BR112019001120B1 - PHOSPHORYL POLYOL ESTER, PHOSPHORYL POLYGLYCEROL ESTER, POROUS POLYMER COATING, ITS PRODUCTION PROCESS AND USE OF POLYOL ESTERS AS ADDITIVES - Google Patents

Abstract

PHOSPHORYL POLYOL ESTER, PHOSPHORYL POLYGLYCEROL ESTER, POROUS POLYMER COATING, ITS PRODUCTION PROCESS AND USE OF POLYOL ESTERS AS ADDITIVES The invention relates to the use of polyol esters as additives in aqueous polymer dispersions to produce porous polymer coatings, preferably to produce porous polyurethane coatings.

Description

[001] The present invention is in the field of plastic coatings, synthetic leathers and polyol esters.

[002] It refers more particularly to the production of porous polymer coatings, especially porous polyurethane coatings, with the use of polyol esters as additives.

[003] Textile products coated with plastics, for example, synthetic leathers, generally consist of a textile carrier on which a layer of porous polymer is laminated, which, in turn, has been coated with a top layer or a coating of top.

[004] The porous polymer layer in this context preferably has pores in the micrometer range and is permeable to air and therefore breathable, that is, permeable to water vapor, but resistant to water. The porous polymer layer often comprises porous polyurethane. Currently, porous polyurethane layers are generally produced by a coagulation method in which DMF is used as a solvent. Due to environmental issues, however, this production method is increasingly criticised, and so it must be gradually succeeded by other, more environmentally friendly technologies. One such technology is based on aqueous polyurethane dispersions, called PUDs. They generally consist of polyurethane microparticles dispersed in water; the solid content is generally in the range of 30 to 60% by weight. To produce a porous polyurethane layer, these PUDs are mechanically foamed, coated onto a carrier (layer thicknesses typically between 300 to 2000 µm) and then dried at elevated temperature. During this drying step, there is evaporation of the water present in the PUD system, which results in the formation of a film of polyurethane particles. In order to further increase the mechanical strength of the film, it is additionally possible to add hydrophilic (poly)isocyanates to the PUD system during the production process, and these can react with free OH radicals present on the surface of the polyurethane particles during the drying, thereby causing additional crosslinking of the polyurethane film.

[005] Both the mechanical and tactile properties of PUD coatings produced in this way are determined to a crucial degree by the cellular structure of the porous polyurethane film. Additionally, the cellular structure of the porous polyurethane film affects the air permeability and breathability of the material. Particularly satisfactory properties can be obtained here with very fine cells evenly distributed. A common way of influencing cell structure during the manufacturing process described above is to add surfactants to the PUD system before or during mechanical foaming. A first effect of appropriate surfactants is that sufficient amounts of air can be pulsed into the PUD system during the foaming operation. Second, surfactants have a direct effect on the morphology of the air bubbles thus produced. The stability of the air bubbles is also influenced to a crucial degree by the type of surfactant. This is especially important during the drying of foamed PUD coatings, as it is thereby possible to prevent drying effects such as cell thickening or drying cracking.

[006] The prior art discloses several ionic and non-ionic surfactants that can be used for the production of porous PUD-based textile composite materials. In this context, anionic surfactants based on ammonium stearate are generally preferred; see, for example, U.S. Document 2015/0284902 A1 or U.S. Document 2006/0079635 A1.

[007] However, the use of ammonium stearate is associated with several disadvantages. First, ammonium stearate is susceptible to water hardness. In polymer dispersions that contain calcium ions, here, it is possible for insoluble calcium soaps to form, which results in flocculation or gelling of the polymer dispersions. Synthetic leather produced on the basis of ammonium stearate, moreover, has the disadvantage that calcium soaps can form on the surface of the synthetic leather in contact with hard water, and these are manifested as white spots. This is undesirable especially in the case of dark colored synthetic leather. Furthermore, ammonium stearate has the disadvantage that it has a high migration capacity in the dry polyurethane film. Especially in contact with water, it is possible here that a lubricating film, which is perceived as unpleasant, appears on the surface of the leatherette coating. A further disadvantage of ammonium stearate is that it generally has to be used in combination with other surfactants in order to achieve fully adequate foam stability; the prior art herein describes sulfosuccimates, for example. These additional components cause increased usage complexity.

[008] The problem addressed by the present invention was therefore that of enabling efficient foaming of PUD systems without having to accept the disadvantages detailed in the prior art that are associated with the use of ammonium stearate. Surprisingly, it was found that the use of polyol esters makes it possible to solve the stated problem.

[009] Therefore, the present invention provides the use of polyol esters as additives in aqueous polymer dispersions for the production of porous polymer coatings, preferably for the production of porous polyurethane coatings. The porous polymer layer to be produced according to the invention (i.e. the porous polymer coating) here preferably has pores in the micrometer range, the average cell size preferably being less than 150 µm, preferably less than 120 μm, with special preference, less than 100 μm, with maximum preference, less than 75 μm. The preferred layer thickness is in the range from 10 to 10,000 µm, preferably from 50 to 5,000 µm, more preferably from 75 to 3,000 µm, especially from 100 to 2,500 µm.

[010] The inventive use of polyol esters surprisingly has several advantages.

[011] This allows for efficient foaming of the polymer dispersion. The foams produced in this way are notable here for an exceptionally fine pore structure with particularly homogeneous cell distribution, which, in turn, has a very advantageous effect on the mechanical and tactile properties of the porous polymer coatings that have been produced on the basis of these foams. In addition, in this way, it is possible to improve the air permeability or breathability of the coating.

[012] An additional advantage of the polyol esters according to the invention is that they make it possible to produce particularly stable foams. This has primarily an advantageous effect on their processability. Secondly, the high foam stability has the advantage that, during drying of corresponding foams, drying defects such as cell thickening or drying cracking can be avoided. Furthermore, the improved foam stability allows for faster drying of the foams, which offers processing advantages from both an environmental and an economic point of view.

[013] Yet another advantage of polyol esters for use according to the invention is that they no longer have the ability to migrate in dry polymer film, especially polyurethane film, particularly when additional (hydrophilic) (poly)isocyanates are added. added to the system during drying.

[014] An additional advantage of polyol esters for use according to the invention is that they can cause an increase in viscosity of the non-dried foamed dispersion. This in turn can have an advantageous effect on the processability of the foam. Furthermore, as the case may be, it may be possible, as a result, to dispense with the use of additional thickening agents to adjust the foam viscosity, or to reduce the usage concentration thereof, which brings economic advantages.

[015] Yet another advantage of polyol esters for use according to the invention is that they have low, if any, susceptibility to water hardness.

[016] An additional advantage of polyol esters for use according to the invention is that they cause adequate stabilization of foams based on aqueous polymer dispersions even without the use of additional surfactants. This can reduce the complexity in assembling a suitable foam formulation on the user's part.

[017] The term "polyol esters" in the context of the present general invention also covers the alkoxylated adducts thereof, which can be obtained by reacting a polyol ester with alkylene oxides, for example, ethylene oxide, propylene oxide and/or or butylene oxide.

[018] The term "polyol esters" in the context of the entire present invention also encompasses ionic derivatives thereof, preferably phosphorylated and sulfated derivatives, especially phosphorylated polyol esters. Such polyol ester derivatives, especially phosphorylated polyol esters, are preferably useful polyol esters according to the invention. Such derivatives and further derivatives of the polyol esters are described in detail hereinafter, and are preferably useful in the context of the invention.

[019] The invention is described further and by way of example hereinafter, with no intention of the invention being restricted to these illustrative embodiments. When ranges, general formulas, or classes of compounds are specified below, they are intended to cover not only the corresponding ranges or groups of compounds that are explicitly mentioned, but also all subranges and subgroups of compounds that can be derived by leaving values individual (tracks) or composites. When documents are cited in the context of the present description, their contents, particularly with respect to the subject matter that forms the context in which the document was cited, are considered in their entirety to form part of the contents of the disclosure of the present invention. Unless otherwise stated, percentages are percentage by weight figures. When the parameters that were determined by the measurement are reported below, the measurements were determined at a temperature of 25 °C and a pressure of 101,325 Pa, unless otherwise indicated.

[020] In the context of the present invention, preference is given especially to those polyesters that are obtainable by esterifying a polyol with at least one carboxylic acid. This corresponds to a preferred embodiment of the invention.

[021] Preferred polyols used for the preparation of polyol esters according to the invention are selected from the group of C3-C8 polyols and the oligomers and/or co-oligomers thereof. Cooligomers result from the reaction of different polyols, for example from the reaction of propylene glycol with arabitol. Especially preferred polyols herein are propane-1,3-diol, propylene glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitan, sorbitol, isosorbide, erythritol, threitol, pentaerythritol, arabitol, xylitol, ribitol, fucitol, mannitol, galactitol, iditol, inositol, volemitol and glucose. Very particular preference is given to glycerol. Preferred polyol oligomers are oligomers of C3-C8 polyols having 1 to 20, preferably 2 to 10, and more preferably 2.5 to 8 repeating units. Diglycerol, triglycerol, tetraglycerol, pentaglycerol, dierythritol, trierythritol, tetraerythritol, di(trimethylolpropane), tri(trimethylolpropane) and di- and oligosaccharides are especially preferred. Very particular preference is given to sorbitan and oligo- and/or polyglycerols. In particular, it is possible to use mixtures of different polyols. Furthermore, it is also possible to obtain alkoxylated adducts of C3-C8 polyols, the oligomers and/or co-oligomers thereof for the preparation of the polyesters according to the invention, which can be obtained by reacting C3-C8 polyols, the oligomers and/or co-isomers thereof with alkylene oxides, for example ethylene oxide, propylene oxide and/or butylene oxide.

[022] For the preparation of polyol esters according to the invention, it is possible to use polyfunctional monocarboxylic acids and/or di- and/or tricarboxylic acids. Preferred carboxylic acids used for preparing the polyol esters according to the invention correspond to the general form R-C(O)OH in which R is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms, preferably 7 to 21 and, more preferably, 9 to 17 carbon atoms. Especially preferred here are carboxylic acids which are selected from butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (dodecanoic acid). tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidonic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z)-9-hexadecenoic acid) , oleic acid ((Z)-9-hexadecenoic acid), elaidic acid ((E)-9-octadecenoic acid), cis-vaccenic acid ((Z)-11-octadecenic acid), linoleic acid ((9Z,12Z )-9,12-octadecadienoic acid), alpha-linoleic acid ((9Z,12Z,15Z)-9,12,15-octadecatrienoic acid), gamma-linoleic acid ((6Z,9Z,12Z)-6,9 acid, 12-octadecatrienoic acid), dihomo-gamma-linoleic acid ((8Z,11Z,14Z)-8,11,14-eicosatrienoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-5,8, 11,14-eicosatetraenoic acid), erucic acid ((Z)-13-docosenoic acid), nervonic acid ((Z)-15-tetracosenoic acid), ricinoleic acid, hydroxystearic acid and undecenylic acid, and also mixtures thereof, for example , rapeseed oil acid, soybean fatty acid, sunflower fatty acid, peanut fatty acid and pine resin fatty acid. Very particular preference is given to palmitic acid and stearic acid, and especially to mixtures of these substances.

[023] Suitable sources of fatty acids or fatty acid esters, in particular glycerides, can be vegetable or animal fats, oils or greases. For example, you can use: lard, beef fat, goose fat, duck fat, chicken fat, horse fat, whale oil, fish oil, palm oil, olive oil, avocado oil, oils Kernel Oil, Coconut Oil, Palm Kernel Oil, Cocoa Butter, Cottonseed Oil, Pumpkin Seed Oil, Maize Kernel Oil, Sunflower Oil, Wheat Germ Oil, Seed Oil grapeseed oil, sesame oil, linseed oil, soybean oil, peanut oil, lupine oil, rapeseed oil, mustard oil, castor oil, jatropha oil, walnut oil, jojoba oil , lecithin, e.g. based on soya, rapeseed or sunflowers, bone oil, ox foot oil, borage oil, lanolin, emu oil, deer fat, marmot oil, mink oil, oil saffron oil, hemp oil, pumpkin oil, oenothera oil, tall oil and also carnauba wax, beeswax, candelilla wax, ouricuri wax, sugar cane wax, retamo wax, trithrinax wax, Raphia, esparto wax, alfalfa wax, bamboo wax, hemp wax, Douglas albeth wax, cork wax, sisal wax, linseed wax, cotton wax, damar wax, tea wax, coffee, rice wax, oleander wax, beeswax or wool wax.

[024] Additionally, it may be advantageous when polyfunctional di- and tricarboxylic acids or cyclic anhydrides of the di- and tricarboxylic acids are used for the preparation of the polyol esters according to the invention, by means of which the polyol polyesters are obtainable. Tetrafunctional and higher functionality carboxylic acids or anhydrides thereof, similarly, are preferably useful in the context of this invention. Preference is given here to aliphatic linear or branched aliphatic di- and/or tricarboxylic acids that have a chain length of 2 to 18 carbon atoms and/or dimer fatty acids that have been obtained by catalytic dimerization of unsaturated fatty acids that have 12 to 22 carbon atoms. Examples of corresponding polyfunctional acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, tapsychic acid, tartronic acid, tartaric acid, malic acid or citric acid . With special preference, polyfunctional di- and tricarboxylic acids are used in combination with monofunctional carboxylic acids as described above, whereby partially cross-linked polyol esters are obtainable.

[025] In a particularly preferred embodiment of the present invention, the polyol esters are selected from the group of sorbitan esters and/or polyglycerol esters. Very particular preference is given to polyglycerol esters, in particular polyglycerol palmitate and polyglycerol stearate and mixtures of these substances.

[026] Polyglycerol esters corresponding to general formula 1 are especially preferred: MaDbTc Formula 1 in which M = [C3H5(OR')2O1/2] D = [C3H5(OR')1O2/2] T = [C3H5O3/2 ] a = 1 to 10, preferably 2 to 3, with special preference, 2 b = 0 to 10, preferably, more than 0 to 5, with special preference, 1 to 4, c = 0 to 3, preferably 0, in that the radicals R' are independently identical or different radicals of the form R''-C(O)- or H, wherein R'' is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms preferably 7 to 21 and more preferably 9 to 17 carbon atoms, where at least one radical R' corresponds to a radical of the form R''-C(O)-.

[027] Polyglycerol esters corresponding to the general formula 2 are even more preferred: MxDyTz Formula 2 in which x = 1 to 10, preferably 2 to 3, with special preference, 2, y = 0 to 10, preferably, more than 0 to 5, with special preference, 1 to 4, z = 0 to 3, preferably, more than than 0 to 2, with special preference 0, with the proviso that at least one radical R' is not hydrogen, yet R' as defined under formula 1.

[028] Polyglycerol esters of the general formula 3 are also preferred: in which k = 1 to 10, preferably 2 to 3, with special preference 2, m = 0 to 10, preferably more than 0 to 5, with special preference 1 to 3, with the proviso that at least one of the radicals R' is a radical of the form R''- C(O)-, and that the total sum of k + m is greater than zero and the fragments having the indices k and m are statistically distributed.

[029] In the context of the present invention, the term "polyglycerol" is especially understood as a polyglycerol that may also contain glycerol. Consequently, for the purposes of calculating amounts, masses and the like, any fraction of glycerol must also be taken into account. In the context of the present invention, polyglycerols are therefore also mixtures comprising at least one oligomer of glycerol and glycerol. Glycerol oligomers are to be understood in each case as all relevant structures, ie, for example, linear, branched and cyclic compounds.

[030] Random distributions are composed of blocks with any desired number of blocks and with any desired sequence, or random distribution; they can also have an alternating structure, or even form a gradient along the chain; in particular, they can also form any of the mixed forms in which groups of different distributions can optionally follow each other. The nature of specific modalities may result in restrictions on random distributions. In all regions not affected by the restriction, there is no change in the random distribution.

[031] Preferably, the polyglycerol esters useful according to the invention have not more than 4, more preferably not more than 3 and even more preferably not more than 2 radicals R' of the form R'' -C(O)-. With special preference, the radical R' is selected from the group of carboxylic acids as described above.

[032] In a similarly preferred embodiment of the present invention, polyglycerol esters used as additives in aqueous polymer dispersions are those obtainable by reacting at least one polyglycerol with at least one carboxylic acid as described above. Suitable reaction conditions for this reaction are temperatures preferably between 200 and 260 °C and preferably a reduced pressure in the range between 0.002 and 0.08 Mpa (20 and 800 mbar), preferably between 0.005 and 0.05 Mpa (50 and 500 mbar ), which enables easier removal of water.

[033] In structural terms, polyol esters can be characterized by means of chemical moisture indices, for example, their hydroxyl number, their acid number and their hydrolysis number. Suitable methods for determining the hydroxyl number are particularly those according to DGF C-V 17 a (53), Ph. Eur. 2.5.3 Method A and DIN 53240. Suitable methods for determining the acid number are particularly those according to DGF C-V 2, DIN EN ISO 2114, Ph. Eur. 2.5.1, ISO 3682 and ASTM D 974. Suitable methods for determining the hydrolysis number are particularly those according to DGF C-V 3, DIN EN ISO 3681 and Ph. Eur. 2.5.6.

[034] It is preferred according to the invention and corresponding to a particularly preferred embodiment of the invention when, for the preparation of the polyglycerol ester, a polyglycerol having an average degree of condensation from 1 to 20, preferably from 2 to 10 and , more preferably, from 2.5 to 8 is used. The average degree of N condensation can be determined here on the basis of the OH number (OHN, in mg KOH/g) of the polyglycerol and is attached to it according to:

[035] The OH number of the polyglycerol can be determined here as described above. Consequently, preferred polyglycerols for preparing the polyglycerol esters according to the invention are preferably those having an OH number of from 1829 to 824, more preferably from 1352 to 888 and most preferably from 1244 to 920 mg KOH/ g.

[036] The polyglycerol used can be supplied here by different conventional methods, for example, glycidol polymerization (for example, base catalyzed), epichlorohydrin polymerization (for example, in the presence of a base such as NaOH) or glycerol polycondensation . According to the invention, preference is given to supplying the polyglycerol by glycerol condensation, especially in the presence of catalytic amounts of a base, especially NaOH or KOH. Suitable reaction conditions are temperatures between 200 and 260 °C and reduced pressure in a range between 0.002 and 0.08 Mpa (20 and 800 mbar), especially between 0.005 and 0.05 Mpa (50 and 500 mbar), which makes it possible to Easier water removal. Furthermore, various commercial polyglycerols are obtainable, for example, from Solvay, Inovyn, Daicel and Spiga Nord S.p.A.

[037] Both the reaction of polyglycerol and the reaction of carboxylic acids, especially fatty acid and/or fatty acid esters (for example, triglycerides), and the supply of polyglycerol can be effected by widely practiced processes that are familiar to the skilled person in technique. Corresponding processes are described, for example, in Rompp - Chemie Lexikon (Thieme-Verlag, 1996).

[038] Preferred sorbitan esters in the context of this invention are those obtained by reacting sorbitol or aqueous sorbitol solutions with at least one carboxylic acid as described above at temperatures from 200 to 260 °C, optionally in the presence of suitable catalysts, by first generating mixtures of 1,4- and 1,5-sorbitan esters. Corresponding processes are described, for example, in Rompp - Chemie Lexikon (Thieme-Verlag, 1996).

[039] It has already become clear that the term "polyol esters" in the context of the entire present invention also encompasses ionic derivatives thereof, preferably phosphorylated and sulfated derivatives, especially phosphorylated polyol esters. Phosphorylated polyol esters are obtainable herein by reacting the polyol esters with an optional, preferably mandatory subsequent phosphorylation reagent and subsequent neutralization (see especially, Industrial Applications of Surfactants. II. Preparation and Industrial Applications of Phosphate Esters. Edited by D. R. Karsa, Royal Society of Chemistry, Cambridge, 1990). Preferred phosphorylating reagents in the context of this invention are phosphorus oxychloride, phosphorus pentoxide (P4O10) and most preferably polyphosphoric acid. The term "phosphorylated polyol esters" within the entire scope of the present invention also covers partially phosphorylated polyol esters, and the term "sulfated polyol esters" within the entire scope of the present invention also covers partially sulfated polyol esters.

[040] Furthermore, it is also possible to obtain ionic derivatives of polyol esters in the context of the present general invention by reacting polyesters with di- or tricarboxylic acid or corresponding cyclic anhydrides, more preferably, succinic anhydride, and optional, preferably mandatory, neutralization. Such polyol esters are particularly preferably useful in the context of the present invention.

[041] Furthermore, it is also possible to obtain ionic derivatives of polyol esters in the context of the present general invention by reacting polyesters with unsaturated di- or tricarboxylic acid or corresponding cyclic anhydrides and subsequent sulfonation and optional, preferably mandatory, neutralization. Such polyol esters are also useful with particular preference in the context of the present invention.

[042] The term "neutralization" over the entire scope of the present invention also covers partial neutralization. For neutralization, which includes partial neutralization, it is possible to use common bases. They include the water-soluble metal hydroxides, for example barium hydroxide, strontium hydroxide, calcium hydroxide, thallium(I) hydroxide and preferably the hydroxides of the alkali metals which dissociate into free metal and hydroxide ions in solutions. aqueous solutions, especially NaOH and KOH. They also include anhydrous bases which react with water to form hydroxide ions, for example barium oxide, strontium oxide, calcium oxide, lithium oxide, silver oxide and ammonia. Like these aforementioned alkalis, substances useful as bases are also those that similarly generate an alkaline reaction on dissolution in water without having HO- (in the solid compound); examples thereof include amines such as mono-, di- and trialkylamines, which may also be functionalized alkyl radicals as, for example, in the case of amide amines, mono-, di- and trialkanolamines, mono-, di- and triaminoalkylamines , and, for example, salts of weak acids, such as potassium cyanide, potassium carbonate, sodium carbonate, trisodium phosphate, and the like.

[043] With regard to ionic derivatives of the polyol esters according to the invention, very particular preference is given to phosphorylated sorbitan esters and/or phosphorylated polyglycerol esters, in particular phosphorylated polyglycerol esters. More particularly, neutralized phosphorylated polyglycerol stearate and polyglycerol palmitate and mixtures of the two substances are preferred ionic derivatives of polyol esters in the context of this invention.

[044] The particularly preferred embodiment of this invention provides for the use according to the invention of polyol esters of formula 1, 2 and/or 3, as specified above, with the additional condition that they have been (at least partially) phosphorylated, so that these polyesters of formula 1, 2 and/or 3 especially carry at least one radical (R'''O)2P(O)- as the radical R', wherein the radicals R''' are, independently, cations, preferably Na+, K+ or NH4+, or ammonium ions of mono-, di- and trialkylamines, which can also be functionalized alkyl radicals, for example in the case of amide amines, of mono-, di- and trialkanolamines , of mono-, di- and triaminoalkylamines, or H or R''''-O-,

[045] wherein R'''' is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms, preferably 7 to 22, and more preferably 9 to 18 carbon atoms, or a polyol radical .

[046] In the case of sulfated polyol esters, preference is given especially to those obtainable by the reaction of polyol esters with sulfur trioxide or amidosulfonic acid. Preference is given here to sulfated sorbitan esters and/or sulfated polyglycerol esters, especially sulfated polyglycerol stearate and sulfated polyglycerol palmitate and mixtures of these two substances. In a particularly preferred embodiment of the present invention, polyesters are not used in pure form, but in a blend with at least one co-surfactant as additives in aqueous polymer dispersions. Preferred cosurfactants according to the invention are, for example, fatty acid amides, alcohol alkoxylates, for example, fatty alcohol ethoxylates, nonylphenol ethoxylates, ethylene oxide-propylene oxide block copolymers, betaines, for example, amidopropyl betaines, amine oxides, quaternary ammonium surfactants or amphoacetates. Additionally, the co-surfactant may comprise silicone-based surfactants, for example trisiloxane surfactants or polyether siloxanes.

[047] Especially preferred cosurfactants are ionic, preferably anionic, cosurfactants. Preferred ionic cosurfactants herein are ammonium and/or alkali metal salts of fatty acids, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyl phosphates, alkyl sulfosuccinates, alkyl sulfosuccinamates, and alkyl sarcosinates. especially preferred alkyl sulfates having 12 to 20 carbon atoms, more preferably having 14 to 18 carbon atoms, even more preferably having more than 16 to 18 carbon atoms. In the case of fatty acid ammonium and/or alkali metal salts, it is preferred when they contain less than 25% by weight of stearate salts, and are especially free of stearate salts.

[048] In the case of use of cosurfactants, it is especially preferred when the proportion of cosurfactant based on the total amount of polyol ester plus cosurfactant is in the range of 0.1 to 50% by weight, preferably in the range of 0.2 to 40 % by weight, more preferably in the range of 0.5 to 30% by weight, even more preferably in the range of 1 to 25% by weight.

[049] As already described, the present invention provides the use of polyol esters as additives in aqueous polymer dispersions for the production of porous polymer coatings. The polymer dispersions herein are preferably selected from the group of aqueous polystyrene dispersions, polybutadiene dispersions, poly(meth)acrylate dispersions, polyvinyl ester dispersions and polyurethane dispersions. The solid content of these dispersions is preferably in the range of 20 to 70% by weight, more preferably in the range of 25 to 65% by weight. Particular preference is given according to the invention to the use of polyol esters as additives in aqueous polyurethane dispersions. Particularly preferred here are polyurethane dispersions based on polyester polyols, polyester amide polyols, polycarbonate polyols, polyacetal polyols and polyether polyols.

[050] The use concentration of the polyol esters according to the invention in aqueous polymer dispersions is preferably in the range of 0.2 to 15% by weight, more preferably in the range of 0.4 to 10% by weight, with particular preference in the range of 0.5 to 7.5% by weight, based on the total weight of the dispersion.

[051] The polyol esters can be added to the aqueous dispersion either pure or diluted in a suitable solvent. Preferred solvents herein are selected from water, propylene glycol, dipropylene glycol, polypropylene glycol, butyldiglycol, butyltriglycol, ethylene glycol, diethylene glycol, polyethylene glycol, polyalkylene glycols based on EO, PO, BO and/or SO and mixtures of these substances. In the case of aqueous solutions or blends of the polyol esters of the invention, it can be advantageous when hydrotropic compounds are added to the blend to improve formulation properties (viscosity, homogeneity, etc.). Hydrotropic compounds here are water-soluble organic compounds that consist of a hydrophilic part and a hydrophobic part, but are too low in molecular weight to have surfactant properties. They cause an improvement in the solubility or solubility properties of organic substances, especially hydrophobic organics in aqueous formulations. The term "hydrotropic compounds" is known to those skilled in the art. Preferred hydrotropic compounds in the context of the present invention are alkali metal ammonium toluenesulfonates, alkali metal ammonium xylenesulfonates, alkali metal ammonium naphthalenesulfonates, alkali metal ammonium cumenesulfonates and phenol alkoxylates, especially phenyl ethoxylates, having up to 6 alkoxylate units.

[052] As well as the polyol esters according to the invention, aqueous polymer dispersions may also comprise additional additives, for example fillers, organic and inorganic pigments, smoothing agents, stabilizing agents such as hydrolysis or UV stabilizing agents, agents antioxidants, absorbents, crosslinkers, leveling additives, thickening agents or optionally, other cosurfactants as described above.

[053] In the context of this invention, very particular preference is given in each case to the inventive use of

[054] (a) polyglycerol esters, especially polyglycerol palmitate and/or polyglycerol stearate, in a blend with an anionic cosurfactant, preferably alkyl sulfates, most preferably cetearyl sulfate,

[055] or

[056] (b) reaction products of polyglycerol esters with di- or tricarboxylic acid or corresponding cyclic anhydrides, more preferably succinic anhydride, and subsequent neutralization, such as, more particularly, alkali metal polyglycerol palmitate succinate and /or alkali metal polyglycerol stearate succinate,

[057] or

[058] (c) neutralized phosphorylated polyglycerol stearate and/or neutralized phosphorylated polyglycerol palmitate.

[059] Advantageously, the polyglycerol esters according to the invention, especially the aforementioned species, are used as additives in aqueous polymer dispersions as a blend in a solvent, the solvent used most preferably being water. In turn, it is preferred here when corresponding blends contain 10% to 50% by weight, more preferably 15% to 40% by weight, even more preferably 20% to 30% by weight, of the polyglycerol esters according to with the invention.

[060] Preferably, the polyol esters according to the invention are used in aqueous polymer dispersions and auxiliary foaming agents or foam stabilizing agents for foaming the dispersions. Additionally, however, they can also be used as drying aids, leveling additives, wetting agents and rheology additives.

[061] Since, as described above, polyol esters cause a distinct improvement in porous polymer coatings produced from aqueous polymer dispersions, the present invention similarly provides aqueous polymer dispersions comprising at least one of the polyol esters of the invention, as described in detail above.

[062] The present invention still further provides porous polymer layers that were produced from aqueous polymer dispersions, obtained using the polyol esters according to the invention as additives, as described in detail above.

[063] Preferably, porous polymer coatings according to the invention can be produced by a process comprising the steps of

[064] a) providing a mixture comprising an aqueous polymer dispersion as described above, at least one of the polyol esters according to the invention and optionally further additives,

[065] b) cause foam in the mixture to generate a homogeneous fine-cell foam,

[066] c) optionally add at least one thickening agent to establish the wet foam viscosity,

[067] d) apply a foamed polymer dispersion coating to a suitable carrier,

[068] e) drying the coating.

[069] With a view to preferred embodiments, especially with a view to preferably useful polyol esters in the process and preferably useful aqueous polymer dispersions, reference is made to the foregoing description and also to the aforementioned preferred embodiments, especially as detailed in the Claims 2 to 10.

[070] It becomes clear that the process steps of the process according to the invention as set out above are not subject to any fixed time sequence. For example, process step c) can be performed at an early stage at the same time as process step a).

[071] It is a preferred embodiment of the present invention when, in process step b), the aqueous polymer dispersion is foamed by applying high shear forces. Foaming can be carried out here with the aid of shear units familiar to the person skilled in the art, for example Dispermats, thinners, Hansa mixers or Oakes mixers.

[072] It is additionally preferred when the wet foam produced at the end of process step c) has a viscosity of at least 3, preferably at least 5, more preferably at least 7.5 and even more preferably, of at least 10 Pa^s. The viscosity of the foam can be determined here, for example, with the aid of a Brookfield viscometer, model LVTD, equipped with an LV-4 spindle. Corresponding test methods for determining wet foam viscosity are known to those skilled in the art.

[073] As already described above, additional thickening agents can be added to the system to adjust the wet foam viscosity.

[074] Preferably, thickening agents that can be advantageously used in the context of the invention are selected here from the class of associative thickening agents. Associative thickening agents herein are substances that cause a thickening effect through association on the surfaces of particles present in polymer dispersions. The term is known to those skilled in the art. Preferred associative thickening agents are selected herein from polyurethane thickening agents, hydrophobically modified polyacrylate thickening agents, hydrophobically modified polyether thickening agents, and hydrophobically modified cellulose ethers. Very particular preference is given to polyurethane thickening agents. Additionally, it is preferred in the context of the present invention when the concentration of the thickening agents based on the total composition of the dispersion is in the range of 0.01 to 10% by weight, more preferably in the range of 0.05 to 5% by weight , most preferably in the range of 0.1 to 3% by weight.

[075] In the context of the present invention, it is additionally preferred when, in process step d), coatings of the foamed polymer dispersion with a layer thickness of 10 to 10,000 μm, preferably 50 to 5,000 μm, more preferably , from 75 to 3,000 μm, with even more preference, from 100 to 2,500 μm, are produced. Coatings of the foamed polymer dispersion can be produced by methods familiar to one skilled in the art, for example, knife coating. It is also possible here to use both direct and indirect processes (so-called transfer coating).

[076] It is also preferred in the context of the present invention when, in process step e), the drying of the foamed and coated polymer dispersion is carried out at elevated temperatures. Preference is given here according to the invention to drying temperatures of min. 50°C, preferably from 60°C, more preferably at least 70°C. Additionally, it is possible to dry the foamed and coated polymer dispersions in multiple stages at different temperatures, so as to avoid the occurrence of drying defects. Corresponding drying techniques are widely spread and are those known to those skilled in the art.

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

[078] In the context of the present invention, preference is especially given to those porous polymer coatings comprising polyol esters, which have an average cell size of less than 250 μm, preferably less than 150 μm, with special preference less than 100 µm, most preferably less than 75 µm. The average cell size can preferably be determined by microscopy, preferably by electron microscopy. For this purpose, a cross-section of the porous polymer coating is viewed through a microscope with sufficient magnification and the size of at least 25 cells is established. In order to obtain sufficient statistics for this evaluation method, the microscope magnification chosen should preferably be such that at least 10 x 10 cells are present in the observation field. The average cell size is then calculated as the arithmetic mean of the displayed cells or cell sizes. This determination of cell size via a microscope is familiar to one skilled in the art.

[079] The porous polymer layers (or polymer coatings) according to the invention, which comprise polyol esters, can be used, for example, in the textile industry, for example, for synthetic leather materials, in the construction industry, in the electronics industry, for example for foamed seals, in the sports industry, for example for the production of sports carpets or in the automotive industry.

[080] The present invention additionally provides phosphorylated polyol esters obtainable by the esterification of a polyol, preferably polyglycerol and/or sorbitan, with at least one carboxylic acid and subsequent reaction with a phosphorylation reagent and optional subsequent neutralization, preferably mandatory,

[081] wherein the phosphorylating reagent especially comprises phosphorous oxychloride, phosphorous pentoxide (P4O10) and/or polyphosphoric acid. The term "phosphorylated polyol esters" again encompasses, hereinafter, partially phosphorylated polyol esters. The term "neutralization" again encompasses, here and henceforth, partial neutralization. Useful preferred bases for neutralization have already been cited above.

[082] With regard to preferred embodiments, especially with a view to preferably useful polyols and carboxylic acids, full reference is made to the foregoing description and preferred embodiments mentioned therein, in order to avoid unnecessary repetition.

[083] Particularly preferred phosphorylated polyol esters are phosphorylated polyglycerol esters, preferably neutralized phosphorylated polyglycerol esters, especially neutralized phosphorylated polyglycerol palmitate, neutralized phosphorylated polyglycerol stearate or a mixture thereof. Similarly, phosphorylated sorbitan esters, preferably neutralized phosphorylated sorbitan esters, are particularly preferred.

[084] Polyglycerols preferably used for the preparation of polyglycerol esters have an OH number from 1829 to 824, more preferably from 1352 to 888, and most preferably from 1244 to 920 mg KOH/g.

[085] Phosphorylated polyol esters, preferably phosphorylated polyglycerol esters, especially phosphorylated and neutralized polyglycerol esters, particularly enable the efficient foaming of PUD systems, associated with all the advantages mentioned at the beginning.

[086] The aforementioned matter, phosphorylated polyol esters, is useful in a highly advantageous way for the implantation of the matter of claims 1 to 10 (that is, the use according to the invention), of claim 11 (that is, the process of according to the invention) and claim 12 (i.e. the polymer coating according to the invention).

[087] The present invention additionally provides sulfated polyol esters, especially sulfated polyglycerol esters, preferably obtainable by reacting the polyol esters, preferably polyglycerol esters, with sulfur trioxide or amidosulfonic acid. They particularly enable the efficient foaming of PUD systems, associated with all the advantages mentioned at the beginning. Also the material, sulfated polyol esters, is useful in a highly advantageous way for the implantation of the material of claims 1 to 12.

[088] The invention additionally provides phosphorylated polyol esters obtainable by

[089] (a) the esterification of a polyol, preferably polyglycerol and/or sorbitan, especially polyglycerol, with at least one carboxylic acid and

[090] (b) subsequent reaction with a phosphorylating reagent and

[091] (c) subsequent neutralization optional, preferably mandatory,

[092] wherein the phosphorylating reagent especially comprises phosphorous oxychloride, phosphorus pentoxide (P4O10) and/or polyphosphoric acid.

[093] In a preferred embodiment of the invention, it is a feature of the phosphorylated polyol ester that it is a phosphorylated polyglycerol ester and/or phosphorylated sorbitan ester, preferably phosphorylated and neutralized polyglycerol ester and/or phosphorylated and neutralized sorbitan ester , especially a neutralized phosphorylated polyglycerol palmitate, a neutralized phosphorylated polyglycerol stearate or a mixture of these substances.

[094] When the polyglycerol used for the preparation of polyglycerol esters has an OH number from 1829 to 824, more preferably from 1352 to 888, and most preferably from 1244 to 920 mg KOH/g, this is again a preferred embodiment of the invention.

[095] Regarding the most preferred configurations, reference is made to the preceding description.

[096] The invention additionally provides a phosphorylated polyglycerol ester corresponding to the general formula 1a: MaDbTc Formula 1a where M = [C3H5(OR')2O1/2] D = [C3H5(OR')1O2/2] T = [ C3H5O3/2] a = 1 to 10, preferably 2 to 3, with special preference, 2 b = 0 to 10, preferably, more than 0 to 5, with special preference, 1 to 4, c = 0 to 3, preferably 0, where the radicals R' are independently identical or different radicals of the form (R'''O)2P(O)-, R''-C(O)- or H, where R'' is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms, preferably 7 to 21 and more preferably 9 to 17 carbon atoms, wherein at least one radical R' corresponds to a radical of the form R ''- C(O)- and wherein at least one radical R' corresponds to a radical of the form (R'''O)2P(O)-, wherein the radicals R''' are each independently , cations, preferably Na+, K+ or NH4+, or ammonium ions of mono-, di- and trialkylamines, which can also be functionalized alkyl radicals as, for example, in the case of amide amines, of mono-, di- and trialkanolamines, of mono-, di- and triaminoalkylamines, or H or R''''-O-, wherein R''' is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms, preferably 7 to 22 and, more preferably, 9 to 18 carbon atoms or a polyol radical, and/or corresponds to the general formula 2a: MxDyTz Formula 2a x = 1 to 10, preferably 2 to 3, with special preference, 2, y = 0 to 10, preferably, more than 0 to 5, with special preference, 1 to 4, z = 0 to 3, preferably, more than than 0 to 2, with special preference 0, with the proviso that at least one radical R' corresponds to a radical of the form R''-C(O)- and at least one radical R' corresponds to a radical of the form (R'''O)2P(O)-, yet R' as defined above, and/or corresponds to the general formula 3a: wherein k = 1 to 10, preferably 2 to 3, with special preference 2, m = 0 to 10, preferably more than 0 to 5, with special preference 1 to 3, with the proviso that at least one radical R' corresponds to a radical of the form R''-C(O)- and at least one radical R' corresponds to a radical of the form (R'''O)2P(O)-, and that the sum total of k + m is more than zero and the fragments that have k and m indices are statistically distributed. With regard to preferred configurations, reference is made to the preceding description.

EXAMPLES SUBSTANCES:

[097] Impranil® DLU: Covestro aliphatic polycarbonate ester-polyether-polyurethane dispersion

[098] Impranil® DL 1537: Covestro aliphatic polyester-polyurethane dispersions

[099] Impranil® DL 1554: Covestro aliphatic polyester-polyurethane dispersions

[0100] Impranil® RSC 1380: Covestro polyester-polyurethane dispersion

[0101] Bayhydur® 3100: hydrophilic aliphatic polyisocyanate from Covestro

[0102] Stokal® STA: ammonium stearate (about 30% in H2O) from Bozetto

[0103] Stokal® SR: tallow fat-based sodium sulfosuccinamate (about 35% in H2O) from Bozetto

[0104] Tego® Viscoplus 3030: associative thickening agent based on polyurethane from Evonik Industries AG.

VISCOSITY MEASUREMENT

[0105] All viscosity measurements were conducted with a Brookfield viscometer, LVTD, equipped with an LV-4 spindle, at a constant rotation speed of 12 rpm. For viscosity measurements, samples were transferred into a 100 ml pot in which the measuring spindle was immersed. The display of a constant viscometer measurement was always expected.

EXAMPLE 1: SYNTHESIS OF POLYGLYCEROL STEARATE

[0106] A mixture of polyglycerol (OHN = 1,124 mg KOH/g, 103.3 g, 0.431 mol) and technical grade stearic acid (palmitic acid:stearic acid = 50:50; 155.0 g, 0.574 mol) was heated to 240 °C during stirring and the formed water was continuously distilled until an acid number of 1.0 mg KOH/g was obtained. The polyglycerol stearate obtained had the following indices:

[0107] Acid number: 1.0 mg KOH/g; hydrolysis number: 129 mg KOH/g; hydroxyl number: 345 mg KOH/g.

EXAMPLE 2: SYNTHESIS OF PHOSPHORYLATED POLYGLYCEROL STEARATE

[0108] A mixture of a polyglycerol stearate (97.62 g) obtained as described in Example 1 and polyphosphoric acid (115% H3PO4, 2.38 g) was heated to 80 °C while stirring for 4 h. Then the mixture had an acid number of 27.6 mg KOH/g. Subsequently, 45% aqueous KOH solution (9.77 g) was added at 80 °C and the mixture was stirred at 80 °C for another 30 min. The mixture had an acid number of 1.3 mg KOH/g.

EXAMPLE 3: SYNTHESIS OF POLYGLYCEROL POTASSIUM STEARATE SUCCINATE

[0109] Polyglycerol stearate (300 g) obtained as described in Example 1 was heated to 80 °C and succinic anhydride (9.15 g) was added in portions during stirring over the course of 1 h. The mixture was stirred at 80 °C for a further 2 h until an acid number of 19.8 mg KOH/g was obtained. Subsequently, 12.90 g of 45% aqueous KOH solution was added and the mixture was stirred for a further 15 min. The obtained potassium polyglycerol stearate succinate had the following characteristics: acid number: 8.8 mg KOH/g.

EXAMPLE 4: FORMULATION AND BLENDING OF SURFACTANTS ACCORDING TO THE INVENTION

[0110] The surfactants according to the invention of Examples 1 and 2 were mixed according to the compositions detailed in Table 1 and then homogenized at 80 °C: TABLE 1: COMPOSITION OF SURFACTANT BLENDS USED HEREIN

EXAMPLE 5:

[0111] 150 g of the Impranil® DLU dispersion was placed in a 500 ml plastic beaker and stirred using a Pendraulik dissolving agent equipped with a dissolving disc (0 = 6 cm) at 500 rpm for 3 min. During this time, the surfactant was gradually added using a syringe. The exact compositions of the samples are listed in Table 2.

[0112] For the foaming of the mixtures, the shear rate was then increased to 2,000 rpm, ensuring that the dissolving disk was always immersed in the dispersion to a sufficient degree that an appropriate vortex was formed. At this speed, the mixtures were foamed to a volume of about 425 ml. The shearing time required for this purpose is similarly observed in Table 2. Then, the shearing rate was reduced to 1,000 rpm, Tego® Viscoplus 3030 was added with the aid of a syringe and the mixture was sheared for another 15 min. At this stage, the dissolving disk was immersed in the mixtures to such an extent that no additional air was introduced into the system, but the complete volume was still in motion. TABLE 2: OVERVIEW OF THE FOAM PRODUCED IN EXAMPLE 4

[0113] In all cases, fine homogeneous foams were obtained at the end of this foaming operation. It was notable that the foams that were produced with surfactants 1 to 3 according to the invention had a slightly higher viscosity instead of a lower thickener concentration (see Table 2). The foams were coated onto a siliconized polyester film with the aid of a film applicator (AB3220 from TQC) equipped with an applicator frame (coating thickness = 800 μm) and then dried at 60 °C for 10 min and at 120 °C for another 5 min.

[0114] Compared to sample 1, dry samples 2 to 4 featured a more homogeneous macroscopic appearance and a more velvety feel. The cellular structure of dried samples was analyzed using a scanning electron microscope. It was possible here to determine an average cell size of around 120 µm in case of comparative sample 1, while inventive samples 2 and 3 had a much finer cell size of around 50 µm.

EXAMPLE 6:

[0115] The compositions listed in Table 2 were foamed analogously to the method described in Example 4 and coated on a siliconized polyester film using an applicator frame (coating thickness = 800 μm). This time, however, the samples were dried at 90 °C for 5 min only and at 120 °C for 3 min. It was possible to observe here that the comparative sample 1, after drying, had distinct defects (drying cracks), while the inventive samples 2 - 4 could be dried without defects despite shortened more severe drying conditions.

[0116] Additionally, for all samples, a coating with a coating thickness of 2,000 μm was produced. They were dried at 60 °C for 10 min, at 90 °C for 10 min and at 120 °C for 10 min. Here too, it was possible to dry samples 2 to 4 comprising the surfactants according to the invention without defects, while the comparative sample had distinct drying cracks 1.

EXAMPLE 7:

[0117] 150 g of polyurethane dispersion and optionally 3 g of Bayhydur® 3100 polyisocyanate were placed in a 500 ml plastic vessel and then, as described in Example 4, foamed, homogenized, coated in a siliconized polyester film ( coating thickness 800 μm) and dried. Tables 3 and 4 generate an overview of the respective composition of the samples. All samples after drying showed a more homogeneous appearance than Sample 1 produced for comparison in Example 4. Scanning Electron Microscope analyzes of the dried foams showed that the cell size in all cases was in the range of 40- 60 µm. These experiments demonstrate the versatile use of the polyglycerol esters according to the invention in several different polyurethane dispersions.

[0118] Additionally, for all samples, a survey with a layer thickness of 2,000 μm was produced after the thickness. These coatings were dried at 60 °C for 10 min, at 90 °C for 10 min and at 120 °C for 10 min. In all cases, the foams could be dried without defects, and homogeneous samples with a velvety feel were obtained. Scanning electron microscope analyzes showed that the cell size of all samples here was also in the range of 40 to 60 µm. TABLE 3: GENERAL VIEW OF THE FOAM PRODUCED IN EXAMPLE 6 TABLE 4: OVERVIEW OF THE FOAM PRODUCED IN EXAMPLE 6

Claims (13)

1. Use of polyol esters as additives in aqueous polymer dispersions characterized in that they are for the production of porous polymer coatings, preferably porous polyurethane coatings in which the polyol esters are obtainable by the esterification of a polyglycerol with at least one carboxylic acid. 2. Use according to claim 1, characterized in that the carboxylic acid corresponds to the general formula R-C(O)OH in which R is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms, preferably 7 to 21 and more preferably 9 to 17 carbon atoms, and preferred carboxylic acids which are selected from butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric 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), Acid palmitoleic acid ((Z)-9-hexadecenoic acid), oleic acid ((Z)-9-hexadecenoic acid), elaidic acid ((E)-9-octadecenoic acid), cis-vaccenic acid ((Z)-11- octadecenic acid), linoleic acid ((9Z,12Z)-9,12-octadecadienoic acid), alpha-linoleic acid ((9Z,12Z,15Z)-9,12,15-octadecatrienoic acid), gamma-linoleic acid (( 6Z,9Z,12Z)-6,9,12-octadecatrienoic acid), dihomo-gamma-linoleic acid ((8Z,11Z,14Z)-8,11,14-eicosatrienoic acid), arachidonic acid ((5Z, 8Z,11Z,14Z)-5,8,11,14-eicosatetraenoic acid), erucic acid ((Z)-13-docosenoic acid), nervonic acid ((Z)-15-tetracosenoic acid), ricinoleic acid, hydroxystearic acid, and undecenylic acid, and also mixtures thereof, for example rapeseed oil acid, soybean fatty acid, sunflower fatty acid, peanut fatty acid and/or pine resin fatty acid, with very particular preference given to palmitic acid and stearic acid and mixtures of these two substances, and/or by the fact that a polyfunctional di- and/or tricarboxylic acid is used, preferably linear or branched aliphatic di- and/or tricarboxylic acids having a chain length of 2 to 18 carbon atoms and/or dimer fatty acids which have been obtained by catalytic dimerization of unsaturated fatty acids having 12 to 22 carbon atoms, and/or by the fact that a carboxylic acid mixture of the general formula R-C( O)OH, as specified above, and polyfunctional di- and/or tricarboxylic acid is used. 3. Use according to claim 1 or 2, characterized in that the polyol esters used include those selected from the group of polyglycerol esters corresponding to general formula 1: MaDbTc Formula 1 in which M = [C3H5(OR ')2O1/2] D = [C3H5(OR')1O2/2] T = [C3H5O3/2] a = 2 to 3, with special preference, 2 b = more than 0 to 5, with special preference, 1 a 4, c = 0, wherein the radicals R' are independently identical or different radicals of the form R''-C(O)- or H, wherein R'' is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical which has 3 to 39 carbon atoms, preferably 7 to 21 and more preferably 9 to 17 carbon atoms, where at least one radical R' corresponds to a radical of the form R''-C(O)-, and/or corresponds to general formula 2: MxDyTz Formula 2where x = 2 to 3, with special preference, 2, y = more than 0 to 5, with special preference, 1 to 4, z = more than 0 to 2, with special preference, 0, with the proviso that at least a radical R' is not hydrogen, yet R' as defined above, and/or corresponds to the general formula 3: wherein k = 2 to 3, with special preference 2, m = more than 0 to 5, with special preference 1 to 3, with the proviso that at least one of the radicals R' is a radical of the form R'' -C(O)-, still R' as defined above, and that the total sum of k + m is greater than zero and the fragments that have the indices k and m are statistically distributed. 4. Use according to claim 3, characterized in that the polyol esters of formulas 1, 2 and/or 3 have been phosphorylated, in particular they carry at least one radical (R'''O)2P(O)- as the radical R', in which the radicals R''' are, independently, cations, preferably Na+, K+ or NH4+, or ammonium ions of mono-, di- and trialkylamines, which can also be functionalized alkyl radicals, for example, in the case of amide amines, of mono-, di- and trialkanolamines, of mono-, di- and triaminoalkylamines, or H or R''''-O-, where R'''' is a saturated hydrocarbyl radical or monovalent aliphatic unsaturated having 3 to 39 carbon atoms, preferably 7 to 22 and more preferably 9 to 18 carbon atoms or a polyol radical. 5. Use according to any one of claims 1 to 4, characterized in that the polyol esters are used in a mixture with at least one ionic cosurfactant, preferably anionic as additives in aqueous polymer dispersions, with preferred ionic cosurfactants being the salts ammonium metal fatty acid alkali, alkyl sulfates, alkyl ether sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyl phosphates, alkyl sulfosuccinates, alkyl sulfosuccinamates and alkyl sarcosinates, with particular preference given to alkyl sulfates having 12 to 20 carbon atoms, preferably additionally having 14 to 18 carbon atoms, even more preferably having more than 16 to 18 carbon atoms, with the proviso that the proportion of ionic cosurfactant based on the amount total polyol ester plus co-surfactant is preferably in the range of 0.1 to 50% by weight, preferably in the range of 0.2 to 40% by weight, more preferably in the range of 0.5 to 30% by weight, even more preferably, in the range of 1 to 25% by weight. 6. Use according to any one of claims 1 to 5, characterized in that the aqueous polymer dispersions are selected from the group of aqueous polystyrene dispersions, polybutadiene dispersions, poly(meth)acrylate dispersions, polystyrene ester dispersions polyvinyl and polyurethane dispersions, especially polyurethane dispersions, wherein the solid content of these dispersions is preferably in the range of 20 to 70% by weight, more preferably in the range of 25 to 65% by weight. 7. Use according to any one of claims 1 to 5, characterized in that the use concentration of the polyol esters in the aqueous polymer dispersion is in the range of 0.2 to 15% by weight, more preferably of 0.4 to 10% by weight, especially from 0.5 to 7.5% by weight, based on the total weight of the dispersion. 8. Use according to any one of claims 1 to 7, characterized in that the polyol esters serve as auxiliary foaming agents or foam stabilizing agents for foaming aqueous polymer dispersions, and as an auxiliary drying agent , leveling additive, wetting agent and/or rheology additive. 9. Process for producing a porous polymer coating, preferably porous polyurethane coating, using polyol esters as defined in claim 1, characterized in that it comprises the steps of a) providing a mixture comprising an aqueous polymer dispersion, at least one polyglycerol ester, and optionally additional additives, b) foaming the mixture to generate a preferably homogeneous fine cell foam, c) optionally adding at least one thickening agent to establish the desired viscosity of the wet foam, d) applying a coating of the polyglycerol ester foamed polymer to a suitable carrier, e) drying the coating. 10. Porous polymer coating, preferably porous polyurethane coating, characterized in that it is obtainable by using polyglycerol esters as additives in aqueous polymer dispersions in the production of such polymer coatings, preferably obtainable by a process as defined in claim 9, with the proviso that the porous polymer coating preferably has an average cell size of less than 150 µm, preferably less than 120 µm, especially preferably less than 100 µm, most preferably less than 75 µm . 11. Polyglycerol phosphorylated ester characterized in that it is obtainable by: (a) the esterification of a polyglycerol, with at least one carboxylic acid, (b) subsequent reaction with a phosphorylation reagent, and (c) optional subsequent neutralization, preferably mandatory, in that the phosphorylating reagent especially comprises phosphorous oxychloride, phosphorous pentoxide (P4O10) and/or polyphosphoric acid, with the proviso that the polyglycerol used for the preparation of the polyglycerol esters preferably has an OH number of 1829 to 824, more preferably, from 1352 to 888 and, with particular preference, from 1244 to 920 mg KOH/g. Phosphorylated polyglycerol ester according to claim 11, characterized in that it is a phosphorylated and neutralized polyglycerol ester, in particular a phosphorylated and neutralized polyglycerol palmitate, a phosphorylated and neutralized polyglycerol stearate or a mixture of these substances. 13. Phosphorylated polyglycerol ester according to claim 11, characterized in that it corresponds to the general formula 1a: MaDbTc Formula 1a in which M = [C3H5(OR')2O1/2] D = [C3H5(OR')1O2/2] T = [C3H5O3/2] a = 2 to 3, with special preference, 2 b = more than 0 to 5, with special preference, 1 to 4, c = 0, wherein the radicals R' are independently identical radicals or other than the form (R'''O)2P(O)-, R''-C(O)- or H, wherein R'' is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms. carbon, preferably 7 to 21 and more preferably 9 to 17 carbon atoms, where at least one radical R' corresponds to a radical of the form R''-C(O)- and where at least one radical R' corresponds to a radical of the form (R'''O)2P(O)-, where the R''' radicals are each independently cations, preferably Na+, K+ or NH4+, or ammonium ions of mono-, di- and trialkylamines, which can also be functionalized alkyl radicals, for example in the case of amide amines, mono-, di- and trialkanolamines, mono-, di- and triaminoalkylamines, or H or R ''''-O-, wherein R'''' is a monovalent aliphatic saturated or unsaturated hydrocarbyl radical having 3 to 39 carbon atoms, preferably 7 to 22 and more preferably 9 to 18 carbon atoms or a polyol radical, and/or corresponds to the general formula 2a: MxDyTz Formula 2a where x = 2 to 3, with special preference, 2, y = more than 0 to 5, with special preference, 1 to 4, z = more than 0 to 2, with special preference, 0, with the proviso that at least one radical R' corresponds to a radical of the form R''-C(O)- and at least one radical R' corresponds to a radical of the form (R'''O)2P(O)-, still R' as defined above, and/or corresponds to general formula 3a: where k = 2 to 3, with special preference 2, m = more than 0 to 5, with special preference 1 to 3, with the proviso that at least one radical R' corresponds to a radical of the form R'' -C(O)- and at least one radical R' corresponds to a radical of the form (R'''O)2P(O)-, yet R' as defined above, and that the total sum of k + m is more than zero and the fragments that have k and k indices are statistically distributed.