Use of carboxylic acid derivatives based on polyamines and / or polyalkanolamines in aqueous polyurethane dispersions

Abstract

The present application describes the use of carboxylic acid derivatives based on polyamines and / or polyalkanolamines as additives in aqueous polymer dispersions for the preparation of porous polymer coatings, preferably for the preparation of porous polyurethane coatings.

Description

TECHNICAL FIELD

[0001] The present invention belongs to the field of plastic coatings and artificial leather.

[0002] It more particularly relates to the production of porous polymer coatings, preferably porous polyurethane coatings, using carboxylic acid derivatives based on polyamines and / or polyalkanolamines as additives. BACKGROUND

[0003] Plastic-coated fabrics such as artificial leather are usually composed of a fabric carrier, on which a porous polymer layer is laminated, which in turn is coated with a top layer or topcoat.

[0004] In the present application, the porous polymer layer preferably has pores in the micrometer range and is air-permeable, thus gas-permeable, i.e. permeable to water vapor, but nevertheless water-repellent. The porous polymer layer usually comprises a porous polyurethane. In order to produce PU-based artificial leather in an environmentally friendly manner, a method based on aqueous polyurethane dispersions has recently been developed. These usually consist of polyurethane microparticles dispersed in water; and the solids content is usually in the range of 30-60% by weight. In order to produce a porous polyurethane layer, these PUDs are mechanically foamed, applied to the carrier (layer thickness usually between 300-2000 pm) and then dried at elevated temperature. During this drying step, the water present in the PUD system evaporates, which leads to the formation of a polyurethane particle film. In order to further increase the mechanical strength of the film, it is also possible to additionally add hydrophilic (poly)isocyanates or carbodiimides to the PUD system during the production process, which can react with the free OH groups present on the surface of the polyurethane particles during the drying step, thus leading to additional crosslinking of the polyurethane film.

[0005] The mechanical and haptic properties of the PUD coating thus produced depend to a crucial extent on the cell structure of the porous polyurethane film. Furthermore, the cell structure of the porous polyurethane film influences the air permeability and gas permeability of the material. Here, very fine, homogeneously distributed cells can be utilized to achieve particularly good properties. A conventional way of influencing the cell structure during the production process described above is to add a foam stabilizer to the PUD system before or during mechanical foaming. The first role of a suitable stabilizer is that a sufficient amount of air can be entrained into the PUD system during the foaming operation. Secondly, the foam stabilizer has a direct influence on the morphology of the air bubbles produced. The stability of the air bubbles is also influenced to a crucial extent by the type of stabilizer. This is particularly important during the drying of the foamed PUD coating, since in this way it is possible to prevent drying defects such as cell coarsening or drying cracks.

[0006] The prior art discloses a number of ionic and non-ionic surfactants which can be used for producing porous PUD-based textile composites. Particularly preferred in this context are anionic surfactants which are usually based on ammonium stearate; see for example US 2015 / 0284902 A1 or US 2006 0079635 A1.

[0007] However, the use of corresponding ammonium stearate-based stabilizers is accompanied by a number of disadvantages. One significant disadvantage here is that ammonium stearate has a very high migration ability in the finished artificial leather. Such an effect is that surfactant molecules accumulate over time at the artificial leather surface, which can lead to a whitening of the leather surface. Furthermore, this surfactant migration can lead to an unpleasantly greasy film on the artificial leather surface, especially when the corresponding material is in contact with water.

[0008] Another disadvantage of ammonium stearate is that it forms insoluble lime soap when it comes into contact with hard water. In the case of artificial leather produced on the basis of ammonium stearate which comes into contact with hard water, a white bloom can thus arise at the artificial leather surface, which is particularly undesirable in the case of dark leathers.

[0009] Yet another disadvantage of ammonium stearate-based foam stabilizers is that they do enable effective foaming of aqueous polyurethane dispersions, but often lead to a rather coarse and irregular foam structure. This can have a disadvantageous effect on the optical and haptic properties of the finished artificial leather.

[0010] Yet another disadvantage of ammonium stearate is that the PUD foams produced often have insufficient stability, which can lead to defects in their processing, especially when the PUD foam is dried at elevated temperatures. As a result of this, for example, the corresponding foam must be dried relatively gently and slowly, which in turn leads to longer processing times in artificial leather production.

[0011] Another disadvantage of ammonium stearate is that it must often be used in combination with other surfactants in order to be able to achieve sufficient foam stability at all; for example, the prior art describes sulfosuccinamates here. These additional components lead to an increase in complexity in use.

[0012] The problem addressed by the present application is therefore to provide an additive for producing PUD-based foam systems and foam coatings which enables effective foaming of PUD systems without having to accept the disadvantages associated with the use of ammonium stearate as stated in the prior art. As an alternative to ammonium stearate-based foam stabilizers, polyol esters and polyol ethers have been identified in the past as effective foam additives for aqueous polyurethane dispersions. These structures are described, for example, in documents EP 3487945 A1 and WO 2019042696 A1. It has now surprisingly been found that the use of carboxylic acid derivatives based on polyamines and / or polyalkanolamines likewise enables the problem to be solved. SUMMARY

[0013] The present application therefore provides the use of carboxylic acid derivatives based on polyamines and / or polyalkanolamines as additives in aqueous polymer dispersions, preferably for the production of porous polymer coatings, preferably in aqueous polyurethane dispersions, preferably as foam additives, especially for the production of porous polyurethane coatings.

[0014] The use of carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the present application has surprisingly manifold advantages here.

[0015] One advantage is that carboxylic acid derivatives based on polyamines and / or polyalkanolamines enable the aqueous PUD systems to be foamed particularly effectively. The foams produced thereby are notable here for a particularly fine cell structure with a particularly homogeneous cell distribution, which in turn has a very advantageous effect on the mechanical and haptic properties of the porous polymer coatings produced on the basis of these foams. Furthermore, the air permeability and breathability of the coatings can be improved in this way.

[0016] A further advantage is that carboxylic acid derivatives based on polyamines and / or polyalkanolamines enable particularly stable foams to be produced. This firstly has an advantageous effect on their processability. Secondly, the advantage of the improved foam stability is that during the drying of the respective foam, drying defects such as cell coarsening or drying cracks can be avoided. Furthermore, the improved foam stability enables the foams to be dried more quickly, which offers process advantages from an environmental and economic point of view.

[0017] A further advantage is that carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the present application have virtually no migratory properties in the finished artificial leather, if at all, and thus do not lead to undesirable surface discoloration or blooming. Furthermore, the surfactants according to the present application are virtually insensitive to hard water, if at all.

[0018] An additional advantage of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the present application is that they can lead to an increase in the viscosity of the foamed, undried dispersion. This in turn can have an advantageous effect on the processability of the foam. Furthermore, depending on the specific case, it can result in the use of additional thickeners for adjusting the foam viscosity being able to be dispensed with or their use concentration being able to be reduced, which brings economic advantages.

[0019] A further advantage of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the present application is that they lead to sufficiently stable foams based on aqueous polymer dispersions even without the use of additional surfactants. This can reduce the complexity for some users in assembling suitable foam formulations.

[0020] Another advantage of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the present application is their excellent hydrolytic stability in a broad pH range and thus also their use in polymer dispersions having very low or very high pH values. The present application is further described in the following by way of example without any intention to limit the present application to these exemplary embodiments. In the case of the following specified ranges, general formulae or classes of compounds, these are intended to include not only the respective ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds obtainable by removing individual values (ranges) or compounds. In the case of references to literature in the context of the present specification, the entire content thereof, in particular with respect to the subject matter forming the context of the reference, is fully incorporated into the disclosure of the present application. Percentages are by weight percent, unless otherwise indicated. In the case of parameters given below which are determined by measurement, the measurement is carried out at a temperature of 25°C and a pressure of 101 325 Pa, unless otherwise indicated. In the case of the use of chemical (empirical) formulae in the present application, the indices specified can be not only absolute numbers, but also average values. For polymeric compounds, the indices preferably represent average values. The structures and empirical formulae presented in the present application represent all possible isomers which result from different arrangements of the repeating units.

[0021] In the context of the present application, the expression "carboxylic acid derivatives based on polyamines and / or polyalkanolamines" encompasses, inter alia, compounds obtainable by reacting at least one polyamine and / or one polyalkanolamine with at least one acyl donor, such as a carboxylic acid, a carboxylic acid ester, a carbonic acid halide or a carboxylic anhydride, particularly preferably a carboxylic acid. For these reactions, suitable catalysts can optionally be used as required, such as organic or inorganic acids, for example p-toluenesulphonic acid, sulphuric acid or methanesulphonic acid, acid salts, carbonic acid chlorides, metal or amphoteric metal oxides, metal alkoxides or carboxylates, such as (ortho)titanate tetrabutylate or tin(II) 2-ethylhexanoate. Further optional auxiliaries, such as activated carbon or entraining agents for the removal of water, can likewise be used. The corresponding reactions are known to the person skilled in the art and are described, for example, in - Chemie Lexikon (Thieme-Verlag, 1996).

[0022] In the context of the present application throughout, the term "polyamine" encompasses, inter alia, saturated or unsaturated, open-chain or cyclic, straight-chain or branched organic compounds having at least two or more terminal amine groups, which chain can have secondary or tertiary amino groups.

[0023] Within the entire scope of the present application, the term "polyalkanolamines" includes, inter alia, saturated or unsaturated, open-chain or cyclic, straight-chain or branched organic compounds having at least two or more terminal OH groups, whose chain can be interrupted by secondary or tertiary amino groups and / or ether groups, wherein these compounds contain at least one amine group and at least two OH groups.

[0024] Within the entire scope of the present application, the expression "carboxylic acid derivatives based on polyamines and / or polyalkanolamines" also includes alkoxylated adducts thereof, which can be obtained by reaction of carboxylic acid derivatives based on polyamines and / or polyalkanolamines with alkylene oxides such as ethylene oxide, propylene oxide and / or butylene oxide.

[0025] The preparation of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the application by using mono- and / or polyfunctional di- and / or tri-carboxylic acids is a particularly preferred embodiment of the present application. Preferred carboxylic acids which can be used for the preparation of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the application conform to the general formula R-C(0)OH, wherein R is a monovalent aliphatic saturated or unsaturated hydrocarbon radical having 3 to 39 carbon atoms, preferably 7 to 21 and more preferably 9 to 17 carbon atoms. Particularly preferred here are carboxylic acids selected from the group consisting of caproic acid (butyric acid), caprylic acid (hexanoic acid), capric acid (octanoic acid), pelargonic acid (nonanoic acid), capuric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z)-9-hexadecenoic acid), oleic acid ((Z)-9-octadecenoic acid), elaidic acid ((E)-9-octadecenoic acid), cis-vaccenic acid ((Z)-11-octadecenoic acid), linoleic acid ((9Z,12Z)-9,12-octadecadienoic acid), a-linolenic acid ((9Z,12Z,15Z)-9,12,15-octadecatrienoic acid), g-linolenic acid ((6Z,9Z,12Z)-6,9,12-octadecatrienoic acid), dihomo-g-linolenic acid ((8Z,11Z,14Z)-8,11,14-eicosatrienoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-5,8,11,14-eicosatetraenoic acid), brassidic acid ((Z)-13-docosenoic acid), nervonic acid ((Z)-15-tetracosenoic acid), ricinoleic acid, hydroxystearic acid and / or undecylenic acid, and mixtures thereof, such as, for example, rapeseed oil acid, soybean fatty acid, sunflower fatty acid, peanut fatty acid and tall oil fatty acid. Very particularly preferred are palmitic acid and / or stearic acid, in particular mixtures of these substances. According to the application, pure fatty acids and also technical-grade qualities thereof having a chain length distribution or containing mixtures of different chain length fatty acids are preferred. Also preferred according to the application are partially hydrogenated fatty acids.

[0026] Suitable sources of fatty acids can be plant or animal fats, oils, or waxes. For example, the following can be used: lard, beef tallow, goose fat, duck fat, chicken fat, horse fat, whale oil, fish oil, palm oil, olive oil, avocado oil, seed oil, coconut oil, palm kernel oil, cocoa butter, cottonseed oil, pumpkin seed oil, corn kernel oil, sunflower oil, wheat germ oil, grapeseed oil, sesame oil, flaxseed oil, soybean oil, peanut oil, lupin oil, rapeseed oil, mustard oil, castor oil, jalapeno oil, walnut oil, jojoba oil, and lecithin, such as those based on soybeans, rapeseed, or... Sunflower oil, bone oil, cow's foot oil, borage oil, lanolin, emu oil, deer fat, marmot oil, mink oil, safflower oil, hemp oil, pumpkin oil, evening primrose oil, tallow, as well as carnauba wax, beeswax, candelilla wax, copra wax, sugarcane wax, vine wax, palm wax, copra wax, tung oil, alfalfa wax, bamboo wax, hemp wax, Douglas fir wax, cork wax, sisal wax, linseed wax, cotton wax, damar wax, tea wax, coffee wax, rice wax, oleander wax, or wool wax.

[0027] Furthermore, it is advantageous to use polyfunctional dicarboxylic acids and / or tricarboxylic acids to prepare the polyamine- and / or polyalkanolamine-based carboxylic acid derivatives according to the present invention. Preferably, these are aliphatic straight-chain or branched dicarboxylic acids and / or tricarboxylic acids having a chain length of 2 to 18 carbon atoms, and / or (technical grade) dimer fatty acids obtained by catalytic dimerization of unsaturated fatty acids having 12 to 22 carbon atoms. Examples of corresponding polyfunctional acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, brassic acid, taprolic acid, malonic acid, tartaric acid, malic acid, itaconic acid, and / or citric acid. Particularly preferably, a combination of polyfunctional dicarboxylic acids and / or tricarboxylic acids with the monofunctional carboxylic acids described above can be used to obtain cross-linked polyamine- and / or polyalkanolamine-based carboxylic acid derivatives.

[0028] The polyamine used to prepare the carboxylic acid derivatives according to the invention is preferably selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethyleneheptamine, dipropylenetriamine, tripropylenetetramine, tetraethylenepentamine, pentaethyleneheptamine, spermine, spermidine, and N-alkylated and N-methylated derivatives of these compounds, polyethyleneimine, polypropyleneimine and / or (co)polymers with amine groups, especially (co)polymers based on allylamine and / or vinylamine, and mixtures of these substances, with polyethyleneimine being particularly preferred.

[0029] The polyalkanolamines used for preparing the carboxylic acid derivatives according to the application are preferably selected from the group consisting of polydiethanolamine, polydipropyl alcohol amine, polydiisopropyl alcohol amine, polytriethanolamine, polytripropyl alcohol amine, polytriisopropyl alcohol amine, polyether amines, in particular based on polyethylene oxide, polypropylene oxide and polyethylene oxide-polypropylene oxide copolymers, and / or (co)polymers with OH and amine groups, in particular copolymers based on allyl alcohol, vinyl alcohol, allyl amine and vinyl amine, and mixtures of these substances, with polytriisopropyl alcohol amine being particularly particularly preferred.

[0030] Furthermore, in the context of the present application, preference is given to polyalkanolamines which are obtainable by condensation of N-(hydroxyalkyl)amines, particularly preferably trialkanolamines of general formula 1,

[0031] polyalkanolamines which are obtainable by condensation of trialkanolamines of formula 1,

[0032]

[0033] wherein R1to R 3 groups are independently identical or different 1,2-alkylene groups having 2 to 4 carbon atoms. Furthermore, preference is also given to polyalkanolamines which are obtainable by co-condensation of N-(hydroxyalkyl)amines, particularly preferably trialkanolamines of general formula 1, with other molecules with hydroxyl groups, such as pentaerythritol, sorbitol, glycol, glycerol or polyglycerol, as described, for example, in document EP 0 057 398.

[0034] Furthermore, polyamine and polyalkanolamine alkoxylate adducts which are obtainable by reacting polyamines and polyalkanolamines, in particular as detailed above, with alkylene oxides such as ethylene oxide, propylene oxide and / or butylene oxide, as described, for example, in document US20100234631 A1, can also be used for preparing the carboxylic acid derivatives according to the application.

[0035] If polyethyleneimines are used for preparing the carboxylic acid derivatives according to the application, these can preferably be obtained by ring-opening polymerization of ethyleneimine. Furthermore, polyethyleneimines having an average molar mass of less than 25 000 g / mol, more preferably less than 12500 g / mol, even more preferably less than 5000 g / mol, even more preferably less than 2000 g / mol are particularly preferred. The average molar mass can preferably be determined here by gel permeation chromatography (GPC). For this purpose, for example, a SECcurity2 GPC system from PCC can be used, calibrated against polystyrene.

[0036] If (co)polymers with amine groups are used for preparing the polyamine-based carboxylic acid derivatives according to the application, these preferably have at least one repeat unit A of general formula 2,

[0037]

[0038] and / or at least one repeating unit B of general formula 3,

[0039]

[0040] wherein R 4 are identical or different monovalent aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 15 carbon atoms, preferably 1 to 10, more preferably having 1 to 5 carbon atoms, or are H, more preferably H.

[0041] In the case of polyalkanolamine-based carboxylic acid derivatives, use is made in their preparation of copolymers which carry OH and amine groups, especially preferred ones of which have, in addition to the repeating units A and / or B, at least one repeating unit C of formula 4,

[0042]

[0043] and / or at least one repeating unit D of general formula 5,

[0044]

[0045] It is likewise preferred that, in addition to the repeating units A to D, an optionally present further monoethylenically unsaturated comonomer or comonomer mixture is introduced by polymerization into the polymer used for the preparation of the carboxylic acid derivatives according to the application in order to thereby obtain a further modified polymer. These comonomers can be nonionic, cationic or anionic monomers. Preferred nonionic comonomers here are unsaturated alcohols, such as vinyl or allyl alcohol and their alkoxylates, unsaturated nitriles, aliphatic or aromatic olefins, N-vinyl lactams, such as N-vinyl pyrrolidone or N-vinyl caprolactam, vinyl esters of organic carboxylic acids, esters of monoethylenically unsaturated carboxylic acids and amides of monoethylenically unsaturated carboxylic acids. Preferred cationic comonomers are vinyl imidazole and monomers containing vinyl imidazole units, their alkyl derivatives and quaternized products, vinyl pyridine and its quaternized products, basic esters of ethylenically unsaturated carboxylic acids with amino alcohols and basic amides of ethylenically unsaturated carboxylic acids with N,N-dialkylaminoalkyl amines. Preferred anionic comonomers are α,β-unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and partial esters of unsaturated dicarboxylic acids.

[0046] In the context of the present application, it is furthermore preferred that the polyamine- and / or polyalkanolamine-based carboxylic acid derivatives according to the present application are produced using (co)polymers which carry amine groups and / or amine and OH groups and have an average molar mass of less than 25 000 g / mol, more preferably less than 12 500 g / mol, even more preferably less than 5000 g / mol, even more preferably less than 2000 g / mol. The average molar mass can here preferably be determined by gel permeation chromatography (GPC). For this purpose, for example, the SECcurity2 GPC system from PCC can be used, calibrated against polystyrene.

[0047] In the context of the present application, it is preferred that the polyamine- and / or polyalkanolamine and carboxylic acid are reacted in such a way that the molar ratio of amine and OH functions which are reactive towards carboxylic acid to carboxylic acid is in the range from 5:1 to 1.5:1, more preferably in the range from 4:1 to 1.7:1, even more preferably in the range from 3.5:1 to 1.9:1, even more preferably in the range from 3:1 to 2:1.

[0048] As already described, the present application envisages the use of the polyamine- and / or polyalkanolamine-based carboxylic acid derivatives as described above as additives in aqueous polymer dispersions, preferably in aqueous polyurethane dispersions. The polymer dispersions here are preferably selected from the group consisting of aqueous polystyrene dispersions, polybutadiene dispersions, poly(meth)acrylate dispersions, polyvinyl ester dispersions and / or polyurethane dispersions. The solids content of these dispersions is preferably in the range from 20 to 70% by weight, more preferably in the range from 25 to 65% by weight. According to the present application, the use of the polyamine- and / or polyalkanolamine-based carboxylic acid derivatives as additives in aqueous polyurethane dispersions is particularly preferred. Polyurethane dispersions based on polyester polyols, polyester amide polyols, polycarbonate polyols, polyacetal polyols and / or polyether polyols are particularly preferred here.

[0049] In the context of the present application, it is preferred that the concentration of the polyamine- and / or polyalkanolamine-based carboxylic acid derivatives is in the range from 0.1 to 20% by weight, more preferably in the range from 0.2 to 15% by weight, particularly preferably in the range from 0.5 to 10% by weight, based on the total weight of the aqueous polymer dispersion.

[0050] The polyamine- and / or polyalkanolamine-based carboxylic acid derivatives are preferably used in aqueous polymer dispersions as blowing aids or foam stabilizers for foaming the dispersions, i.e. as blowing additives. However, in addition, they can also be used as drying aids, levelling additives, wetting agents and rheological additives, which likewise correspond to preferred embodiments of the present application.

[0051] In addition to the polyamine- and / or polyalkanolamine-based carboxylic acid derivatives according to the application, the aqueous polymer dispersions can also comprise further additives / formulation components, such as dyes or pigments, fillers, matting agents, stabilizers such as hydrolysis or UV stabilizers, antioxidants, absorbers, crosslinking agents, levelling additives, thickeners and / or further co-surfactants.

[0052] The polyamine- and / or polyalkanolamine-based carboxylic acid derivatives can be added to the aqueous dispersion in pure form or in a blend in a suitable solvent. In this regard, preferred solvents are selected from the group consisting of water, propylene glycol, dipropylene glycol, polypropylene glycol, butyl diglycol, butyl triglycol, ethylene glycol, diethylene glycol, polyethylene glycol, polyalkylene glycols based on ethylene oxide, propylene oxide, butylene oxide and / or styrene oxide (EO, PO, BO, SO), alcohol alkoxylates based on EO, PO, BO and / or SO, and mixtures of these substances, very particularly preferably aqueous dilutions or blends. The blends or dilutions of polyamine- and / or polyalkanolamine-based carboxylic acid derivatives preferably contain at least 5% by weight, more preferably at least 10% by weight, even more preferably at least 15% by weight of polyamine- and / or polyalkanolamine-based carboxylic acid derivatives.

[0053] In the case of aqueous dilutions or blends of polyamine- and / or polyalkanolamine-based carboxylic acid derivatives according to the application, it can be advantageous to add a hydrotropic compound to the blend. Hydrotropic compounds here are water-soluble organic compounds consisting of a hydrophilic and a hydrophobic part, but have too low a molecular weight to have surfactant properties. The term "hydrotropic compound" is known to the person skilled in the art. In the context of the present application, preferred hydrotropic compounds are alkali metal and ammonium salts of toluenesulfonic acid, alkali metal and ammonium salts of xylene sulfonic acid, alkali metal and ammonium salts of naphthalenesulfonic acid, alkali metal and ammonium salts of cumenesulfonic acid, and phenol alkoxylates having up to 6 alkoxylate units, in particular phenol ethoxylates.

[0054] It can also be advantageous if the carboxylic acid derivatives based on polyamines and / or polyalkanolamines are not used in pure form, but as additives in aqueous polymer dispersions, preferably in aqueous polyurethane dispersions, in combination with further co-surfactants. For example, these can be used to improve the system compatibility or, in the case of pre-formulated surfactant mixtures, to improve the formulation properties. Preferred co-surfactants in this context according to the application are, for example, free fatty alcohols, fatty acid amides, ethylene oxide-propylene oxide block copolymers, betaines, such as amido propyl betaines, amine oxides, quaternary ammonium surfactants, amphoteric acetates, ammonium and / or alkali metal salts of fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl benzene sulfonates, alkyl phosphates, alkyl sulfosuccinates, alkyl sulfosuccinamates and / or alkyl sarcosinates, and mixtures of these substances, very particularly preferably free fatty alcohols having 12 to 40, more preferably 14-30, even more preferably 16-24 carbon atoms, and alkyl sulfates having 12 to 40, more preferably 14-30, even more preferably 16-24 carbon atoms, and mixtures of these substances. Furthermore, the co-surfactants can comprise silicone-based surfactants, such as trisiloxane surfactants or polyether siloxanes. In the case of ammonium and / or alkali metal salts of fatty acids, it is preferred that they contain less than 25% by weight of stearate, in particular no stearate.

[0055] In the case of a combination of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the application as described above with further co-surfactants, it is particularly preferred that the combination of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the application and the co-surfactants comprises 1 to 60% by weight, preferably 2 to 50% by weight, more preferably 3 to 40% by weight, even more preferably 5 to 30% by weight of the co-surfactants.

[0056] As described above, the use of carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the application leads to a significant improvement in the porous polymer coating produced from the aqueous polymer dispersion, the application likewise provides an aqueous polymer dispersion comprising at least one carboxylic acid derivative based on polyamines and / or polyalkanolamines, as described in detail above.

[0057] The application further provides a porous polymer layer produced from an aqueous polymer dispersion, which is obtained by the use of the carboxylic acid derivatives based on polyamines and / or polyalkanolamines according to the application as described in detail above.

[0058] Preferably, the porous polymer coating according to the application can be produced by a method comprising the following steps:

[0059] a) providing a mixture comprising at least one aqueous polymer dispersion, at least one carboxylic acid derivative based on a polyamine and / or a polyalkanolamine according to the present application, and optionally further additives,

[0060] b) foaming the mixture to give a foam,

[0061] c) optionally adding at least one thickening agent to adjust the viscosity of the wet foam,

[0062] d) applying a coating of the foamed polymer dispersion to a suitable carrier,

[0063] e) drying / curing the coating.

[0064] The porous polymer coating has pores preferably in the micrometer range, preferably an average cell size of less than 350 pm, further preferably less than 200 pm, especially preferably less than 150 pm, most preferably less than 100 pm. The average cell size can preferably be determined by microscopy, preferably by electron microscopy. For this purpose, the cross-section of the porous polymer coating is observed by means of a microscope with sufficient magnification and the size of at least 25 cells is determined. The average cell size is then calculated as the arithmetic mean of the observed cell or cell sizes.

[0065] In view of the preferred configurations, especially in view of the carboxylic acid derivatives based on a polyamine and / or a polyalkanolamine and the polymer dispersions which can preferably be used in the process, reference is made to the preceding description as well as the aforementioned preferred embodiments, especially as detailed in the claims.

[0066] It is clear that the method steps of the process according to the present application as described above do not undergo any fixed order in time. For example, method step c) can be carried out simultaneously with method step a) at an early stage.

[0067] One preferred embodiment of the present application is that in method step b) the aqueous polymer dispersion is foamed by applying high shear forces. The foaming can here be carried out with the aid of shear units familiar to the person skilled in the art, such as Dispermats, dissolvers, Hansa mixers or Oakes mixers.

[0068] Furthermore, it is preferred that the wet foam produced at the end of method step c) has a viscosity of at least 5 Pa s, preferably at least 10 Pa s, more preferably at least 15 Pa s, and even more preferably at least 20 Pa s, but not more than 500 Pa s, preferably not more than 300 Pa s, more preferably not more than 200 Pa s and even more preferably not more than 100 Pa s. The viscosity of the foam can here preferably be determined by means of a Brookfield viscometer LVT type with LV-4 spindle. The corresponding test method for determining the viscosity of the wet foam is known to the person skilled in the art.

[0069] One preferred embodiment of the present application is that in method step b) the foam is very homogeneous and has very fine cells. If desired, the person skilled in the art will be able to verify this in a routine manner by simple direct visual inspection by the naked eye or with optical aids such as a magnifying glass, a microscope, if necessary. "Fine cells" relates to the cell size. The smaller the average cell size, the finer the foam. If desired, the fine cell content can be determined, for example, with an optical microscope or a scanning electron microscope. "Homogeneous" means cell size distribution. A homogeneous foam has a very narrow cell size distribution, such that all the cells are approximately the same size. This can in turn be quantified with an optical microscope or with a scanning electron microscope.

[0070] As already described above, additional thickeners can be added to the system to adjust the viscosity of the wet foam.

[0071] The thickener which can advantageously be used in the context of the present application is preferably selected from the class of associative thickeners. Associative thickeners here are substances which cause a thickening effect by association at the surface of the particles present in the polymer dispersion. The term is known to the person skilled in the art. Preferred associative thickeners here are selected from the group consisting of polyurethane thickeners, hydrophobically modified polyacrylate thickeners, hydrophobically modified polyether thickeners and hydrophobically modified cellulose ethers. Very particularly preferred are polyurethane thickeners. Furthermore, it is preferred in the context of the present application that the concentration of the thickener is in the range from 0.01 to 10% by weight, more preferably in the range from 0.05 to 5% by weight, most preferably in the range from 0.1 to 3% by weight, based on the total composition of the dispersion.

[0072] It is furthermore preferred in the context of the present application that in method step d) a coating of the foamed polymer dispersion is produced which has a layer thickness of from 10 to 10 000 pm, preferably from 50 to 5000 pm, more preferably from 75 to 3000 pm, even more preferably from 100 to 2500 pm. The coating of the foamed polymer dispersion can be produced by methods familiar to the person skilled in the art, for example by knife coating. Direct or indirect coating methods (so-called transfer coating) can be used here.

[0073] It is also preferred in the context of the present application that the drying of the foamed and coated polymer dispersion in process step e) is carried out at elevated temperature. According to the present application, the preferred drying temperature here is a minimum of 50°C, preferably 60°C, more preferably at least 70°C. Furthermore, the foamed and coated polymer dispersion can be dried in several stages at different temperatures in order to avoid the occurrence of drying defects. The corresponding drying techniques are widespread in industry and are known to the person skilled in the art.

[0074] As already described, process steps c) to e) can be carried out by means of the widely practiced methods known to the person skilled in the art. An overview of these is given, for example, in "Coated and laminated Textiles" (Walter Fung, CR-Press, 2002).

[0075] In the context of the present application, those porous polymer coatings are particularly preferred which comprise a carboxylic acid derivative based on a polyamine and / or a polyalkanolamine and have an average cell size of less than 350 pm, preferably less than 200 pm, particularly preferably less than 150 pm, most preferably less than 100 pm. The average cell size can preferably be determined by means of a microscope, preferably by means of an electron microscope. For this purpose, the cross section of the porous polymer coating is observed by means of a microscope having a sufficient magnification and the size of at least 25 cells is determined. In order to obtain a sufficient statistical quantity for this evaluation method, the magnification of the microscope selected should preferably be such that there are at least 10 x 10 cells in the observation field. The average cell size is then calculated as the arithmetic mean of the cell sizes or cell sizes observed. The determination of the cell size by means of a microscope is familiar to the person skilled in the art.

[0076] The porous polymer layer (or polymer coating) comprising at least one carboxylic acid derivative based on a polyamine and / or a polyalkanolamine according to the present application and optionally further additives according to the present application can be used, for example, in the textile industry, such as for artificial leather materials, in the construction industry, in the electronics industry, in the sports industry or in the automotive industry. For example, based on the porous polymer coating according to the present application, everyday items such as shoes, shoe insoles, bags, suitcases, small boxes, clothing, automotive parts, preferably covers for seats, door parts, dashboard parts, steering wheels and / or handles, and gear lever covers, fitting items such as table mats, back cushions or seat cushions, gap fillers in electronic devices, cushioning and damping materials in medical applications or adhesive tapes can be produced. These everyday items form a further part of the subject matter of the present application. DETAILED DESCRIPTION

[0077] Example

[0078] Substance

[0079] DLU: aliphatic polycarbonate-polyether-polyurethane dispersion from Covestro.

[0080] WX 151 : aqueous polyurethane dispersion from Cromogenia.

[0081] PC 287 PRG: aqueous polyurethane dispersion from Cromogenia.

[0082] STA: stearic acid ammonium from Bozetto (about 30% in H2O).

[0083] SR: sodium soaps of tallow based sulfosuccinamates from Bozetto (about 35% in H2O).

[0084] ECO Pigment Black: aqueous pigment dispersion (black) from Cromogenia.

[0085] 250: polyether siloxane based levelling additive from Evonik.

[0086] PV 301 : polyurethane based associative thickener from Evonik.

[0087] TH 27: isocyanate based crosslinking additive from Cromogenia.

[0088] Viscosity measurement

[0089] All viscosity measurements were carried out using a Brookfield viscosimeter LVTD equipped with a #64 spindle at a constant rotational speed of 12 rpm. For the viscosity measurement, the sample was transferred into a 100 ml beaker, the measuring spindle was immersed therein to the prescribed depth. Constant viscosimeter readings were always awaited.

[0090] Method for determining the acid value:

[0091] Suitable methods for determining the acid value are, inter alia, those according to DGF C-V 2, DIN EN ISO 2114, Ph. Eur. 2.5.1, ISO 3682 and ASTM D 974.

[0092] Method for determining the amine value:

[0093] Dissolve the appropriate starting weight in 50 ml of tetrahydrofuran. After dissolution, add 50 ml of anhydrous acetic acid (99-100%). Then, titrate the sample with a 0.1 M solution of perchloric acid in dioxane using an automated titrator.

[0094] Example 1 : Synthesis of polyethyleneimine palmitoylamide with 6.90 equivalents of palmitic acid

[0095] Palmitic acid (108.5 g, 0.423 mol, 6.90 equivalents, C16 ≥ 99%) and polyethyleneimine (49.05 g, 0.0613 mol, 800 g / mol, 1.00 equivalents, from BASF) were used. The mixture of FG was heated to 170°C while stirring and passing N2 through it. During this process, the water formed was continuously removed by distillation until an acid value of 3.2 mg KOH / g and an amine value of 226 mg KOH / g were achieved.

[0096] Example 2: Synthesis of polyethyleneimine palmitoylamide with 8.30 equivalents of palmitic acid

[0097] Palmitic acid (114.9 g, 0.448 mol, 8.30 equivalents, C16 ≥ 99%) and polyethyleneimine (43.2 g, 0.0540 mol, 800 g / mol, 1.00 equivalents, from BASF) were used. The mixture of FG was heated to 175°C while stirring and passing N2 through it. During this process, the water formed was continuously removed by distillation until an acid value of 2.1 mg KOH / g and an amine value of 173 mg KOH / g were achieved.

[0098] Example 3: Synthesis of polyethyleneimine palmitoylamide with 10.3 equivalents of palmitic acid

[0099] Palmitic acid (121.9 g, 0.475 mol, 10.3 equivalents, C16 ≥ 99%) and polyethyleneimine (36.7 g, 0.0459 mol, 800 g / mol, 1.00 equivalents, from BASF) were used. The mixture of FG was heated to 175°C while stirring and passing N2 through it. During this process, the water formed was continuously removed by distillation until an acid value of 14.2 mg KOH / g and an amine value of 158 mg KOH / g were achieved.

[0100] Example 4: Blending of surfactants according to the application

[0101] According to the composition detailed in Table 1, the surfactants according to the invention from Examples 1-3 were blended and then homogenized at 80°C:

[0102] Table 1: Composition of surfactant blends used below

[0103]

[0104] Example 5: Foaming test

[0105] To test the efficacy of the additive combination according to the present application, a series of foaming experiments was performed. For this purpose, in a first step, a polyurethane dispersion from Covestro DLU was used. The foaming stabilizers used were the surfactant formulations 1-3 of the present application (see Table 1), as well as two surfactant combinations as a comparison: STA (stearic acid ammonium) and SR (sodium sulfosuccinimide). Table 2 gives an overview of the composition of the individual experiments.

[0106] All foaming experiments were performed manually. For this purpose, the polyurethane dispersion and the surfactant were first placed in a 500 ml plastic cup and homogenized with a dissolver equipped with a dispersing disc (diameter = 6 cm) at 1000 rpm for 3 minutes. To foam the mixture, the speed was then increased to 2000 rpm, ensuring that the dissolver disc was always immersed in the dispersion to a sufficient extent to form an adequate vortex. At this speed, the mixture was foamed to a volume of about 425 ml. The mixture was then sheared at 1000 rpm for a further 15 minutes. In this step, the dissolver disc was immersed sufficiently deep into the mixture so that no more air was introduced into the system, but the entire volume was still in motion.

[0107] Table 2: Overview of the foam formulations

[0108]

[0109] In all cases, a fine, homogeneous foam was obtained at the end of this foaming operation. It is worth noting that the foams produced with the surfactants 1-3 of the present application had a higher viscosity (see Table 2). The foams were applied to a siliconized polyester film with the aid of a film applicator equipped with an applicator frame (AB3220 from TQC) (coating thickness = 800 pm), then dried at 60°C for 5 minutes and at 120°C for a further 5 minutes.

[0110] Compared to sample #4, the dried samples #1-#3 of the present application had a more homogeneous macroscopic appearance and a softer feel. In addition, in the electron microscope studies, a finer pore structure could be determined.

[0111] Example 6: Migration test

[0112] To assess the surface migration of the surfactants according to the present application, artificial leather materials were produced by the following method. First, a topcoat layer was applied to a siliconized polyester film (layer thickness 100 pm). This was then dried at 100 °C for 3 minutes. Subsequently, a foam layer was coated onto the dried topcoat layer (layer thickness 800 pm), dried at 60 °C for 5 minutes and at 120 °C for 5 minutes. In the last step, an aqueous adhesive layer (layer thickness 100 pm) was coated onto the dried foam layer, and then a fabric carrier was laminated to the still moist adhesive layer. The finished laminate was again dried at 120 °C for 5 minutes and then separated from the polyester film.

[0113] All coating and drying operations were carried out here using a Labcoater LTE-S from Mathis AG. The topcoat and adhesive layers were here formulated according to the compositions listed in Table 3; the foam layer used was the foam formulation listed in Table 2, which was foamed by the method described in Example 5.

[0114] Table 3: Topcoat and adhesive formulations for producing artificial leather materials

[0115]

[0116] To assess the migration of the surfactants, after production the artificial leather samples were placed in water at 100 °C for 30 minutes and then dried overnight at room temperature. After this treatment, the samples were examined for surface discoloration. The comparative sample produced with the STA / SR surfactant (foam formulation #4, Table 2) had clearly visible white spots on the artificial leather surface, while no such surface discoloration was observed in the case of the samples produced with the surfactants according to the present application (foam formulations #1-#3, Table 2).

Claims

1. Use of a carboxylic acid derivative based on a polyamine and / or a carboxylic acid derivative based on a polyalkanolamine as an additive in an aqueous polymer dispersion, characterized in that the carboxylic acid derivative based on a polyamine and / or the carboxylic acid derivative based on a polyalkanolamine being obtainable by reacting a polyamine and / or a polyalkanolamine with at least one acyl donor; and characterized in that the polyamine is selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethyleneheptamine, dipropylenetriamine, tripropylenetetramine, spermine, spermidine, and N-alkylated, N-methylated derivatives of these compounds, polyethylenimine, polypropylenimine and / or (co)polymers carrying amine groups, and mixtures of these substances.

2. Use according to claim 1, wherein the additive is a foam additive.

3. Use according to claim 1, wherein the aqueous polymer dispersion is an aqueous polyurethane dispersion.

4. Use according to claim 1, wherein the acyl donor is selected from the group consisting of carboxylic acids, carboxylic acid esters, carbonic acid halides or carboxylic acid anhydrides.

5. Use according to claim 4, wherein the acyl donor is a carboxylic acid.

6. Use according to claim 1, wherein the (co)polymer is an (co)polymer based on allylamine and / or vinylamine.

7. Use according to claim 1, wherein the polyamine is polyethylenimine.

8. Use according to claim 1, characterized in that, the carboxylic acid corresponding to the general formula R-C(0)OH, wherein R is a monovalent aliphatic, saturated or unsaturated hydrocarbon group having 3 to 39 carbon atoms, and / or characterized in that a multifunctional dicarboxylic acid and / or a tricarboxylic acid is used, and / or characterized in that a mixture of a carboxylic acid of the general formula R-C(0)OH as specified above with a multifunctional dicarboxylic acid and / or a tricarboxylic acid is used.

9. Use according to claim 8, wherein R is a monovalent aliphatic, saturated or unsaturated hydrocarbon group having 7 to 21 carbon atoms.

10. Use according to claim 9, wherein R is a monovalent aliphatic, saturated or unsaturated hydrocarbon group having 9 to 17 carbon atoms.

11. Use according to claim 8, wherein the carboxylic acid is selected from the group consisting of caproic acid (butyric acid), caprylic acid (hexanoic acid), capric acid (octanoic acid), pelargonic acid (nonanoic acid), capuric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z)-9-hexadecenoic acid), oleic acid ((Z)-9-octadecenoic acid), elaidic acid ((E)-9-octadecenoic acid), cis-vaccenic acid ((Z)-11-octadecenoic acid), linoleic acid ((9Z,12Z)-9,12-octadecadienoic acid), a-linolenic acid ((9Z,12Z,15Z)-9,12,15-octadecatrienoic acid), g-linolenic acid ((6Z,9Z,12Z)-6,9,12-octadecatrienoic acid), dihomo-g-linolenic acid ((8Z,11Z,14Z)-8,11,14-eicosatrienoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-5,8,11,14-eicosatetraenoic acid), brassidic acid ((Z)-13-docosenoic acid), nervonic acid ((Z)-15-tetracosenoic acid), ricinoleic acid, hydroxystearic acid and / or undecylenic acid, and mixtures thereof.

12. Use according to claim 8, wherein the carboxylic acid is selected from the group consisting of rapeseed oil acid, soybean fatty acid, sunflower fatty acid, peanut fatty acid and / or tall oil fatty acid.

13. Use according to claim 8, wherein the carboxylic acid is selected from the group consisting of palmitic acid and stearic acid, and mixtures of both.

14. Use according to claim 8, wherein the multifunctional dicarboxylic and / or tricarboxylic acid is an aliphatic straight-chain or branched dicarboxylic and / or tricarboxylic acid having a chain length of 2 to 18 carbon atoms, and / or a dimeric fatty acid obtained by catalytic dimerization of unsaturated fatty acids having 4 to 22 carbon atoms.

15. Use according to any one of claims 1 to 14, characterized in that, The polyalkanolamine is selected from the group consisting of polyethylene glycol amine, polypropylene glycol amine, polyisopropylene glycol amine, polyethylene triamine, polypropylene triamine, polyisopropylene triamine, polyether amine, and / or (co)polymer carrying OH and amine groups, and mixtures of these.

16. Use according to claim 15, wherein the polyalkanolamine is selected from the group consisting of polyethylene oxide, polypropylene oxide and polyethylene oxide- polypropylene oxide copolymers.

17. Use according to claim 15, wherein the (co)polymer carrying OH and amine groups is a copolymer based on allyl alcohol, vinyl alcohol, allyl amine and / or vinyl amine.

18. Use according to claim 15, wherein the polyalkanolamine is polyisopropylene triamine.

19. Use according to any one of claims 1 to 14, characterized in that, The polyamine-based carboxylic acid derivative is the reaction product of at least one polyethyleneimine with at least one carboxylic acid, wherein the polyethyleneimine has an average molar mass of less than 25000 g / mol, wherein the average molar mass can be determined by gel permeation chromatography (GPC).

20. Use according to claim 19, wherein the polyethyleneimine has an average molar mass of less than 12 500 g / mol.

21. Use according to claim 19, wherein the polyethyleneimine has an average molar mass of less than 5000 g / mol.

22. Use according to claim 19, wherein the polyethyleneimine has an average molar mass of less than 2000 g / mol.

23. Use according to any one of claims 1 to 14, characterized in that, The polyalkanolamine can be obtained by condensation of N-(hydroxyalkyl)amines.

24. Use according to any one of claims 1 to 14, characterized in that, The polyalkanolamine can be obtained by condensation of trialkanolamines of general formula 1 : wherein R 1 to R 3 groups are independently the same or different 1,2-alkylene groups having 2 to 4 carbon atoms.

25. Use according to any one of claims 1 to 14, characterized in that, The polyalkanolamine can be obtained by co-condensation of N-(hydroxyalkyl)amines and other molecules carrying hydroxyl groups.

26. Use according to claim 25, wherein the other molecules carrying hydroxyl groups are selected from pentaerythritol, sorbitol, ethylene glycol, glycerol or polyglycerol.

27. Use according to any one of claims 1 to 14, wherein the polyalkanolamine is obtained by co-condensation of trialkanolamines of general formula 1 and other molecules carrying hydroxyl groups: wherein R 1 to R 3 groups are independently the same or different 1,2-alkylene groups having 2 to 4 carbon atoms.

28. Use according to claim 27, wherein the other molecules carrying hydroxyl groups are selected from pentaerythritol, sorbitol, ethylene glycol, glycerol or polyglycerol.

29. Use according to any one of claims 1 to 14, characterized in that, The polyamine-based carboxylic acid derivative is the reaction product of an amine- bearing (co)polymer with at least one carboxylic acid, wherein the amine-bearing (co)polymer has at least one repeating unit A of general formula 2: and / or at least one repeating unit B of general formula 3: wherein R 4 groups are identical or different monovalent aliphatic or aromatic, saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, or are H.

30. The use of claim 29, wherein the R 4 group has 1 to 10 carbon atoms.

31. The use of claim 29, wherein the R 4 group has 1 to 5 carbon atoms.

32. The use of claim 29, wherein the R 4 group is H.

33. The use according to claim 29, characterized in that, The polyalkanolamine-based carboxylic acid derivative is the reaction product of an amine- and OH group-bearing (co)polymer with at least one carboxylic acid, wherein the amine- and OH group-bearing (co)polymer has at least one repeating unit C of formula 4 in addition to at least one repeating unit A (formula 2) and / or B (formula 3): and / or at least one repeating unit D of general formula 5:

34. Use according to any one of claims 1 to 14, characterized in that, In the preparation of the polyamine-based carboxylic acid derivative and / or the polyalkanolamine-based carboxylic acid derivative, the reaction of the polyamine and / or polyalkanolamine and the carboxylic acid is such that the molar ratio of amine and OH functional groups reactive towards carboxylic acid to carboxylic acid is in the range of 5:1 to 1.5:

1.

35. Use according to claim 34, wherein the molar ratio is in the range of 4:1 to 1.7:

1.

36. Use according to claim 35, wherein the molar ratio is in the range of 3.5:1 to 1.9:

1.

37. Use according to claim 36, wherein the molar ratio is in the range of 3:1 to 2:

1.

38. The use according to any one of claims 1 to 14, characterized in that, The polyamine-based carboxylic acid derivative and / or the polyalkanolamine-based carboxylic acid derivative is used as an additive in an aqueous polymer dispersion in combination with at least one further co-surfactant.

39. The use according to claim 38, wherein the co-surfactant comprises a fatty alcohol, a fatty acid amide, an ethylene oxide-propylene oxide block copolymer, a betaine, an amine oxide, a quaternary ammonium surfactant, an amphoteric acetate, an ammonium and / or alkali metal salt of a fatty acid, an alkyl sulfate, an alkyl ether sulfate, an alkyl sulfonate, an alkyl benzene sulfonate, an alkyl phosphate, an alkyl sulfosuccinate, an alkyl sulfosuccinamate, an alkyl sarcosinate and / or a silicone-based co-surfactant, and mixtures of these substances.

40. The use according to claim 38, wherein the co-surfactant is a free fatty alcohol having 12 to 40 carbon atoms, and an alkyl sulfate having 12 to 40 carbon atoms, and mixtures of these substances.

41. The use according to claim 39, wherein the betaine is amidopropyl betaine.

42. The use according to claim 40, wherein the free fatty alcohol has 14-30 carbon atoms.

43. The use according to claim 40, wherein the free fatty alcohol has 16-24 carbon atoms.

44. The use according to claim 40, wherein the alkyl sulfate has 14-30 carbon atoms.

45. The use according to claim 40, wherein the alkyl sulfate has 16-24 carbon atoms.

46. The use according to claim 38, wherein the aqueous polymer dispersion is an aqueous polyurethane dispersion.

47. The use according to any one of claims 1 to 14, characterized in that, The aqueous polymer dispersion is selected from the group consisting of an aqueous polystyrene dispersion, a polybutadiene dispersion, a poly(meth)acrylate dispersion, a polyvinyl ester dispersion and a polyurethane dispersion, wherein the solid content of these dispersions is in the range of 20 to 70 wt.-%, based on the total dispersion.

48. The use according to claim 47, wherein the solid content of these dispersions is in the range of 25 to 65 wt.-%.

49. The use according to claim 47, wherein the aqueous polymer dispersion is an aqueous polyurethane dispersion.

50. The use according to any one of claims 1 to 14, characterized in that, The concentration of the polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative is in the range of 0.1 to 20 wt.-%, based on the total weight of the aqueous polymer dispersion.

51. The use according to claim 50, wherein the concentration is in the range of 0.2 to 15 wt.-%.

52. The use according to claim 51, wherein the concentration is in the range of 0.5 to 10 wt.-%.

53. An aqueous polymer dispersion containing a polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative, which carboxylic acid derivative is described in the use according to any one of claims 1 to 52, wherein the solid content of these dispersions is in the range of 20 to 70 wt.-%, based on the total dispersion, and wherein the concentration of the polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative is in the range of 0.2 to 20 wt.-%, based on the total weight of the aqueous polymer dispersion.

54. The aqueous polymer dispersion according to claim 53, which is an aqueous polyurethane dispersion.

55. The aqueous polymer dispersion according to claim 54, wherein the solids content of the dispersions is in the range of 25 to 65 wt.-%.

56. The aqueous polymer dispersion according to claim 53, wherein the concentration of the polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative is in the range of 0.4 to 15 wt.-%.

57. The aqueous polymer dispersion according to claim 53, wherein the concentration of the polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative is in the range of 0.5 to 10 wt.-%.

58. A method for the preparation of a porous polymer coating using a polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative as an additive in an aqueous polymer dispersion, the carboxylic acid derivative being described in the use according to any one of claims 1 to 52, the method comprising the following steps: a) providing a mixture comprising at least one aqueous polymer dispersion, at least one polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative, and optionally further additives, b) foaming the mixture to obtain a foam, c) optionally adding at least one thickening agent to adjust the viscosity of the wet foam, d) applying a coating of the foamed polymer dispersion to a suitable support, e) drying the coating.

59. The method according to claim 58, wherein the aqueous polymer dispersion is an aqueous polyurethane dispersion.

60. The method according to claim 58, wherein the porous polymer coating is a porous polyurethane coating.

61. The method according to claim 58, wherein the foamed polymer dispersion is a foamed polyurethane dispersion.

62. A porous polymer coating obtainable by using a polyamine-based carboxylic acid derivative and / or polyalkanolamine-based carboxylic acid derivative as an additive in an aqueous polymer dispersion in the preparation of the polymer coating, which is obtainable by the method according to claim 58.

63. The porous polymer coating according to claim 62, which is a porous polyurethane coating.

64. The porous polymer coating according to claim 62, wherein the aqueous polymer dispersion is an aqueous polyurethane dispersion.

65. An article of everyday use comprising the porous polymer coating according to claim 62.

66. The article of everyday use according to claim 65, which is a shoe, shoe insole, bag, suitcase, small box, clothing, automotive part, upholstered article, gap filler in electronic devices, cushioning and damping material in medical applications, or adhesive tape.

67. The article of everyday use according to claim 66, wherein the automotive part is a seat cover, door part, dashboard part, covering of steering wheel and / or handle, and gear lever cover, and / or wherein the upholstered article is a table mat, a cushion or a seat. ​

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