethylene glycol and adipic acid the OH number 44, 170 g of a «> -Bishydroxymethyl-polydimethylsiloxane the OH number 99 and 88 g of perfluorooctanesulfonic acid-N, N-bis- (2-hydroxyethyl-) amide are after Dehydration at SlOeC with 710 g of isophorone diisocyanate to an NCO value of 6.4, c achieved.

The prepolymer melt is dissolved in 3650 g of toluene and cooled to 250C. A solution of 374 g of isophoronediamine in 3650 g of isobutanol is then added dropwise to. After a viscosity of 30,000 mPas has been reached, the mixture is stopped with 20 g of butanone oxime and stirred for 2 hours at 50 ° C. A goat polyurethane urea solution is obtained with a viscosity (25'C) of 35,000 mPas.

810 g of this solution are diluted with 165 g of toluene and with 25 g the aqueous melamine resin solution described under 1 / II) and 5 g of the under 31II) silicone resin described. An aqueous solution is then stirred from 6 g of commercially available carboxymethyl cellulose (WalocelB MT 4000 GB, Wolff-Walsrode AG), 12 g of triethanolamine and 82 g of water and then added with high-speed stirring 750 g of water to it. The approx. 15 dough spreading paste has a viscosity (25-C) of approx. 10,000 mPas.

Leave with the base coat paste 211) and the top coat paste 1011) using the direct coating process on fabrics made from natural and synthetic fibers Produce coatings that are permeable to water vapor.

Water vapor permeability: 5-10 mg / cm2h Water resistance:> 1000 mm WS Example 11 1) Base line 900 g of a polytetramethylene glycol polyether the OH number 112 and 56 g of an a, w-bishydroxymethyl-polydimethylsiloxane with the OH number 200 are dehydrated and then at 1000C with 625 g of 4,4'-diisocyanatodiphenylmethane implemented up to an NCO value of 7.9%.

it is diluted with 800 g of methyl ethyl ketone, and 74.5 g of ethylene glycol are added and stir at 80'C until an NCO value of 1.0% is reached. It is then diluted with a further 2850 g of methyl ethyl ketone and cooled to 25iC. A solution of 15 g of hydrazine hydrate in 250 g of water is added dropwise at this temperature and then stir for 3 h at 50 ° C. A cloudy but homogeneous solution is formed with a solids content of 30% and a viscosity (25'C) of approx. 20,000 mPas. The base coat paste prepared therefrom analogously 1 / II) has a solids content of approx. 15% and a viscosity (25-C) of approx. 10,000 mPas.

II) Top coat 2240 g of a dehydrated polyester made from 1,4-butanediol and adipic acid with an OH number of 50 are mixed with 666 g of isophorone diisocyanate in a reaction screw and 340 g of isophoronediamine reacted at temperatures between 80 and 1800C. Of the extruded melt strand is granulated after cooling.

300 g of this polyurethane urea granulate are dissolved in 350 g of toluene and 350 g of isobutanol dissolved; the 30 goat solution has a viscosity (25es) of 35,000 mPas.

300 g of this solution are mixed with 510 g of the polyurethane urea solution according to Example 1 / I) and 165 g of toluene mixed. Then add 20 g of the under 1 / II) described melamine resin solution and 5 g of the fluorocarbon resin solution described under 1lIII) added. Furthermore, 100 g of the under are added one after the other with thorough stirring 1 / II) described neutralized aqueous polyacrylic acid dispersion and 750 g of water to. The top coat paste thus obtained has a viscosity (25-C) of approx.

12,000 mPas with a solids content of approx. 15%.

Leave with the base coat paste 11 / I) and the top coat paste 11 / II) according to the procedure given in Example 1 on fabrics made of natural and Synthetic fibers produce coatings that are permeable to water vapor.

Water vapor permeability: 7-10 mglcm2h Water resistance:> 1200 mm WS

Claims (10)

Claims 1. A method for producing water vapor permeable Coatings on textile or leather substrates in direct or transfer processes according to the principle of evaporation coagulation using polyurethane plastics containing, optionally pigmented, spreadable pastes, characterized in that that, as spreadable pastes, multiphase mixtures of A) 5 - 50 L by weight are inherently hydrophobic Polyurethanes and / or polyurethane ureas containing 1 to 30% by weight of structural components from the group of silicone resins, polyethers containing aromatic molecular segments or polyester and / or perfluorocarbon resins, incorporated, B) 0-30 % By weight per se hydrophobic polyurethanes and / or polyurethane ureas, which without the special structural components mentioned under A) are built up, C) 4.5 - 50 % By weight of organic solvents for A) and B), D) 0-40% by weight of organic solvents Nonsolvents for A) and B), E) 0.5-10% by weight of polymers, which are free of urethane and urea groups and with bases in whole or in part Carrying neutralized carboxyl groups, F) 10 - 70% by weight of water and G) O - 5% by weight of of crosslinking agents, water repellants, stabilizers and / or others Coating aids are used. 2. The method according to claim 1, characterized in that the polyurethanes or polyurethane ureas A) 1-20% by weight of compounds containing polysiloxane segments with at least two terminal and / or pendent, isocyanate-reactive Groups included as structural components. 3. The method according to claim 1, characterized in that the polyurethanes or polyurethane ureas A) 1-20 wt. by alkoxylation of aromatic Hydroxy-functional compounds produced with at least two phenolic hydroxyl groups Containing polyethers as structural components, these polyethers being less than 10% by weight consist of oxyethylene segments -CH2-CH2-0-. 4. The method according to claim 1, characterized in that the polyurethanes or polyurethane ureas A) 1-20% by weight of polyesters of isomeric phthalic acids with at least two terminal and / or pendent hydroxyl groups as structural components contain. 5. The method according to claim 1, characterized in that the polyurethanes or polyurethane ureas A) 1-20% by weight of compounds containing perfluoroalkyl groups with at least two terminal and / or pendent, isocyanate-reactive Groups included as building components. 6. The method according to claim 1 to 5, characterized in that the Polyurethanes or polyurethane ureas A) two or more of the in the claims 3 - 5 named special structural components 3 a-d in a total of 1-20 Weight included. 7. The method according to claim 1 to 6, characterized in that the organic solvents C) alcohols and / or ketones each having 4 to 6 carbon atoms and that the organic non-solvents D) are aromatic and / or aliphatic Hydrocarbons with 6-10 carbon atoms and / or fatty acid esters with 3-7 Are carbon atoms. 8. The method according to claim 1 to 7, characterized in that the polymers free of urethane and urea groups E) homo- or copolymeric poly- acrylic- and / or polymethacrylic acids and / or cellulose derivatives containing carboxyl groups are whose carboxyl groups are wholly or partially neutralized with bases. 9. The method according to claim 1 to 8, characterized in that one as spreadable pastes, multiphase, stable mixtures of A) 5-30% by weight are inherently hydrophobic Polyurethane ureas composed of 1) 10-40% by weight of aliphatic polyisocyanates and 2) at least 40 wt. Aliphatic polyhydroxyl compounds of molecular weight 500-5000 and 3a) 0-15 wt. DihydroxymethylpoAydimethylsiloxanes of molecular weight 300-3000 and / or 3b) 0-15 wt. Alkoxylated bis (hydroxyphenyl) alkanes from Molecular weight 300 - 2000 with less than 10 wt .-% oxyethylene segments -CH2-CH2-O- andl or 3c) 0-15 wt. k at least two terminal and / or pendent hydroxyl groups containing polyesters of isomeric phthalic acids with a molecular weight of 250 - 2000 undloder 3d) 0-15 wt. Diols with at least three perfluorinated ones Perfluoroalkyl groups containing carbon atoms and having a molecular weight of 300 - 2000, where the sum of the percentages of the structural components 3a) to 3d) is 1-20%, and 4a) 0-20% by weight of polyhydroxyl compounds with a molecular weight of 62-399 and / or 4b) 2-20% by weight of polyamines and / or hydrazine and / or hydrazine derivatives of molecular weight 32 »and 60 to 399 and 5) 0-5% by weight of other structural components, B) if necessary 0-30 wt, -L of per se hydrophobic polyurethanes and / or polyurethane ureas, those produced without the special structural components 3a) -3d) mentioned under A) are, C) 4.5-40% by weight alcohols and / or ketones each having 4-6 carbon atoms, D) at least 5 wt .-, c aromatic and / or aliphatic hydrocarbons with 6-10 carbon atoms and / or fatty acid esters with 3-7 carbon atoms, E) 0.5-5% by weight of poly (meth) acrylic acids completely or partially neutralized with bases and / or (meth) acrylic acid copolymers F) 20-60% by weight of water and G) 0-5% by weight, c Crosslinking agents, water repellants, stabilizers and / or other coating auxiliaries used. 10. Spreading pastes, in the form of multiphase, stable mixtures from A) 5-30 wt., C per se hydrophobic polyurethane ureas, which are composed of 1) 10-40 wt. -, c aliphatic polyisocyanates and -2) at least 40% by weight of aliphatic polyhydroxyl compounds of molecular weight 500-5000 and 3a) 0-15 6ew. -, c dihydroxymethylpolydimethylsiloxanes of molecular weight 300-3000 and / or 3b) 0-15% by weight of alkoxylated bis (hydroxyphenyl) alkanes of molecular weight 300-2000 with less than 10 6 wt .-, c oxyethylene segments -CH2-CH2-0- and / or 3c) 0-15 wt., C at least two end and / or The polyesters of the isomeric phthalic acids have pendant hydroxyl groups of molecular weight 250-2000 and / or 3d) 0-15 wt., c diols with at least three perfluoroalkyl groups containing perfluorinated carbon atoms of molecular weight 300 - 2000, whereby the sum of the percentages of the structural components 3a) to 3d) 1-20%, and 4a) 0-20% by weight, c polyhydroxyl compounds of molecular weight 62 - 399 and / or 4b) 2-20% by weight of polyamines and / or hydrazine and / or hydrazine derivatives of molecular weight 32 and 62 to 399 and 5) 0-5 wt .-, c of other structural components, B) optionally 0-30 wt., C per se hydrophobic polyurethanes and / or polyurethane ureas, those produced without the special structural components 3a) -3d) mentioned under A) are, C) 4.5-40 wt .-, c alcohols and / or ketones each with 4-6 carbon atoms, D) at least 5% by weight of aromatic and / or aliphatic hydrocarbons 6-10 carbon atoms and / or fatty acid esters with 3-7 carbon atoms, E) 0.5-5 6ew .-, c PolyEmeth -) - acrylic acids completely or partially neutralized with bases and / or (Meth) acrylic acid copolymers F) 20-60 parts by weight of water and G) 0-5% by weight of crosslinking agents, Water repellants, stabilizers and / or other coating auxiliaries.