DE3522464A1 - 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 hydrophobic polyurethanes and/or polyurethane ureas per se which contain incorporated 1-30% by weight of synthesis components from the silicone resin group, the polyethers or polyesters containing aromatic molecular segments and/or the perfluorocarbon resins, B) 0-30% by weight of hydrophobic polyurethane(urea)s per se, which are synthesised without the special synthesis components mentioned in 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) 0-10% by weight, preferably 0.5-5% by weight, of polymers which are free of urethane and urea groups and carry carboxyl groups completely or partially neutralised with bases, F) 10-70% by weight of water and G) 0-5% by weight of crosslinking agents, hydrophobicising agents, stabilisers against discoloration and degradation and/or other coating auxiliaries. The coating pastes are used in the direct or transfer process for the production of water vapour-permeable coatings by the principle of evaporative coagulation.

Description

The invention relates to PU-containing Coating pastes, as well as a new method of manufacture of water vapor permeable coatings on textile or leather substrates in direct or transfer processes using the principle of evaporation coagulation of these containing polyurethane plastics Coating pastes.

The coating pastes are multi-phase, stable mixtures

• A) 5 - 50 wt .-% per se hydrophobic polyurethanes and / or polyurethane ureas, the 1 - 30 wt .-% structural components from the group
  the silicone resins, the aromatic molecular element-containing polyether or polyester and / or the perfluorocarbon resins, incorporated,
• B) 0-30% by weight of hydrophobic polyurethane (urea) per se, those without the special ones mentioned under A) Assembly components are constructed,
• C) 4.5 - 50 wt .-% of organic solvents for A) and B),
• D) 0 to 40% by weight of organic non-solvents for A) and B),
• E) 0-10% by weight, preferably 0.5-5% by weight, of polymers, which are free of urethane and urea groups are and partially or completely neutralized with bases Carry carboxyl groups,
• F) 10-70% by weight of water and
• G) 0-5% by weight of crosslinking agents, water repellents, Stabilizers against discoloration and Degradation and / or other coating aids.

Textile or leather coatings that are highly permeable for water vapor and at the same time one have high water resistance, especially on the Clothing and footwear sector, of increasing interest. The advantage of such coated materials is that the clothing made from it on the one hand optimally protects, but on the other hand the body moisture can escape in the form of water vapor. These Have properties in both health and hygienic Terms as well as in terms of comfort a high priority.  

An important process, microporous and therefore water vapor permeable That’s how it creates coatings the so-called bath coagulation, e.g. in the DE-AS 12 70 276 and DE-AS 17 69 277 is described. Here, a substrate with one in an organic Solvent-dissolved polyurethane or polyurethane urea coated and the coated product in a bath of a miscible with the solvent Non-solvent (e.g. water). The coagulation of the polyurethane takes place through the extraction of the solvent by the non-solver.

The disadvantages of this method are that required complete removal of the solvent very large amounts of nonsolvent are needed, and that the process takes a long time. Furthermore are to carry out this procedure as well Processing of the resulting solvent / non-solvent mixtures special, relatively complex Equipment required.

There has been no shortage of attempts at permeable to water vapor Coatings in the manner of a simple direct or transfer coating on conventional textile coating machines to manufacture. Most of these Experiments take the path of so-called evaporation coagulation. In principle, this procedure is carried out that one dissolved in a volatile solvent Polymers a certain amount of a less volatile Non-solvent is added and so resulting solution, dispersion or suspension on a Substrate is painted. The coating is through  gentle heating dried, preferred at first the volatile solvent evaporates. The result is, that the polymer coagulates in the layer and after final Drying has a microporous structure. This procedure is e.g. described in DE-PS 16 94 059; here polyurethanes are used, which in volatile organic solvents, e.g. Tetrahydrofuran or methyl ethyl ketone are colloidally dissolved and with organic non-solvents with higher evaporation rates, such as. White spirit, to be mixed. A a similar procedure is described in Swiss Patent 4 81 971, with the extension, that there among those to be added to the polymer solutions Non-solvents is also called water. Another one The method according to DE-PS provides an example of this type 20 04 276. Here are hydrophilic polyurethanes Based on aromatic diisocyanates used that certain Proportions of polyoxyethylene compounds as structural components contain. Solutions of these polyurethanes in certain organic solvents, e.g. Methyl ethyl ketone, are using water as a non-solvent mixed and applied to a substrate, whereupon the Coating through selective evaporation and is then dried.

The above, according to the principle of evaporation coagulation However, working methods still show serious Defects. There is a major disadvantage in that the selective evaporation of the more volatile Solvent fractions take a lot of time and one  extremely precise temperature control is required. The handling of the corresponding products on the coating machines is therefore complicated and especially only with slow ones Driving speeds possible. Another serious one Disadvantage, in particular the method mentioned according to DE-PS 20 04 276, is in the difficult Processability of the polyurethane solutions described there or suspensions justified. Although the solids content is low, these products are, indeed before the one that takes place at the time of application Water addition, highly viscous. They are called "muddy Suspensions "are strongly prone to premature Drying with formation of gel particles and Specks and are therefore difficult to handle by the coater. In addition, the coatings according to the latter patent the disadvantage of lack Lightfastness.

The object of the present invention was therefore to Process for the production of water vapor permeable Coatings to provide that on conventional Coating machines in direct or transfer processes can be done and that the above does not have the disadvantages described in detail.

This task could be accomplished by providing the following Multi-phase, according to the invention, described in more detail stable coating pastes and their use in the coating process according to the direct or transfer procedure solved according to the principle of evaporation coagulation will.  

The invention is based on the surprising observation that from per se hydrophobic polyurethanes or Polyurethane ureas, the specific ones defined below Silicone, polyether, polyester or perfluorocarbon resin Sigments included built in and those in organic Solvents are solved, especially by Addition of certain non- Polyurethane resins with side or terminal carboxylate groups and of certain amounts of water multi-phase, stable coating pastes are available that yourself in surprisingly easier, faster and safely on conventional coating machines can be processed into microporous coatings. These are preferably those according to the invention Base polymers based on polyurethane ureas aliphatic polyisocyanates, which is advantageous lightfast water vapor permeable coatings result.

The inventive method has the advantage that the Polyurethane solutions are low viscosity before adding water and in this respect from the coater, who is just about to do it Application that produces ready-to-use coating pastes, are easy and safe to use. Furthermore stand out according to the inventive method by adding resin containing carboxylate groups and Water-based coating pastes through particularly good Storage stability and processing security.

The present invention therefore relates to a process for the production of water vapor-permeable coatings on textile or leather substrates in the direct or transfer process according to the principle of evaporation coagulation using optionally pigmented coating pastes containing polyurethane plastics, characterized in that
that multi-phase mixtures as coating pastes

• A) at least 5 wt .-%, preferably 5 - 50 wt .-%, per se hydrophobic polyurethanes and / or polyurethane ureas, the
  1 to 30% by weight, preferably 1 to 20% by weight, in particular 1.5 to 15% by weight, of special structural components from the group
  the silicone resins, the aromatic polyethers containing aromatic molecule segments, the polyesters containing aromatic molecular segments and / or the perfluorocarbon resins, but not present,
• B) 0-30% by weight of hydrophobic polyurethanes and / or polyurethane ureas without the mentioned special construction components manufactured are,
• C) 4.5-50% by weight of organic solvents for A) and B),
• D) 0 - 40 wt .-% organic non-solvents for A) and B),  
• E) 0-10% by weight, preferably 0.5-10% by weight, particularly preferably 0.5 - 5 wt .-%, polymers that are free of Urethane and urea groups are and side and / or completely or partially with bases carry neutralized carboxyl groups,
• F) 10-70% by weight of water and
• G) 0-5% by weight of crosslinking agents, water repellents, Stabilizers against discoloration and degradation, and / or other coating aids,
• be used. (The sum of percentages A) to G) should add up to 100 each.)

The coating pastes can also be any conventional ones Amounts of dyes, pigments or powders for coloring, and optionally fillers.

Another object of the invention are those listed above Spreading pastes in the form of multi-phase, stable mixtures from A) - G) as described above.

To carry out the method according to the invention coating pastes used 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 organic non-solvent D) and the coating aid G), with aqueous or organic solutions or dispersions of the partially or completely neutralized Caboxyl groups  bearing polymers E) are mixed and then optionally the remainder of the water F) was added becomes.

The components are particularly preferably A) and B) are polyurethane ureas based on aliphatic Polyisocyanates.

The polyurethanes or polyurethane ureas A) are in Polyaddition products obtainable in a manner known per se from polyisocyanates and compounds with active Hydrogen atoms. Essential characteristic of these polymers but is that they are hydrophobic, i.e. without further Auxiliaries no stable dispersions or solutions with water, and that they have certain structural components from the group of silicone resins, the aromatic Polyether containing molecular segments, the aromatic Polyester and / or the perfluorocarbon resins containing molecular segments built in included.

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 having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical with 7 to 15 carbon atoms. A detailed list of suitable diisocyanates can be found, for example, in DE-OS 31 34 112, DE-OS 28 54 384 and DE-OS 29 20 501.

Examples of such preferred diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, 1-methyl-1,5-diisocyanatopentane, 2-methylpentane diisocyanate-2,5, 2-ethyl-butane-diisocyanate-1,4, 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'-diisocyanates, lysine alkyl ester diisocyanates, Oligomers or homopolymers of m- or p- Isopropenyl α, α-dibenzyl diisocyanates according to EP-A 1 30 313, 1-alkyl-2-isocyanatomethyl-isocyanato-cyclohexane, 1- Alkyl-4-isocyanatomethyl-isocyanato-cyclohexane after EP-A 1 28 382, 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 α, α, α ′, α′-tetramethyl-m- or -p-xylylene diisocyanate as well as those connections Mixtures.

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

It is of course also possible with the invention Processes in polyurethane chemistry per se  known higher functional polyisocyanates or known modified, for example carbodiimide groups, Allophanate groups, isocyanurate groups, urethane groups and / or polyisocyanates having biuret groups to use (with).

2.) Water-insoluble polyhydroxyl compounds in the Polyurethane chemistry known per se with molecular weights over 400, for example 400-10,000, preferably from 500 - 5000 and melting points below 60 ° C, preferably below 45 ° C. The corresponding ones are preferred Dihydroxy compounds used. The shared use of in the sense of the isocyanate polyaddition reaction tri- or higher functional connections in small Proportions to achieve a certain degree of branching is as possible as the already mentioned, possible Use of tri- or higher functional polyisocyanates for the same purpose. Furthermore, it is preferred that the corresponding polyhydroxyl compounds predominantly made from aliphatic components are.

Hydroxyl compounds to be preferably used are Hydroxypolyesters known per se in polyurethane chemistry, Hydroxypolyethers, hydroxypolythioethers, hydroxypolycarbonates and / or hydroxypolyesteramides. In the Question coming hydroxyl-containing polyester are e.g. Implementation groups of polyvalent, preferably divalent and possibly additionally trivalent Alcohols with polyvalent, preferably dihydric Carboxylic acids.  

Are trihydric or higher alcohols for production the polyester is used, so is the (co-) use monovalent carboxylic acids possible. Leave the other way around monovalent when using higher quality carboxylic acids Use alcohols.

Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding Polycarboxylic acid esters of lower alcohols or their mixtures used to manufacture the polyester will. The polycarboxylic acids are preferably more aliphatic and / or cycloaliphatic in nature and can optionally, e.g. substituted by halogen atoms and / or be unsaturated. As examples of this are called:

Succinic acid, adipic acid, suberic acid, azelaic acid, Sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrachlorophthalic anhydride, Endomethylene tetrahydrophthalic anhydride, glutaric anhydride, Maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids.

If necessary, (also) to be used monovalent carboxylic acids are preferably saturated or unsaturated fatty acids, such as. 2-ethylhexanoic acid, palmitic acid, Stearic acid, oleic acid, ricinoleic acid, linoleic acid, ricinenic acid, Linolenic acid and technical fatty acid mixtures, as e.g. from natural raw materials (e.g. Coconut fat, linseed oil, soybean oil, castor oil) can be obtained.  

As polyhydric alcohols are e.g. Ethylene glycol, propanediol (1,2) and - (1,3), butanediol- (1,4), - (2,4) and / or - (2,3), hexanediol- (1,6), octanediol- (1,8), neopentylglycol, Cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, Hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, Methylglycoside, also diethylene glycol, dipropylene glycol, Polypropylene glycols, dibutylene glycol and polybutylene glycols in question. The polyester can have proportionally terminal carboxyl groups. Also Polyester from lactones, e.g. ε-caprolactone or hydroxycarboxylic acids, e.g. ω-hydroxycaproic acid applicable.

The polyethers which are preferred in accordance with the invention and preferably have two hydroxyl groups are those of the type known per se and are, for example, polymerized by themselves with tetrahydrofuran or epoxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin, for example in the presence of BF ₃ or by Accumulation of these epoxides, optionally in a mixture or in succession, on starting components with reactive hydrogen atoms such as alcohols and amines, for example water, ethylene glycol or propylene glycol (1,2).

In order to ensure the essential characteristic of the hydrophobicity of the polyurethane (ureas) according to the invention, the polyethers used as structural components may only contain a maximum of enough ethylene oxide units that the resulting polyurethane (ureas) contain less than 2% by weight of oxyethylene segments -CH ₂ -CH ₂ -O- included. Ethylene oxide-free polyethers are preferably used to produce the polyurethane (ureas) according to the invention.

Also modified by vinyl polymers, such as they e.g. by polymerizing styrene, acrylonitrile arise in the presence of polyethers (US Pat. No. 3,383,351, 33 04 273, 35 23 093, 31 10 695, DE-PS 11 52 536) suitable. Those that may also be used proportionately Highly functional polyethers are created in an analogous manner by known alkoxylation of higher functionality Starter molecules e.g. Ammonia, ethanolamine, Ethylenediamine, trimethylolpropane, glycerin or sucrose.

Among the polythioethers are, in particular, the condensation products of thiodiglycol with yourself and / or with other glycols, dicarboxylic acids, formaldehyde, Aminocarboxylic acids or amino alcohols listed.

Coming as polycarbonates having hydroxyl groups those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol- (1,6), with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be.

The polyester amides and polyamides include e.g. the from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines  and their mixtures obtained, mainly linear Condensates. Already urethane or urea groups Containing polyhydroxyl compounds can be used.

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

3.) According to the invention in the manufacture of the hydrophobic Polyurethane (urea) in the sense of isocyanate Addition reaction of at least difunctional compounds from the group of silicone resins (3a), the aromatic Polyether (3b) containing molecular segments, the aromatic Polyester (3a) and / or the perfluorocarbon resins (3d).

In detail, it is about
3a) Compounds containing polysiloxane segments with at least two terminal and / or pendant groups which are reactive toward isocyanates, with molecular weights of 194-10,000, preferably from 300 to 3000. Difunctional polysiloxanes with organofunctional end groups are preferably used. These compounds have structural units of the formula -O-Si- (R) ₂ -, where R is a C ₁ -C ₄ -alkyl or a phenyl radical, but preferably a methyl radical.

Organofunctional, linear polysiloxanes suitable as starting material according to the invention are, for example, in DE-AS 11 14 632, 11 90 176, 12 48 287, 25 43 638 or in DE-OS 23 56 692, 24 45 648, 23 63 452, 24 27 273 or 25 58 523. 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:

The organofunctional polysiloxanes have at least 1, preferably 3 to 30, structural units of the formula -O-Si (R) ₂ - (R is preferably methyl) with a molecular weight of 194 to 20,000, particularly preferably between 300 and 3000.

Hydroxymethyl-poly-dimethylsiloxanes of the general formula are particularly preferred as starting compounds according to the invention as they are produced in a manner known per se, for example by the process of DE-AS 12 36 505.

3b) According to the invention, component A also contains di- or higher-functional, preferably difunctional, hydroxy-functional polyethers which are produced by oxalkylation of aromatic compounds with at least two phenolic hydroxyl groups and which contain less than 10% by weight of oxyethylene segments -CH ₂ -CH ₂ -O- exist and molecular weights from 226 to 3000, preferably from 300 to 2000, are used. Examples of compounds with at least two phenolic hydroxyl groups for the preparation of the aromatic polyethers suitable according to the invention are hydroquinone, the isomeric naphthalene diols, but preferably diols of the general formula to use.

In the last-mentioned formula, X represents one of the divalent radicals -S-, -O-, -SO ₂ -, -CO- or -C (R ₁ R ₂ ) - where R ₁ and R _{2 are} identical or different and are hydrogen or C ₁ -C ₄ alkyl radicals, or wherein R ₁ and R ₂ form a 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 (CH ₃ ) ₂ -.

The aromatic hydroxypolyethers suitable according to the invention are prepared in a manner known per se by polyaddition of cyclic ethers onto the aromatic polyols mentioned above. Examples of suitable cyclic ethers are ethylene oxide, propylene oxide, butylene oxide, styrene oxide or mixtures of these compounds. In the case of the (co-) use of ethylene oxide, only such proportions of these compounds may be used that, in accordance with the above-mentioned condition, the resulting aromatic polyethers contain less than 10% by weight of oxyethylene segments -CH ₂ -CH ₂ -O-. Preferably only propylene oxide is used.

As aromatic hydroxyl polyethers are adducts of bisphenol A and propylene oxide are particularly preferred.  

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

3c) polyester of the isomeric phthalic acids with at least two terminal and / or pendant hydroxyl groups and Molecular weights from 250 to 5000, preferably from 250 to 2000 can be used. Difunctional are preferred Polyester of this type used. It deals known condensation products polyvalent, preferably with dihydric alcohols Phthalic acid, isophthalic acid and / or terephthalic acid, these aromatic acids optionally also, e.g. can be substituted by halogen atoms. Instead of the free dicarboxylic acids you can of course the corresponding carboxylic acid esters are also lower Alcohols or (in the case of phthalic acid) also their anhydride for the preparation of the invention suitable aromatic polyester can be used.

Furthermore, according to the invention, A can also

3d) compounds containing perfluoroalkyl groups at least two terminal and / or lateral, opposite Isocyanate reactive groups and molecular weights from 250 to 5000, preferably from 300 to 2000 be used. Diols of the above are preferred Type used that have at least three perfluorinated carbon atoms in the form of in the main chain of the diol built-in and / or laterally arranged to this Contain perfluoroalkyl groups, under "perfluoroalkyl groups" saturated, perfluorinated, alphatic Radicals that are linear,  have branched or cyclic structure can. Diols of the abovementioned are particularly preferred Type with pendant perfluoroalkyl groups used, such as are described in DE-OS 33 19 368. Examples of such particularly well-suited structural components are the N-sulfonylperfluoroalkyl aminoalkanol derivatives the general formula:

C _n F _{2n + 1} -SO ₂ -N (-X-OH) ₂

wherein
X is a linear or branched, saturated alkylene radical having 2 to 4 carbon atoms and
n stands for an integer greater than 2, preferably 5 to 12.

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

Specifically, these are:

4a) Low molecular weight, monomeric and / or oligomeric polyhydroxyl compounds. The monomeric polyols preferably have Molecular weights of 62-399 and include Connections such as Ethanediol, 1,2-propanediol and -1.3, 1,4-butanediol, -2.3 and -1.3, neopentyl glycol, Hexanediol-1,6, 1,4,3,6-dianhydrohexite, trimethylolpropane, Glycerin and pentaerythritol. Examples of oligomers  Chain extenders are difunctional condensation products on average from the above tri- or tetrafunctional alcohols and monofunctional carboxylic acids with average molecular weights of 200 - 399. As carboxylic acids for this come the above as possible structural components of the higher molecular weight hydroxyl polyesters called saturated and / or 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. Traded in the polyamines it is preferably aliphatic or cycloaliphatic Diamines, although sometimes also in part tri- or higher functional polyamines to achieve a certain degree of branching can also be used can. Examples of suitable aliphatic polyamines are ethylene diamine, trimethylene diamine, tetramethylene diamine, Hexamethylenediamine, 1,2-propylenediamine, the mixture of isomers of 2,2,4- and 2,4,4-trimethylhexamethylene diamine and bis (2-aminoethyl) amine (diethylene triamine).

Examples of suitable cycloaliphatic polyamines which can be used as individual stereoisomers or as any mixtures of stereoisomers are:

Araliphatic polyamines, e.g. m- and p-xylylenediamine, as well as m- or p-α, α, α ′, α′-tetramethyl-xylylenediamine, can be used as chain extenders use for the polyurethane ureas according to the invention.  

Examples of suitable hydrazine chain extenders are: hydrazine, which is preferably in the form its hydrate is to be used and hydrazine derivatives at least two free hydrazine amino groups, such as e.g. Carbodihydrazide, adipic acid dihydrazide, terephthalic acid dihydrazide or β-semicarbacido-propionic acid hydrazide.

5.) Installable, monofunctional chain terminators 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 similar Built-in Stabilizers are e.g. N, N-dimethyl-N'-hydroxyethyl hydrazine, 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.

Installable crosslinkers, lubricants, antiblocking agents, Means for improved dyeability 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 preferably made so that first from the under 1) described polyisocyanates, those described under 2) higher molecular weight polyhydroxyl compounds and described under 3), reactive towards isocyanates  Compounds from the group of silicone resins and / or the aromatic polyether and / or the aromatic Polyester and / or the perfluorocarbon resins NCO prepolymers with at least two terminal isocyanate groups be produced and then in known per se Way with the chain extenders described under 4) be implemented. Preferably the Chain extension carried out in organic solution, the organic solvents being the following group of solvents described under C) Need to become. It is just as possible and often even advantageous, mixtures of solvents and non-solvents for the resulting polyurethanes or polyurethane ureas A) as the reaction medium use in the chain extension, whereby guaranteed must be that the polyurethanes or polyurethane ureas A), at least in colloidal form, in solve these mixtures. In this case the solvents from that described under C) below Group of solvents and the non-solvents the group of non-solvents described below under D) selected.

Works in chain extension in organic solution generally with a solids content of 10 - 50, preferably 20-40% by weight. The viscosities of the chain-extended polyurethane (urea) solutions, measured at room temperature, are reduced to 10,000 - 100,000, preferably 20,000-60,000 mPas / 25 ° C. To It is recommended to ensure good viscosity stability  after reaching the desired solution viscosity monofunctional chain terminators 5.), like e.g. the oximes described in DE-OS 31 42 706, in the add necessary small amounts.

In principle, it is also possible to use the polyurethanes or Polyurethane ureas A) in a manner known per se With the help of suitable mixing units, e.g. Reaction screws, manufacture in the melt and the after cooling, e.g. in the form of granules Solids for the production of the invention Coating pastes in the stated solvents or solvents / Dissolve non-solvent mixtures.

The nature and proportions of the production of A) raw materials used are otherwise chosen so that the resulting polyurethanes or Polyurethane ureas A) 1 to 30, preferably 1 to Contain 20 wt .-% of polymer segments by the Installation of one or more of the above under 3a - d) described structural components from the group of silicone resins, the aromatic polyether, the aromatic Polyester and / or the perfluorocarbon resins were created are.

The component is particularly preferably A) To polyurethane ureas that are made from

• 1) 10-40% by weight, preferably 15-35% by weight, of the aliphatic described above under 1.) Polyisocyanates and  
• 2) at least 40% by weight, preferably 45 to 80 % By weight, described above under 2.) higher molecular weight polyhydroxyl compounds and
• 3a) 0-15% by weight of those described above under 3a) Silicone resins and / or
• 3b) 0-15% by weight of those described above under 3b) aromatic polyether and / or
• 3c) 0 to 15% by weight of those described above under 3c) aromatic polyester and / or
• 3d) 0 to 15% by weight of those described above under 3d) Perfluorocarbon resins,
• where the sum of the percentages of the construction components 3a) - 3d) is 1 - 20% by weight, and
• 4a) 0-20% by weight of those described above under 4a) low molecular weight polyhydroxyl compounds from Molecular weights 62-399 and / or
• 4b) 2-20% by weight, preferably 3 to 20% by weight, of the polyamines described above under 4b) and / or hydrazines, and
• 5.) 0 - 5% by weight of other PU structural components, e.g. built-in stoppers, built-in crosslinkers or built-in stabilizers,
• are made.

In addition to component A), it may optionally be the second Polyurethane (urea) component B) in the formulation the coating pastes according to the invention also used will. B) is a completely analogous structure to A) hydrophobic polyurethanes or polyurethane ureas, but not the special polymer segments 3a) - 3d) included, which by installing the under 3a) - 3d) described connections arise.

For the production of component B) can therefore same range of starting materials as above in the manufacture of the component A), with the exception of those listed under 3a) to 3d) mentioned special construction components.

The organic solvents suitable according to the invention C) are organic compounds, preferably of the boiling point range 50 to 150 ° C, with which stable solutions the polyurethanes or polyurethane ureas A) and B) have it made. The term "solutions" includes in this context not only real, optically clear Polymer solutions, but also sedimentation-stable, Organic solution systems containing colloid or microgel components. These are, for example, tetrahydrofuran, Diisopropyl ether, dioxane, glycol monomethyl ether, but preferably alcohols and / or ketones with each 4 to 6 carbon atoms, particularly preferably isobutanol and / or methyl ethyl ketone.

The organic non-solvents suitable according to the invention D) are organic compounds, preferably the  Boiling point range 50 to 150 ° C, with which without other additives no stable solutions of the polyurethanes or have polyurethane ureas A) and B) produced. These non-solvents are preferably used aromatic and / or aliphatic hydrocarbons with 6 to 12 carbon atoms and / or fatty acid esters with 3 to 7 carbon atoms. Particularly preferred are toluene, the isomeric xylenes and / or as "Solvenaphtha" known commercial mixtures of higher boiling Hydrocarbons used.

The in combination with the previously mentioned components for the production of the coating pastes according to the invention, if appropriate Polymers E) to be used are non-polyurethanes, i.e. Polymers without urethane and urea groups, the side and / or terminal with bases entirely or partially neutralized carboxylate groups. It is preferable to use homo- or copolymers Polyacrylic and / or polymethacrylic acids and / or Cellulose derivatives containing carboxyl groups such as e.g. Carboxymethyl cellulose. Be particularly preferred fully or partially neutralized poly (meth) acrylic acids or (meth) acrylic acid copolymers used. These are resins made by polymerization of acrylic acid and / or methacrylic acid with itself or with other vinyl or vinylidene monomers, such as e.g. Styrene, styrene derivatives, (meth) acrylic acid esters with 1 to 8 carbon atoms in the alcohol component e.g. also Ω-Hydroxyalkyl esters of (meth) acrylic acid and / or Acrylonitrile have been obtained. The (meth) acrylic acid content in the (co) polymer is between 1 and 100% by weight, preferably between 2.5 and 60% by weight. These  Polyacrylic resins generally have average molecular weights from more than 100,000 up to the microgel Area.

Any can be used to neutralize the carboxyl groups organic or inorganic bases can be used. Ammonia or organic amines, such as e.g. Triethylamine, tributylamine, N, N-dimethylbenzylamine, N-methylmorpholine or organic amino alcohols, such as e.g. Ethanolamine, N, N-dimethylethanolamine, diethanolamine, N-methyldiethanolamine or triethanolamine used.

The polymers E) suitable according to the invention can be advantageous in the form of their aqueous solutions or dispersions are used, which already means that for the production the coating pastes according to the invention necessary Water F) can be introduced. It is also just as possible, with the polymer E) only a part of water F) to introduce and the remaining amount subsequently to admit. If the polymer E), what less is preferred, as a solid or in the form of an organic Solution used, so of course the total amount of water F) are added subsequently.

In addition to the main components A) -F) mentioned so far the coating pastes according to the invention, if appropriate coating aids G), such as e.g. Crosslinker and / or contain water repellents. As Crosslinkers, in particular to improve the fastness properties of the coatings made from the coating pastes  can serve against cleaning processes For example, melamine-formaldehyde resins blocked or free polyisocyanates, polyaziridines, epoxy resins and / or epoxy resin-polyamine combinations or Mixtures of such crosslinkers. As a water repellent can e.g. commercially available silicones and / or fluorocarbon resins be added. Included are the rapid crosslinking of the necessary usual resins Catalysts.

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

The coating pastes are produced in each case by mixing an organic, hydrophobic polyurethane Phase with an aqueous phase to form a stable, multi-phase, emulsion-like mixture. How described above, it is preferred that the organic phase the polyurethane (ureas) A) and optionally B), the organic solvent C), if appropriate the organic non-solvents D) and optionally contains the coating aids G). The polymer E) containing carboxylate groups is preferred in the total or a subset of  Water F) included. It follows that the manufacture the coating pastes both in a one-step, as well can be done in multi-stage processes. A multi-stage The procedure is, for example, when the organic polyurethane phase with a solution or dispersion of the carboxylate polymer E) in a subset of the water F) is mixed and then the remaining amount of water F) added to the resulting mixture becomes. Similarly, subsets can also the organic solvent C) or the organic Non-solvent D) still added to that already water-containing mixture are added.

The mixing of the organic with the aqueous phases for the preparation of the coating pastes suitable according to the invention is with the usual in coating technology Stirring units, e.g. Dissolvers or dispersers perform. The prank phases can therefore be out the organic and aqueous described above Pre-products from the user of these coating systems can be easily produced. The ready to use Pastes are characterized by high homogeneity and good Storage stability and thus offer high processing reliability.

If necessary, the coating pastes can also be pigmented Form can be applied. The pigmentation takes place then preferably at the level of the spreading paste itself; however, it is also possible to use the preliminary products, e.g. pigment the organic polyurethane solutions.  The usual organic in the textile coating or inorganic pigments and powders, but also soluble dyes can be used.

To carry out the method according to the invention the coating pastes described above according to in known methods of textile coating either directly doctored on textile or leather substrates or after processed the trans procedure, i.e. first on Removed release paper. The coatings are then Temperatures in the drying tunnel of the textile coating machine from about 40 - 120 ° C, preferably exposed to 50 - 80 ° C, where the temperature may be successive can be increased. This occurs as a result of being selective Evaporation of the solvent coagulation.

The direct coating process is usually carried out with worked two strokes. On the dried first Dash (base dash) becomes a dash as a second dash doctored and under the conditions described above dried. The ones suitable for the top coat Spreading pastes are also those of the inventive type described above; their base polyurethanes can be identical to those of the base stroke phases or be different from it.

The simplest is the transfer (or reverse) procedure Case after drying the applied on the release paper first line, which the Dash marks, a sticky line on what  lamination of the textile substrate, drying and then peeling off the release paper. This Adhesive line can either be made from coating pastes of the inventive type described above or from conventional dispersion or solution adhesive products, if necessary mechanically or with the help of Foaming agents are foamed.

In principle, it is also possible to produce coatings in a three- or multi-layer structure using the process according to the invention, the top coat optionally being a compact, non-coagulated layer with a low circulation of, for example, 3-15 g / m ³ , preferably 4-6 g / m ³ can.

The coagulation and drying times are per line about 1 - 3 min, which is measured by other evaporation coagulation methods comparatively high working speeds enabled on the coating machines. When the coating pastes thermally curing crosslinkers are added, can then be added to the drying process after crosslinking at temperatures of about 120-200 ° C, preferably 140-160 ° C, made will.

Those obtained by the method described above Coatings have a high water vapor permeability with good water resistance and high Resistance to aging and cleaning processes on. The appropriately coated textiles  or leather are e.g. for the production of high quality Sports and rainwear, sports and leisure equipment as well as shoe materials.

The following examples are provided for further explanation the invention. All percentages refer to unless otherwise noted, percentages by weight.

The coating tests listed in the examples were carried out according to the following methods:

• - Water resistance according to DIN 53 886, measured in mm water column (mm WS)
• - Water vapor permeability according to IUP 15 (DIN 53 333), measured in mg / cm ³ · h
• - Scrubb test according to SNV 198 498 (Swiss standards association)

Examples example 1 I) Preparation of a polyurethane urea solution

2193 g of a polyester of diethylene glycol and adipic acid the OH number 44 and 79 g of an α, ω-bishydroxymethyl Polydimethylsiloxane with an OH number of 200 are dewatered and then with 710 g of isophorone diisocyanate implemented. After 2 hours of reaction at 100 - 100 ° C achieved an NCO value of 5.9% (theory: 6.2%). The prepolymer thus obtained is diluted with 3916 g of toluene and cooled to 25 ° C. One leaves this solution under with good stirring, a solution of 374 g of isophoronediamine in Add 3916 g of isobutanol dropwise. If a viscosity of 30 000 - 40 000 mPas is reached, the chain extension stopped by adding 40 g of butanone oxime. The mixture is subsequently stirred at 50 ° C. for 2 hours and a polyurethane urea solution is obtained with a viscosity (25 ° C) of approx. 40,000 mPas. The polyurethane A) contains the components 1 - 5 in% by weight (based on PU solids) of 20.9 / 64.6 / 2.3 / 11.0 / 1.2.

II) Preparation of the base coat paste

815 g of the solution described under 1 / I) are included Diluted 160 g toluene. Then you add 13 g of a 75% Solution of a blocked polyisocyanate with a blocked  NCO content of approx. 10% (described in DE-OS 3,313,236, Example 4) and 12 g of a 50% strength aqueous solution Melamine resin solution (hexamethoxymethylmelamine) added. It creates a homogeneous, stable solution with a viscosity (25 ° C) of approx. 10,000 mPas.

100 g of the following are stirred into this organic solution described aqueous dispersion of a neutralized Polyacrylic acid. With high-speed stirring 750 g of water are finally added. You get a white, two-phase coating paste with a solids content of approx. 15% and a viscosity (25 ° C) of approx. 12,000 mPas.

This paste contains components A - G in the following % By weight: A: B: C: D: E: F: G = 13.2 / 0 / 15.4 / 24.1 / 1.0 / 44.9 / 1.4.

Preparation of the neutralized polyacrylic acid dispersion:

250 g of a 25% aqueous dispersion of a copolymer from 55% ethyl acrylate and 45% methacrylic acid are diluted with 625 g of water and with 125 g of triethanolamine neutralized. The neutralized copolymer exists 40% from a water-soluble portion of the average molecular weight 250,000 and about 60% a higher molecular weight microgel fraction.  

III) Preparation of the top coat paste

810 g of the solution described under 1 / I) with 165 g Diluted toluene. Then add 20 g of that described under 1 / II) 50% aqueous melamine resin solution and 5 g a 40% solution of a fluorocarbon resin (Scotchgard® FC-326, 3M) added. A homogeneous, stable solution with a viscosity (25 ° C) of approx. 10,000 mPas.

100 g of the solution described under 1 / II) are stirred into this solution neutralized aqueous polyacrylic acid dispersion and finally gives with high-speed stirring 750 g of water. A white, two-phase is obtained Spreading paste with a solids content of approx. 15% and a viscosity of approx. 10,000 mPas. This paste contains 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 / 1.4.

IV) Direct coating

• a) Polyamide substrate:
• A polyamide fabric of approx. 100 g / m ³ product weight is coated with the base coat paste 1 / II) using an air knife. The driving conditions are:
  • Drying temperature: 70 ° C / 80 ° C / 80 ° C
    Speed: 6 m / min
    Edition (dry): 5 g / m ³
• On the second coating unit, the top coat is applied with the top coat paste 1 / III) over a doctor blade.
  • Squeegee gap: 0.23 mm
    Drying temperature: 70 ° C / 70 ° C / 70 ° C
    then crosslinking at: 140 - 160 ° C
    Edition (dry): 20g / m ³
• With a total print run of 25 g / m ^{3, the} article is characterized by high water resistance and high water vapor permeability.
  • Water resistance:
    - Original 1200 - 1300 mm WS
    - 30 ° C wash 1 × 950 - 1050 mm WS
    30 ° C wash 3 × 800 - 900 mm WS
    - Dry cleaning 1 × 850 - 900 mm WS
    Dry cleaning 3 × 600 - 700 mm WS
    Water vapor permeability: 7 mg / cm ³ h
    Scrubb test, 1000 strokes, wet: without damage
• b) Cotton substrate:
• A cotton fabric with a fabric weight of approx. 140 g / m ³ is hydrophobicized using conventional methods (with PERLIT® SE (20 g / l) and PERLIT® SI / SW (20 g / l), Bayer AG, D-5090 Leverkusen), and after squeezing in the moist state with the base coat paste 1 / II) coated with an air knife.
  • Drying temperature: 70 ° C / 80 ° C / 100 ° C
    Speed: 6 m / min
    Edition (dry): 7 g / m ³
• On the second coating unit, the top coat paste 1 / III) is spread over a doctor blade.
  • Squeegee gap: 0.35 mm
    Drying temperature: 70 ° C / 70 ° C / 70 ° C
    then crosslinking at 140 - 160 ° C
    Edition (dry): 28 g / m ³
• Water resistance:
  - Original 1400 - 1500 mm WS
  - 30 ° C wash 1 × 1000 - 1100 mm WS
  30 ° C wash 3 × 800 - 900 mm WS
  - Dry cleaning 1 × 950 - 1050 mm WS
  Dry cleaning 3 × 650 - 750 mm WS
  Water vapor permeability: 10 mg / cm ³ h
  Scrubb test, 1000 strokes, wet: without damage
• c) Substrate blended fabrics made of cotton and polyester or polyamide:
  Mixed fabrics made of cotton and polyester or polyamide (approx. 130 g / m ³ fabric weight) are coated with the base coat paste 1 / II) after the water repellency in accordance with b), as described under b). The topcoat paste 1 / III) is then knife-coated on the second coating unit, as also described under b).

V) Transfer coating

• a) Spreading paste for the production of the water vapor-permeable top coat:
  1000 g of the water-containing top coat paste described under 1 / III) are pigmented with 25 g ACRAMIN®-Braun FRL (Bayer AG, D-5090 Leverkusen).
• b) coating paste for producing a thin pre-coat (not according to the invention):
  1000 g of the polyurethane urea solution described under 1 / I) are diluted with 150 g toluene and 150 g isobutanol and pigmented with 40 g ACRAMIN®-Braun FRL.
• c) Spreading paste for the production of a water vapor permeable adhesive coating:
  1000 g of the water-containing base coat elements described under 1 / II) are pigmented with 25 g ACRAMIN®-Braun FRL.
• d) Dispersed whipped foam for producing a foamed adhesive coat (not according to the invention):
  A mixture of 500 g of the aqueous polyurethane dispersion described below and 500 g of the aqueous polyacrylate dispersion described below, 6 g of a 50% aqueous ammonium stearate solution, 10 g of the 25% aqueous polyacrylic acid dispersion described under 1 / II) and 20 g of a 50% strength aqueous melamine resin solution (hexamethoxymethylmelamine) are adjusted to a pH of 9 with concentrated aqueous ammonia solution and whipped to a foam (500 g / l) using a high-speed stirrer.
• Composition of the polyurethane dispersion:
  82.4% polyester from 1,6-hexanediol, neopentylglycol and adipic acid with OH number 66 (weight ratio hexanediol: neopentylglycol = 65:35), 14.6% hexamethylene diisocyanate, 2.4% Na salt of 2-aminoethyl-2 -aminoethanesulfonic acid and 0.6% ethylenediamine; Solid 40% dispersed in water.
• Composition of the polyacrylate dispersion:
  96% butyl acrylate, 1% itaconic acid, 2.5% acrylamide and 0.5% N-methylolacrylamide; Solid 40% dispersed in water.
• e) Two-stroke article:
  On the first coating unit of a tandem coating system, the coating paste a) is knife-coated onto a commercially available release paper.
  • Squeegee gap: 0.18 mm
    Drying temperature: 70 ° C / 70 ° C / 70 ° C
    Residence time in the drying tunnel: 2.5 min
    Edition (dry): 15 g / m ³
• Paste c) is applied to the second coating unit with a doctor blade gap of 0.25 mm, and then a roughened cotton fabric of about 140 g / m ³ weight is laminated on.
  • Drying temperature: 60 ° C / 70 ° C / 90 ° C
    then crosslinking at: 150 - 160 ° C
• A soft, supple article with a total circulation of approx. 35 g / m ³ and a water vapor permeability of 9 mg / cm ³ h is obtained, which is suitable for the production of light outerwear.
• f) Two-stroke article:
  Dispersion whipped foam paste d) is applied to the dried top coat described under e) with a doctor blade gap of 0.3 mm on the second coating unit. The cotton substrate described under e) is then laminated on. The adhesive coat dries at 80 ° C / 120 ° C / 160 ° C. A soft, full article is obtained with a total circulation of approx. 60 g / m ³ and a water vapor permeability of 10 mg / cm ³ .
• g) Article with three lines:
  On the first coating unit of a three-line system, the coating paste b) is knife-coated onto a commercially available release paper and a thin, compact pre-coat of 6 g / m ³ solid layer is produced by drying at 60-120 ° C.
• On the second coating unit with paste a) the water vapor permeable top coat is knife-coated; Driving conditions: as described under e); Edition (dry): 15 g / m ³ .
• On the 3rd coating unit, the dispersion foam foam paste d) is applied with a doctor blade gap of 0.3 mm. The cotton substrate described under e) is then laminated on. The adhesive coat dries at 80 ° C / 120 ° C / 160 ° C. A soft, very full article is obtained with a total circulation of approx. 65 g / m ³ and a water vapor permeability of 7 mg / cm ³ h.

Example 2 I) base line:

Polyurethane urea solution and coating paste made from it.
2193 g of a polyester of diethylene glycol and adipic acid with an OH number of 44 and 79 g of an α, ω-bishydroxymethylpolydimethylsiloxane with an OH number of 200 are reacted with 577 g of isophorone diisocyanate as described in Example 1 / I); NCO content: 4.5%.

The prepolymer thus obtained is obtained by adding 2420 g Dilute toluene and cool to 20 ° C. Just before The beginning of the following chain extension is diluted still further with 1470 g of isobutanol.

Chain extension: A separately made solution of 272 g IPDA in a mixture of 1224 g toluene and 1224 g of isobutanol quickly become the with good stirring cooled prepolymer solution dripped. With increasing Viscosity is gradually added 950 g of isobutanol. If a viscosity of 30,000 to 40,000 mPas is reached, is stopped by adding 30 g of butanone oxime.

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

815 g of the polyurethane urea solution described above are diluted with 165 g of toluene. This dilute solution add 15 g of that described in Example 1 / II) blocked polyisocyanate and 5 g of an epoxy resin (LEKUTHERM®X 50, Bayer AG). One continues to stir 100 g of the neutralized aqueous described under 1 / II) Polyacrylic acid dispersion and dispersed then 750 g of water. The coating paste has one Solids content of approx. 15% and a viscosity (25 ° C) of 10,000 mPas.

II) Top line:

Polyurethane urea solution and coating paste made of it:
1913 g of a polyester of 1,4-butanediol and adipic acid (OHZ 50) and 85 g of an α, ω-bishydroxymethyl-polydimethylsiloxane of OHZ 200 are mixed in a reaction screw with 644 g of isophorone diisocyanate and 323 g of isophorone diamine at temperatures between 80-180 ° C implemented. The extruded melt strand is granulated after cooling. 300 g of polyurethane urea granules are dissolved in 350 g of toluene and 350 g of isobutanol, the 30% solution has a viscosity (25 ° C) of 30,000 mPas.

810 g of this solution are diluted with 165 g of toluene. 20 g of a 50% strength aqueous solution are added to this solution Melamine resin according to Example 1 / II) and 5 g of a silicone resin (SILOPREN®E 50, Bayer AG). Then be 100 g of the neutralized aqueous described under 1 / II) Polyacrylic acid dispersion and 750 g of water mixed in. The approx. 15% coating paste has a viscosity of approximately 15,000 mPas.

III) Direct coating

A polyamide fabric of approx. 90 g / m ³ weight is coated with the base coat paste 2 / I) 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 m / min
  Edition: 5 g / m ³

On the second coating unit, the top layer paste 2 / II) applied by roller squeegee:  

• Drying temperature: 70 ° C over the entire channel
  Squeegee gap: 0.30 mm
  Edition (dry): 27 g / m ³

After crosslinking (1 min / 160 ° C) the article is as in Example 1 / IVb), hydrophobized.

• Water resistance:
  - Original 1500 mm WS
  - 30 × ° C wash 1 × 1000 mm WS
  30 × ° C wash 3 × 900 mm WS
  - Dry cleaning 1 × 800 mm WS
  Dry cleaning 3 × 700 mm WS
  Water vapor permeability: 5 mg / cm ³ h
  Scrubb test, 1000 strokes, wet: without damage

Example 3 I) baseline

1913 g of a polyester made from diethylene glycol and adipic acid the OH number 44 and 138 g of a polymer from bisphenol A and propylene oxide of OH number 205 are after dewatering with 348 g tolylene diisocyanate 2.4 / 2.6 (65:35) implemented. After 1 hour of reaction at 100 ° C an NCO value of 3.5% is reached.

The NCO prepolymer is dissolved in 2997 g of toluene and pre Beginning of chain extension diluted with 1997 g isobutanol. A solution of 170 g of isophoronediamine is added dropwise at 25 ° C. in 1000 g of isobutanol. After reaching  the addition reaction becomes a viscosity of 50,000 mPas stopped by adding 20 g of butanone oxime. The Solution is 30%.

815 g of the polyurethane urea solution described above are diluted with 165 toluene. This dilute solution add 15 g of that described in Example 1 / II) Polyisocyanate and 5 g of a polyaziridine, e.g. in P 3 415 920. Still stirring 100 g of the neutralized aqueous solution described below Polyacrylic acid dispersion and then mixes 750 g of water under. A white, two-phase is obtained Spreading paste of approx. 15% solids content with a Viscosity (25 ° C) of approx. 15,000 mPas.

Preparation of the polyacrylate dispersion:
250 g of the 25% polyacrylic acid dispersion described under 1 / II) are diluted with 662 g of water and neutralized with 88 g of N-methylmorpholine.

II) Top line

2040 g of a polyester made from diethylene glycol and adipic acid the OH number 44 and 110 g of a polyether from bisphenol A and propylene oxide from OHZ 205 are known Method at 100 - 110 ° C with 666 g isophorone diisocyanate implemented. After 2 hours of reaction is one NCO value of 5.9 reached.

The prepolymer is in 3722 g of toluene and 1000 g of isobutanol solved. at 25 ° C with a solution of  375 g isophoronediamine in 2722 g isobutanol. After reaching a viscosity of 40,000 mPas with 20 g Butanone oxime stopped the polar addition reaction. The Solution is 30%.

810 g of the 30% solution are mixed with 160 g of ethyl acetate diluted. To this solution add 25 g of the under 1 / II) described 50% aqueous melamine resin and 5 g a silicone resin (BAYSILON®OF / OH 502, Bayer AG). Farther 100 g of the neutralized, described under 3 / I) are stirred, aqueous polyacrylic acid dispersion and then mix in 750 g of water. The two-phase Spreading paste has about 15% solids content and a viscosity (25 ° C) of 10,000 mPas.

III) Direct coating

A polyester fabric of 80 g / m ³ weight is coated analogously to 2 / III) with the base coat paste 3 / I) using an air knife and the top coat paste 3 / II) using a roller knife.

• Total circulation: 25 g / m ³
  Water resistance:
  Original 1100 mm WS
  - 30 ° C wash 1 × 900 mm WS
  30 ° C wash 3 × 800 mm WS
  - Dry cleaning 1 × 700 mm WS
  Dry cleaning 3 × 600 mm WS
  Water vapor permeability: 5 mg / cm ³ h
  Scrubb test, 1000 strokes, wet: without damage

Example 4 I) baseline

Coating paste according to example 2 / I)

II) Top line

1913 g of a polyester made from diethylene glycol and adipic acid the OHZ 44 and 102 g of a polyester made of ethylene glycol and phthalic acid of OHZ 275 are at 100 - 110 ° C with 666 g of isophorone diisocyanate. After 2- hour reaction an NCO value of 6.0 is reached. The prepolymer melt is dissolved in 5063 g of toluene. At 25 ° C is a solution of 340 g for chain extension Isophoronediamine added dropwise in 4000 g of isobutanol. To The polyaddition reaction is terminated after reaching a viscosity of 40,000 mPas 20 g butanone oxime added. The solution is 25%.

In 965 g of this solution, 25 g of the one described under 1 / II) Melamine resin solution and 10 g of the under 3 / II) described silicone resin stirred. Before dispersing with 750 g of water, 100 g of that described under 3 / I) neutralized, aqueous polyacrylic acid Dispersion incorporated. The coating paste has a viscosity (25 ° C) of 12,000 mPas.  

III) Direct coating

Analogously to Example 3 / III), a polyester fabric with the Paste 2 / I) primed and further coated with Paste 4 / II).

• Total circulation: 30 g / m ³
  Water resistance:
  - Original 1200 mm WS
  - 30 ° C wash 1 × 900 mm WS
  - Dry cleaning 1 × 700 mm WS
  Water vapor permeability: 4 mg / cm ³ h
  Scrubb test, 1000 strokes, wet: without damage

Example 5 I) baseline

1720 g of a polyester of 1,6-hexanediol, neopentyl glycol (Glycol ratio = 65:35) and adipic acid from OHZ 56.79 g of an α, ω-bishydroxymethyl-polydimethylsiloxane the OHZ 200 are analogous to 1 / I) with 555 g of isophorone diisocyanate converted to an NCO prepolymer; NCO value: 5.1%.

After dissolving the prepolymer in 3050 g of toluene and 1050 g Isobutanol is made with a solution of 255 g of isophoronediamine in 2000 g of isobutanol the polyurethane urea  built up. The polyaddition reaction is stopped using 20 g butanone oxime. The 30% solution has a viscosity (25 ° C) of 39,000 mPas.

815 g of this solution are diluted with 165 g of xylene. This diluted solution is added 20 g of the under 1 / II) described blocked polyisocyanate added. To the the solution thus obtained is added to 100 g of the solution described below neutralized polyacrylic acid dispersion and then Add 750 g of water. The two-phase coating paste has a viscosity (25 ° C) of approx. 15,000 mPas.

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

II) Top line

1720 g of the polyester used in 5 / I) and 79 g of the in 5 / I) used dimethylpolysiloxane with 710 g Isophorone diisocyanate converted to an NCO prepolymer; NCO value: 7.1%. The prepolymer is in 3350 g Toluene and 1350 g of isobutanol dissolved and analogous to 5 / I) 375 g of isophoronediamine reacted in 2000 g of isobutanol. The 20% solution has a viscosity (25 ° C) of 42,000 mPas.

815 g of this solution are diluted with 165 g of butyl acetate and blocked with 20 g of the described under 1 / II)  Polyisocyanate, 100 g of that described under 5 / I) neutralized polyacrylic acid dispersion and 750 g of water mixed well; Viscosity of the coating paste: approx. 15,000 mPas (25 ° C).

III) Direct coating

Analogously to Example 3 / III), a polyester fabric with the Paste 5 / I) primed and further coated with Paste 5 / II).

• Total circulation: 30 g / m ³
  Water resistance:
  - Original 1500 mm WS
  - 30 ° C wash 1 × 1200 mm WS
  - Dry cleaning 1 × 900 mm WS
  Water vapor permeability: 8 mg / cm ³ h
  Scrubb test, 1000 strokes, wet: without damage

Example 6 I) baseline

1720 g of a polypropylene glycol polyether of OHZ 56 and 79 g of an α, ω-bishydroxymethyl polydimethylsiloxane OHZ 200 are analogous to 1 / I) with 577 g of isophorone diisocyanate converted to an NCO prepolymer; NCO value: 5.6%.  

The NCO prepolymer melt is dissolved in 3090 g of toluene, diluted at 20 ° C with 1090 g isobutanol and with a solution of 272 g isophoronediamine in 2000 g isobutanol implemented. The 30% solution has a viscosity (25 ° C) of 42,000 mPas.

815 g of this solution are diluted with 165 g of toluene, then add 15 g of the blocked described under 1 / II) Polyisocyanate, 10 g of that described under 1 / II) aqueous melamine resin solution, 100 g of the under 1 / II) described neutralized polyacrylic acid dispersion and 750 g of water. The two-phase coating paste has a viscosity (25 ° C) of approx. 17,000 mPas.

II) Top line

2376 g of the prepolymer melt described under 6 / I) are dissolved in 3160 g of toluene and at 25 ° C with 1160 g Diluted isobutanol. The prepolymer solution is under Cooling at 25 ° C with a solution of 336 g of 4,4'-diaminodicyclohexylmethane in 2000 g isobutanol to the polyurethane urea implemented. The 30% solution has one Viscosity (25 ° C) of 42,000 mPas.

810 g of this solution are diluted with 165 g of toluene and with 25 g of the aqueous melamine resin solution described under 1 / II) and 5 g of the silicone resin described under 3 / II) transferred. Then you put 100 g of aqueous, neutralized polyacrylic acid described under 3/1) Add dispersion and 750 g of water. The approx  15% coating paste has a viscosity (25 ° C) of approx. 11,000 mPas.

Medium base paste 6 / I) and top coat paste 6 / II) can be used on fabrics made from natural and synthetic fibers Produce water vapor permeable coatings.

• Water vapor permeability: 4 - 8 mg / cm ³ h
  Water resistance: ≦ λτ1000 mm WS

Example 7 I) baseline

Analogously to 6 / I), 1720 g of a polytetramethylene glycol polyether the OHZ 56 instead of the one used there Polypropylene glycol ether with the others mentioned there Components implemented. The 30% polyurethane urea solution has a viscosity (25 ° C) of approx. 35,000 mPas. The base coat paste prepared from it analogously to 6 / I) has a solids content of approx. 15% and a viscosity (25 ° C) of 15,000 mPas.

II) Top line

1440 g of a polytetramethylene glycol polyether from OHZ 56 and 158 g of an α, ω-bishydroxymethyl-polydimethylsiloxane the OHZ 200 are analogous to 1 / I) with 710 g of isophorone diisocyanate  converted to an NCO prepolymer; the NCO value is determined to be 7.8%. The prepolymer melt is dissolved in 3120 g of toluene, at 25 ° C with 1120 g of isobutanol diluted and with cooling with a solution of 375 g of isophoronediamine reacted in 2000 g of amyl alcohol. The 30% polyurethane urea solution has a viscosity (25 ° C) of approx. 42,000 mPas. The same from it 6 / II) prepared top layer paste has a solid content 15% and a viscosity (25 ° C) of 15,000 mPas.

Fabrics made from natural and synthetic fibers can be used with the Coat base coat paste 7 / I) and top coat paste 7 / II). The articles are characterized by soft Handle, little blocking surface, good adhesion to the substrate, good water vapor permeability and high water resistance (≦ λτ1200 mm WS).

Example 8 I) baseline

Spreading paste according to Example 2 / I).

II) Top line

2193 g of a polyether made from diethylene glycol and adipic acid the OHZ 44 and 79 g of an α, ω-bishydroxymethylpolydimethylsiloxane the OHZ 200 with 760 g 4,4'-  Diisocyanato-dicyclohexyl-methane at 110 ° C in the Melt implemented. After 2 hours of reaction, the NCO content determined to be 5.0%.

The melt is dissolved in 3900 g of toluene and 1900 g n-Butanol diluted at 25 ° C. Allow to cool a solution of 323 g of isophoronediamine in 2000 g of n-butanol flow to. The 30% solution has a viscosity (25 ° C) of 32,000 mPas. The prepared from it analogously 6 / II) Top coat paste has a solids content of 15% and a viscosity (25 ° C) of 15,000 mPas.

III) Direct coating

A polyamide fabric of 100 g / m ³ weight is primed with the base coat paste 2 / I) (air knife) and then the top coat 8 / II) is applied using a roller knife; Driving conditions: analog 2 / III).

• Total circulation: 35 g / m ³
  Water resistance:
  - Original 1800 mm WS
  - 30 ° C wash 1500 mm WS
  - Dry cleaning 1000 mm WS
  Water vapor permeability: 8 mg / cm ³ h
  Srubb test, 1000 strokes, wet: without damage

Example 9 I) baseline

Coating paste according to example 2 / I)

II) Top line

1190 g of a polyester of 1,6-hexanediol, neopentyl glycol (Glycol ratio = 65:35) and adipic acid OHZ 66 and 176 g perfluorooctanesulfonic acid-N, N-bis- (2-hydroxyethyl) - amide with 490 g of isophorone diisocyanate implemented at 100-110 ° C to an NCO prepolymer. To 2 hours reaction an NCO value of 5.2% is reached. The prepolymer melt is dissolved in 2400 g of toluene, cooled to 25 ° C and diluted with 1200 g of isobutanol. With cooling, a solution of 205 g of isophoronediamine added dropwise in 1200 g of isobutanol. You get a 30% solution with a viscosity (25 ° C) of approx. 45,000 mPas. The top coat paste prepared from it 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 of 100 g / m ³ weight is primed with the base coat paste 2 / I) (air knife) and then the top coat 9 / I) is applied using a roller knife; Driving conditions: analog 2 / III).

• Total circulation: 35 g / m ³
  Water resistance:
  - Original 1600 mm WS
  - 30 ° C wash 1300 mm WS
  - Dry cleaning 1100 mm WS
  Water vapor permeability: 7 mg / cm ³ h
  Scrubb test, 1000 strokes, wet: without damage

Example 10 I) baseline

Coating paste according to example 2 / I)

II) Top line

1785 g of a polyester made from diethylene glycol and adipic acid the OH number 44, 170 g of an α, ω-bishydroxymethyl polydimethylsiloxane with OH number 99 and 88 g perfluorooctanesulfonic acid N, N-bis (2-hydroxyethyl) amide are after dewatering at 110 ° C with 710 g of isophorone diisocyanate achieved at an NCO value of 6.4%. The prepolymer melt is dissolved in 3650 g of toluene and cooled to 25 ° C. Then you drop a solution of 374 g of isophoronediamine in 3650 g of isobutanol. To A viscosity of 30,000 mPas is reached with 20 g Butanone oxime stopped and stirred at 50 ° C for 2 h. A 30% polyurethane urea solution is also obtained a viscosity (25 ° C) of 35,000 mPas.  

810 g of this solution are diluted with 165 g of toluene and with 25 g of the aqueous melamine resin solution described under 1 / II) and 5 g of the silicone resin described under 3 / II) transferred. Then you stir an aqueous Solution of 6 g of commercially available carboxymethyl cellulose (Walocel® MT 4000 GB, Wolff-Walsrode AG), 12 g triethanolamine and 82 g of water and then give in high-speed stirring 750 g of water. The approx. 15% Spreading paste has a viscosity (25 ° C) of approx.10,000 mPas.

With the base coat paste 2 / I) and the top coat paste 10 / I) can be applied using the direct coating process on fabrics made of natural and synthetic fibers permeable to water vapor Make coatings.

• Water vapor permeability: 5-10 mg / cm ³ h
  Water resistance: ≦ λτ 1000 mm WS

Example 11 I) baseline

900 g of a polytetramethylene glycol polyether OH number 112 and 56 g of an α, ω-bishydroxymethyl-polydimethylsiloxane the OH number 200 are drained and then at 100 ° C with 625 g of 4,4'-diisocyanato-diphenylmethane implemented up to an NCO value of 7.9%. it is diluted with 800 g of methyl ethyl ketone, gives 74.5 g Add ethylene glycol and stir at 80 ° C until an NCO value  of 1.0% is reached. Then with another 2850 g Diluted methyl ethyl ketone and cooled to 25 ° C. At a temperature of 15 g is dropped at this temperature Hydrazine hydrate in 250 g of water and then stirred for 3 h 50 ° C after. A cloudy but homogeneous solution is created with a solids content of 30% and a viscosity (25 ° C) of approx.20,000 mPas. The resulting analog 1 / II) prepared base coat paste has a solids content of approx. 15% and a viscosity (25 ° C) of approx. 10,000 mPas.

II) Top line

2240 g of a dehydrated polyester from 1,4-butanediol and adipic acid with an OH number of 50 are reacted in a reaction screw with 666 g of isophorone diisocyanate and 340 g of isophorone diamine at temperatures between 80 and 100.degree. The extruded melt strand is granulated after cooling.
300 g of these polyurethane urea granules are dissolved in 350 g of toluene and 350 g of isobutanol; the 30% solution has a viscosity (25 ° C) 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 that described under 1 / II) Melamine resin solution and 5 g of that described under 1 / III) Add fluorocarbon resin solution. Furthermore there 100 g of the under  1 / II) described neutralized aqueous polyacrylic acid Dispersion and 750 g of water. The so received Top coat paste has a viscosity (25 ° C) of approx. 12,000 mPas with a solids content of approx. 15%.

With the base coat paste 11 / I) and the top coat paste 11 / II) can be according to that given in Example 1 Procedure on fabrics made from natural and synthetic fibers Produce water vapor permeable coatings.

• Water vapor permeability: 7-10 mg / cm ² h
  Water resistance: ≦ λτ 1200 mm WS

Example 12 I) baseline

1000 g of the 30% polyurethane solution described in Example 5 / I) with 50 g of toluene and 50 g of isobutanol diluted. 20 g of the are added to this dilute solution Blocked polyisocyanate and described under 1 / II 15 g of a melamine resin described in 1 / II. Farther add 100 g of a 40% polyacrylate solution Ethyl acetate (copolymer of 95% by weight ethyl acrylate, 2.5% by weight acrylic acid and 2.5% by weight acrylic acid β-hydroxypropyl ester), 10 g of a 20% solution of p-toluenesulfonic acid in isopropanol and 100 g of one aqueous ammonia solution (10% by weight ammonia conc., 90 wt .-% water) added. By incorporating 700 g Finally, water is obtained from a two-phase coating paste with a viscosity of approx. 18000 mPa.s / 25 ° C.  

II) Top line

1000 g of the 30% strengths described in Example 5 / II Polyurethane solution are as described in 12 / I / base line, diluted with 50 g toluene and 50 g isobutanol. 20 g of the solution from Example 1 / II are added to this solution described melamine resin, 50 g of 12 / I / base coat described 40% polyacrylate solution in Ethyl acetate, 10 g of a 20% solution of p-toluenesulfonic acid in isopropanol and 100 g of an aqueous Ammonia solution as described in 12 / I / base line. After 900 g of water have been stirred in proportionately, a viscous, two-phase coating paste with a viscosity of 15000 mPa.s / 25 ° C.

III) Direct coating

Analogously to Example 3 / III, a polyester fabric with the Coating paste 12 / I primed and with the top coat paste 12 / II further coated.

• Total circulation: 35 g / m ²
  Water resistance:
  - Original 2000 mm WS
  - 30 ° C wash 1 × 1600 mm WS
  - Dry cleaning 1 × 1200 mm WS
  Water vapor permeability: 8 mg / cm ² × h
  Scrubb test, 1000 strokes, wet: without damage

Example 13 I) baseline

1000 g of the 30% polyurethane solution described in Example 5 / I be with 50 toluene in 50 g of isobutanol diluted. 20 g of the are added to this dilute solution Blocked polyisocyanate and described under 1 / II 15 g of a melamine resin described in 1 / II. 10 g of a 20% solution of p-toluenesulfonic acid are also added in isopropanol and 100 g of an aqueous Ammonia solution (10% by weight ammonia conc. +90% by weight Water). Obtained by incorporating 700 g of water finally a two-phase coating paste with a Viscosity of 20,000 mPas / 25 ° C.

II) Top line

1000 g of the 30% polyurethane solution described in Example 5 / II be as described in 12 / I with 50 g Toluene and 50 g of isobutanol diluted. About this solution 20 g of the melamine resin described in Example 1 / II are added, 10 g of a 20% solution of p-toluenesulfonic acid in isipropanol and 100 g of an aqueous ammonia solution as in 12 / I. After stirring in 100 g of water gives a viscous two-phase Spreading paste with a viscosity of approx. 18,000 mPas at 25 ° C.  

III) Direct coating

Analogously to Example 3 / IIIc, a polyester fabric with the Coating paste 13 / I primed and with top coat paste 13 / II further coated.

• Total circulation: 35 g / m ²
  Water resistance:
  - Original 2000 mm WS
  - 30 ° C wash 1 × 1800 mm WS
  - Dry cleaning 1 × 1000 mm WS
  Water vapor permeability: 4 mg / cm ² h
  Scrubb test, 1000 strokes, wet: without damage

Example 14 I) base paste

Spreading paste according to Example 12 / I

II) Top line

1000 g of the 30% strength described in Example 8 / II Polyurethane solution with 50 g of toluene and 50 g of isobutanol diluted. 20 g of the in. Are added to this solution Example 1 / II described melamine resin and 10 g of one 20% solution of p-toluenesulfonic acid and 100 g of one  aqueous ammonia solution as in 12 / I. After proportional Stirring 900 g of water gives a viscous, two-phase coating paste with a viscosity of approx. 18,000 mPas / 25 ° C.

III) Direct coating

Analogously to Example 3 / III, a polyester fabric with the Spreading paste 14 / I primed and with the top coat paste 14 / II treated further.

• Total circulation: 30 g / m ²
  Water resistance:
  - Original 1800 mm WS
  - 30 ° C wash 1 × 1500 mm WS
  - Dry cleaning 1 × 1000 mm WS
  Water vapor permeability: 6 mg / cm ² h
  Scrubb test, 1000 strokes, wet: without damage

Claims (11)

1. A process for the production of water vapor permeable coatings on textile or leather substrates in the direct or transfer process according to the principle of evaporation coagulation using polyurethane plastics containing, optionally pigmented coating pastes, characterized in that multiphase mixtures as coating pastes

• A) 5 to 50% by weight of hydrophobic polyurethanes and / or polyurethane ureas, the 1 to 30% by weight of structural components from the group consisting of silicone resins, aromatic molecular segments containing polyethers or polyesters and / or perfluorocarbon resins,
  built-in included,
• B) 0-30% by weight of hydrophobic polyurethanes and / or polyurethane ureas per se, which are built up without the special structural components mentioned under A),
• C) 4.5-50% by weight of organic solvents for A) and B),
• D) 0 to 40% by weight of organic non-solvents for A) and B),
• E) 0-10% by weight, preferably 0.5-5% by weight, of polymers which are free from urethane and urea groups and carry carboxyl groups which are completely or partially neutralized with bases,
• F) 10-70% by weight of water and
• G) 0-5% by weight of crosslinking agents, water repellents, stabilizers and / or further coating aids

be used. 2. The method according to claim 1, characterized in that that the polyurethanes or polyurethane ureas A) 1-20 wt .-% containing polysiloxane segments Connections with at least two terminal and / or lateral, reactive to isocyanates Groups included as structural components. 3. The method according to claim 1, characterized in that the polyurethanes or polyurethane ureas A) contain 1-20% by weight of hydroxyfunctional polyethers prepared by oxalkylation of aromatic compounds having at least two phenolic hydroxyl groups as synthesis components, these polyethers being less than 10 wt .-% consist of oxyethylene segments -CH ₂ -CH ₂ -O-. 4. The method according to claim 1, characterized in that the polyurethanes or polyurethane ureas A) 1-20% by weight of polyesters of the isomeric phthalic acids with at least two end and / or side branches Contain hydroxyl groups as structural components. 5. The method according to claim 1, characterized in that the polyurethanes or polyurethane ureas A) 1-20% by weight of perfluoroalkyl groups Connections with at least two end and / or lateral, isocyanate reactive Groups included as structural components. 6. The method according to claim 1 to 5, characterized in that that the polyurethanes or polyurethane ureas A) two or more of the claims 3 - 5 special assembly components 3 a-d in a total amount of 1-20% by weight contain. 7. The method according to claim 1 to 6, characterized in that that the organic solvent C) Alcohols and / or ketones with 4 to 6 each Are carbon atoms and that the organic Non-solvent D) aromatic and / or aliphatic Hydrocarbons with 6-10 carbon atoms and / or fatty acid esters with 3-7 carbon atoms are. 8. The method according to claim 1 to 7, characterized in that of urethane and urea groups free polymers E) homo- or copolymeric polyacrylic  and / or polymethacrylic acids and / or carboxyl groups containing cellulose derivatives, the All or part of carboxyl groups with bases are neutralized. 9. The method according to claim 1 to 8, characterized in that multi-phase, stable mixtures as coating pastes

• A) 5-30 wt .-% in itself hydrophobic polyurethane ureas, which
  • 1) 10-40 wt .-% aliphatic polyisocyanates and
  • 2) at least 40% by weight of aliphatic polyhydroxyl compounds with a molecular weight of 500 - 5000 and
  • 3a) 0-15% by weight of dihydroxymethylpolydimethylsiloxanes with a molecular weight of 300-3000 and / or
  • 3b) 0-15% by weight of alkoxylated bis- (hydroxyphenyl) alkanes with a molecular weight of 300-2000 with less than 10% by weight of oxyethylene segments -CH ₂ -CH ₂ -O- and / or
  • 3c) 0-15% by weight of at least two terminal and / or pendant hydroxyl-containing polyesters of the isomeric phthalic acids with a molecular weight of 250-2000 and / or
  • 3d) 0-15% by weight of diols with at least three perfluoroalkyl groups containing perfluorinated carbon atoms and having a molecular weight of 300-2000,
  • the sum of the percentages of the structural components 3a) to 3d) being 1-20%, and
  • 4a) 0-20% by weight of polyhydroxyl compounds with a molecular weight of 62-399 and / or
  • 4b) 2-20 wt .-% 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) optionally 0-30% by weight of per se hydrophobic polyurethanes and / or polyurethane ureas which are produced without the special structural components 3a) -3d) mentioned under A),
• C) 4.5-40% by weight of alcohols and / or ketones, each with 4-6 carbon atoms,
• D) at least 5% by weight of aromatic and / or aliphatic hydrocarbons with 6-10 carbon atoms and / or fatty acid esters with 3-7 carbon atoms,
• E) 0-10% by weight, preferably 0.5-5% by weight, of poly- (meth) acrylic acids and / or (meth) acrylic acid copolymers neutralized in whole or in part with bases
• F) 20-60 wt .-% water and
• G) 0-5% by weight of crosslinking agents, water repellents, stabilizers and / or further coating aids are used.

10. Spreading pastes, in the form of multi-phase, stable mixtures

• A) 5-30 wt .-% in itself hydrophobic polyurethane ureas, which
  • 1) 10-40 wt .-% aliphatic polyisocyanates and
  • 2) at least 40% by weight of aliphatic polyhydroxyl compounds with a molecular weight of 500-5000 and
  • 3a) 0-15% by weight of dihydroxymethylpolydimethylsiloxanes with a molecular weight of 300-3000 and / or
  • 3b) 0-15% by weight of oxalkyllylated bis- (hydroxyphenyl) alkanes of molecular weight 300-2000 with less than 10% by weight of oxyethylene segments -CH ₂ -CH ₂ -O- and / or
  • 3c) 0-15% by weight of at least two terminal and / or pendant hydroxyl-containing polyesters of the isomeric phthalic acids with a molecular weight of 250-2000 and / or
  • 3d) 0-15% by weight diols with at least three perfluoroalkyl groups containing perfluorinated carbon atoms and having a molecular weight of 300-2000,
  • the sum of the percentages of the structural components 3a) to 3d) being 1-20%, and
  • 4a) 0-20% by weight of polyhydroxyl compounds with a molecular weight of 62-399 and / or
  • 4b) 2-20 wt .-% polyamines and / or hydrazine and / or hydrazine derivatives of molecular weight 32 and 62 to 399 and
  • 5) 0-5% by weight of other structural components,
• B) optionally 0-30% by weight of per se hydrophobic polyurethanes and / or polyurethane ureas which are produced without the special structural components 3a) -3d) mentioned under A),
• C) 4.5-40% by weight of alcohols and / or ketones, each with 4-6 carbon atoms,
• D) at least 5% by weight of 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 and / or (meth) acrylic acid copolymers neutralized in whole or in part with bases
• F) 20-60 wt .-% water and
• G) 0-5% by weight of crosslinking agents, water repellents, stabilizers and / or further coating aids.