MXPA01006125A - Process for the preparation of an aqueous dispersion of an anionic polyurethane free of volatile tertiary amines - Google Patents

Abstract

The present invention relates to a process for the preparation of an aqueous dispersion of an anionic polyurethane. According to the invention a tertiary amine functional urethane polymer or oligomer acts as acid neutralizing agent. The process of the invention comprises the steps of:dispersion of an anionic isocyanate functional polyurethane prepolymer in water in the presence of a tertiary amine functional urethane polymer or oligomer and chain extending of the anionic polyurethane prepolymer with a reactive hydrogen functional material during or after the dispersion in water. Furthermore the invention deals with dispersions obtained by the present process, which may comprise usual additives such as coloring agents, pigments, matting agents, silicones, flow agents and the like. Finally the invention relates to a coated substrate or film, which is obtained by applyingthe above dispersion onto a substrate such as leather, artificial leather, metal, wood, glass, plastic, paper, paper board, textile, non-woven, cloth, foam etc.

Description

AN ANIONIC POLYURETHANE FREE OF TERTIARY VOLATILE AMINES The present invention relates to a process for the preparation of aqueous dispersions of anionic polyurethanes, to the dispersions obtained and to a film or coated substrate obtained with said dispersion. Introduction Aqueous dispersions of polyurethanes are well known as bases for the preparation of coating compositions. They can be used for a protective or decorative coating, optionally in combination with additives such as coloring agents, pigments, agents that aim to achieve a matt effect, and the like. Polyurethanes may possess many desirable properties such as good chemical resistance, water resistance, solvent resistance, strength, abrasion resistance, durability. The dispersibility of polyurethanes in water can be achieved through the incorporation of appropriate pendant chain ionic groups, non-ionic pendant chain hydrophilic groups, or in-chain hydrophilic groups in the polymer structure. of polyurethane. If appropriate, external surfactants may also be applied. polyurethane main chain, such as carboxyl, sulfonic, sulfate or phosphate groups. They are introduced by reacting a reactive hydrogen functional compound having at least one acid group with a polyisocyanate. More common is the incorporation of a functional carboxylic acid compound. The carboxylic acid functions are generally neutralized before or during the dispersion of the polyurethane prepolymer in water with a volatile tertiary amine. The anorganic bases are less convenient, since the polyurethane will generally coagulate when they are applied or will provide coatings or films highly sensitive to water. To avoid coagulation it is appropriate to incorporate a large number of hydroxylic polyethoxy chains into the polymer system, but the coatings prepared from these dispersions will also be very sensitive to water.

A disadvantage of the use of volatile tertiary amines as a neutralizing agent is that they evaporate during the formation of the film, and therefore will cause unacceptable environmental pollution. The present invention provides a process for preparing aqueous dispersions of anionic polyurethanes that do not contain volatile tertiary amines.

In accordance with the present invention there is provided a process for the preparation of an aqueous dispersion of an anionic polyurethane wherein a functional urethane amine urethane oligomer or polymer acts as an acid neutralizing agent. The process according to the present invention comprises the steps of: dispersing an anionic isocyanate functional polyurethane prepolymer in water in the presence of a tertiary functional amine urethane oligomer or polymer and chain extension of the polyurethane prepolymer with a functional material of Reactive hydrogen during or after dispersion in water. The anionic group in the polyurethane to be neutralized can be a carboxylic acid group. The tertiary amine functional urethane urethane polymer or oligomer of the invention is prepared by the reaction of an isocyanate-functional polyurethane or polyisocyanate prepolymer with a reactive hydrogen functional material containing tertiary amine functions. The urethane oligomer or polymer containing tertiary amine functions can be prepared as a pure polymeric or oligomeric material, can be prepared in a solvent system, or can be prepared as an aqueous dispersion. The tertiary amine functional urethane urethane oligomer or polymer of the invention can be prepared by the steps of: isocyanate containing tertiary amine functions of a polyisocyanate, and a polyol containing tertiary amine functions, - chain extender and / or partially cover the prepolymer with a reactive hydrogen functional material. As mentioned above the tertiary amine functional urethane urethane polymer or oligomer can occur in an aqueous dispersion which is prepared by the steps of: - preparing an isocyanate functional polyurethane prepolymer containing tertiary amine functions of a polyisocyanate, and a polyol containing tertiary amine functions dispersion of the prepolymer in water, - chain extending and / or partially covering the prepolymer with a reactive hydrogen functional material during or after dispersion in water. The polyol containing tertiary amine functions and used for the preparation of the polyurethane prepolymer is N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, 3-diisopropyl-amino-1, 2-propanediol, 3- (dimethylamino). -1,2-propanediol, 3- (diethylamino) -1,2-propanediol, triethanolamine, tripropanolamine, triisopropanolamine and is preferably N-methyldiethanolamine or (3-dimethylamino-propyl) diisopropanolamine. used in the preparation of the functional urethane amine urethane polymer or oligomer or dispersion thereof is a monoalcohol, monoamine, polyamine, tertiary functional amine polyol or a mixture thereof. When the reactive hydrogen functional material is a polyol or a polyamine it can be a polyol containing a tertiary amine function as described above or is a diamine which is bis (3-aminopropyl) methylamine. To obtain a maximum tertiary amine concentration, the functional material of reactive hydrogen for prepolymer coverage is preferably a monoamine or mono-alcohol containing a tertiary amine function, which may be 2- (diethylamino) ethylamine, 3- (diethylamino) propylamine, N, N, N'-trimethylethylene-diamine, N, N, N '-trimethyl-1,3-propane-diamine, N, N, 2, 2-tetra-methyl-l, 3-propane-diamine, N, N-diethylethanolamine, l-dimethylamino-2-propanol, 3-dimethyl-amino-1-propanol, 2-dimethyl-amino-2-methyl-1-propanol, 1-diethylamino-2-propanol, 3-diethyl- amino-l-propanol, 2- (diisopropylamino) ethanol, 5-diethylamino-2-pentanol, 2- (dibutyl-amino) ethanol and is preferably 2- (dimethylamino) -ethylamine, 3- (dimethylamino) propylamine or N , N-dimethyl-ethanolamine or bis (3-dimethylaminopropyl) amine, or mixtures thereof. The polyisocyanate which is used for the preparation of the diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, 1,6-hexanediisocyanate, dicyclohexylmethane-, 4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, or tetramethylxylene-diisocyanate, N ', N ", N' '' -tris (6-isocyanato-hexyl) isocyanurate, or N, N'-bis (6-isocyanatohexyl) -N- (6-isocyanatohexylamido) urea , or mixtures thereof. In order to obtain a fine particle size dispersion it is appropriate to incorporate hydrophilic groups into the tertiary amine functional prepolymer. For this reason other polyols can be present during the formation of the prepolymer which can be a polyethoxy diol, a poly (ethoxy / -propoxy) diol, a pendant chain-containing ethoxy or (ethoxy / propoxy) diol, a diol which contains a carboxylic acid or sulphonic acid or salt, or mixtures thereof. The prepolymer obtained can be chain extended or partially covered and partially chain extended. The reactive functional material of reactive hydrogen for chain extension is a diamine which can be: 1,2-diamino-propane, 1,3-diaminopropane, hydrazine, 5-amino-1,3,3-trimethyl-cyclohexanemethylamine , methylpentanediamine, hexanediamine, butyldiamine, poly (ethoxy / propoxy) diamine, polyethoxy diamine, polypropoxy diamine, bis (3-amino-propylamine) or a methylamine 5-amino-1,3, 3-themselves. The anionic polyurethane prepolymer used in the process is prepared by conventional methods. EP 308115 presents an overview of suitable polyols and polyisocyanates as well as reactive hydrogen functional compounds for chain extending the prepolymer. Essentially the anionic polyurethane in the process contains carboxylic acid groups which are neutralized by the urethane functional oligomer or polymer tertiary amine. The ratio of tertiary amine functions in the neutralizing agent to the carboxylic acid functions in the anionic polyurethane is from 0.5 to 1.5 and preferably from 0.7 to 1.2. Both the anionic polyurethane and the tertiary amine functional urethane urethane oligomer or polymer or dispersion thereof may contain additional functional groups in order to improve water dispersibility, to improve adhesion to substrates in the application, for performance reasons, or as Potential sites for crosslinking. Suitable functions are the polyalkoxy functions with a high concentration of ethoxy functions, are quaternary amine or tertiary amine functions, perfluor functions, incorporated silicone functions, hydrazide functions or hydrazone functions, ketone, acetoacetate, or aldehyde functions, or mixtures thereof.

The method of the invention are stable for extended periods of time. If desired, smaller amounts of solvents may be included in the dispersions. Many additional ingredients can also be found present in the application stage, for example, fillers, dyes, pigments, silicones, flow agents, foaming agents, agents that aim to achieve a matt effect, and the like. The aqueous polymer dispersions produced by the method of the invention can be used in adhesives, sealants, printing ink and coatings. The invention further comprises the dispersions obtained by the process and the coated substrates or films obtained by applying the dispersions on a substrate such as leather or artificial leather, metals, wood, glass, plastics, paper, cardboard, textile, non-woven, cloth , foam and the like by conventional methods, including spraying, flow coating, transfer coating, roller coating, brushing, dipping, dispersion and the like. Various aspects, features and embodiments of the present invention are illustrated through the following examples. These examples are merely illustrative and are not intended to limit the invention as claimed Examples Example 1 Preparation of a tertiary amine functional polyurethane dispersion. A mixture of 69.07 g (58.5 mmol) of 2- (hydroxy-methyl) -2- [(hydroxymethyl) oxyethylated) -butane-1-ol having a molecular weight of 1180 and can be obtained from Th. Goldschmidt as Tegomer D-3403 (hereinafter referred to as Tegomer D-3403) and 59.85 g (503 mol) of methyldiethanol-amine in 135 g of Proglyde DMM (non-protic solvent obtainable from The Dow Chemical Company) was heated at 60 degrees C during shaking. 186.08 g (837 mmol) of 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter referred to as IPDI) were added and the mixture was heated to 95 degrees C. The mixture was stirred for 2 hours at 95 degrees C and cooled. The content-NCO was 4.52%. The NCO amount was determined by adding a solution of dibutylamine to a sample of the product that reacts with isocyanate functions that are present in the sample. The remaining DBA was evaluated with 1 MHC1. In the calculation, a correction was made for the tertiary amines. 100 g of the isocyanate functional product was mixed with 1 g of sodium dioctylsulfosuccinate and the mixture was slowly added to a mixture of 5.27 g of 3- (dimethylamino) -The mixture was stirred for 30 min. The reaction was verified by the disappearance of the NCO-signal in the Infrared spectrum. The product was characterized by a solid amount of 30%, a pH of 9.58, a viscosity of 1100 cps. The amount of tertiary amine in the product was 0.64 meq / g. Example 2 Preparation of a tertiary functional amine polyurethane dispersion. Example 1 was repeated with the difference that 3- (dimethylamino) propylamine was replaced with 10.06 g of bis (3-dimethylaminopropyl) amine and 158.34 g of water were added. The product was characterized by a solid amount of 30%, a pH of 9.40, a viscosity of 800 cps. The amount of tertiary amine in the product was 0.81 meq / g. Example 3 Preparation of a functional chain extender hydrazone 100 g (1 mole) of ethylacrylate was added in the space of 45 min to 170 g (1 mole) of isophorone diamine at 40-45 degrees C. The mixture was stirred for 4 hours. hours at 40-45 degrees C. The reaction was verified by the disappearance of the double bond signals at 960 and 1600 cm-1 in the infrared spectrum. The intermediate product was a functional isophorone diamine ethyl N-aminopropionate. 50 g hydrazine hydrate (1 mole) was heated and stirred at 55-60 degrees C for 5 hours. The reaction was verified by the disappearance of the carbonyl signal at 1740 cm "1 of the ester carbonyl and the appearance of the carbonyl signal of the hydrazide carbonyl at 1650 cm" 1 in the infrared spectrum. The second intermediate was a functional isophorone diamine N-hydrazido-propionate. 58 g (1 mol) of acetone was added to the product obtained at room temperature and the mixture was stirred for 15 min. The product was a diamine of isophorone substituted in an N by a 3-propionylhydrazone. The product contained 2, 65 meq / g of hydrazone functions and 5.29 meq / g of amine functions. Example 4 Preparation of a tertiary amine and polyurethane functional hydrazone dispersion. Example 1 was repeated with the difference that the hydrazine was replaced by 10.17 g of the product of Example 3 and 158.41 g of water were added. The product was characterized by a solid amount of 30%, a pH of 9.40, a viscosity of 400 cps. The amount of tertiary amine in the product was 0.60 meq / g and the amount of hydrazone was 0.098 meq / g. Example 5 Preparation of a tertiary amine and polyurethane functional hydrazone dispersion.

Hydrazine and 3- (dimethylamino) propylamine were replaced by 19.32 g of the product of Example 3 and 157.61 g of water were used. The product was characterized by a solid amount of 30%, a pH of 9.40, a viscosity of 600 cps. The amount of tertiary amine in the product was 0.40 meq / g and the amount of hydrazone was 0.185 meq / g. Example 6 Preparation of a tertiary amine functional urethane oligomer. A mixture of 25.49 g (21.6 mmol) of Tegomer D-3403 and 28.20 g (316.8 mmol) of dimethylethanolamine in 53.02 g of Proglyde DMM was heated to 60 degrees C during stirring. 70.03 g (120 mmol) of N, N ', N "-tris (6-isocyanato-hexyl) isocyanurate were added and the mixture was heated to 95 degrees C. The mixture was stirred for 2 hours at 95 degrees C. The absence of residual isocyanate was verified by IR-spectroscopy and the mixture was cooled. The product was characterized by a solid amount of 70%, a viscosity of 14,000 cps. The amount of tertiary amine functions per gr was 1.79 meq / g. Example 7 Preparation of anionic polyurethane dispersions wherein a polyurethane functions as a carboxylic acid. First, an isocyanate-functional polyurethane prepolymer was prepared: 128.55 g (137.49 mmol) of Ruco S1015-120 (a polyester obtained from Occidental with a molecular weight of approximately 935 g), 374.07 g (124.69 mmol) of Ruco S1015-35 (a polyester obtained from Occidental with a molecular weight of approximately 3000 g) and 37.8 g (266.48 mmol) of 2,2-dimethylol propanoic acid in 84 g of dipropylene glycol dimethyl ether was heated to 80 degrees C. 211.47 g (951.59 mmol) of IPDI were added and the mixture was heated to 100 degrees C during stirring. The mixture was reacted at 100 degrees C for 2 hours. After 1 hour 0.1 g of tinoctoate was added as a catalyst. The reaction mixture was cooled and the NCO-amount of the prepolymer obtained appeared to be 3.95%. The amount of carboxylic acid functions is 0.336 meq / g. A product of Example 1, 2, 4, or 5 in an amount which is present in Table 1 together with 4 g of sodium dioctylsulfosuccinate was mixed in 100 g of the prepolymer by high shear mixing, followed immediately by an amount of water as presented in the table. When the mixture became homogeneous the dispersed polyurethane prepolymer was chain extended with the addition of 2.23 g of hydrazine hydrate and stirring. characterized by a solid amount of 30%, a pH between 6.8 and 7 when a stoichiometric amount of the tertiary amine functional urethane polymer was used, a pH of 6.6 when the ratio of tertiary amine functions: carboxylic acid functions it was 0, 7 and a pH of 7.9 when the ratio of tertiary amine functions: carboxylic acid functions was 1.2. 200 D films were prepared. All were clear flexible films. Table 1 Amount of tertiary amine functional urethane urethane oligomer or polymer used as a carboxylic acid neutralizing agent in Example 7 Example 8 Preparation of anionic functional polyurethane hydrazone dispersions wherein the action of a tertiary amine functional polyurethane as a neutralizing agent for carboxylic acid functions is compared with triethylamine or sodium hydroxide as a neutralizing agent. Preparation of dispersions of functional anionic polyurethane hydrazone wherein the action of a tertiary amine functional polyurethane as a neutralizing agent for carboxylic acid functions is compared with triethylamine or sodium hydroxide as a neutralizing agent. 88.24 g (86.68 mmol) of a polypropylene glycol with a molecular weight of 1018, 132.36 g (66.18 mmol) of a polypropylene glycol with a molecular weight of 2000 and 15.96 (112, 52 mmol) of 2,2-dimethylolpropanoic acid in 21 g of dipropylene glycol dimethyl ether was heated to 80 degrees C. The mixture was added dropwise to at degrees C during stirring. The mixture was reacted for 2 hours at 100 degrees C. After 1 hour 0 was added, 1 g of tinoctoate as a catalyst. The reaction mixture was cooled and the NCO-amount of the prepolymer obtained appeared to be 5.18%. A stoichiometric amount of product of example 4 or of sodium hydroxide or triethylamine ccn with respect to the carboxylic acid function in the prepolymer was added to 100 g of the prepolymer by high shear mixing in a weight amount presented in the table. 2 together with 2 g of sodium dioctylsulfosuccinate, followed immediately by an amount of water as presented in table 2. When the mixture was homogenously prepared the dispersed polyurethane prepolymer was chain extended by the addition of 1.53 g of hydrazine followed by 12.83 g of the product of Example 4 in 20 g of water and stirring for 30 minutes. The aqueous polyurethanes obtained are characterized by an amount of solid of 30% and depending on the neutralizing agent using a pH as shown in the table. Table 2 Comparison of carboxylic acid neutralizing agents and a carboxylic acid neutralizing agent according to the invention or with a stoichiometric amount of an NCO-crosslinker with respect to the incorporated hydrazone functions. The NCO crosslinker was XR-5350 (obtainable from Stahl Holland). The weight increase of the films in water was measured after the treatment of the films with water for 24 hours. The results are presented in table 3.

The results show that the sensitivity to water is polyurethane in which the carboxylic acid functions were neutralized with the product of Example 4 and with triethylamine, while the films of the polyurethanes with NaOH as a neutralizing agent are more sensitive to water. The films containing a hydrazone function that are crosslinked by the NCO-crosslinker have a lower weight increase in water. As the tertiary amine functional product of Example 4 also contains hydrazone functions, these will bind to the anionic polyurethane polymer chain during film formation. Table 3 Comparison of water uptake of anionic polyurethane dispersion films of which the carboxylic acid functions were neutralized with various neutralizing agents

Claims (17)

1. A process for the preparation of an aqueous dispersion of an anionic polyurethane characterized in that a functional urethane amine urethane polymer or oligomer acts as an acidic neutralizing agent. The process according to claim 1, characterized in that the process comprises the steps of: dispersing an anionic isocyanate functional polyurethane prepolymer in water in the presence of a tertiary functional amine urethane polymer or oligomer and prepolymer chain extension of anionic polyurethane with a reactive hydrogen functional material during or after dispersion in water. 3. The process according to claim 1 and 2, characterized in that said anionic group in the polyurethane to be neutralized is a carboxylic acid group. The process according to claims 1-3, characterized in that said tertiary amine functional urethane polymer or oligomer is prepared by the reaction of a functional polyurethane prepolymer of an isocyanate or a polyisocyanate with a reactive hydrogen functional material containing tertiary amine functions. 5. The process according to claims 1-4, characterized in that said oligomer or urethane polymer preparation of an isocyanate functional polyurethane prepolymer containing tertiary amine functions of a polyisocyanate and a polyol containing tertiary amine functions, chain extender and / or partially covering the prepolymer with a reactive hydrogen functional material. The process according to claims 1-4, characterized in that the tertiary amine functional urethane urethane oligomer or polymer can occur in an aqueous dispersion which is prepared by the steps of: preparing an isocyanate-functional polyurethane prepolymer containing functional tertiary amine of a polyisocyanate and a polyol containing tertiary amine functions. Dispersion of the prepolymer in water, chain extender and / or partially cover the prepolymer with a reactive hydrogen functional material during or after dispersion in water. The process according to claim 5 or 6, characterized in that said tertiary amine-containing polyol which is used to prepare the polyurethane prepolymer is N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, 3-diisopropylamino- 1, 2-propanediol, 3- (dimethylamino) -1,2-propanediiol, 3- (diethylamino) -1,2-triisopropanolamine, and is preferably N-methyldiethanolamine, or (3-dimethylamino-propyl) diisopropanolamine. The process according to claims 4-6, characterized in that said reactive hydrogen functional material is a mono-alcohol, monoamine, polyamine, tertiary amine functional polyol or a mixture thereof. The process according to claim 8, characterized in that the functional material of reactive hydrogen is a polyol containing tertiary amine functions according to claim 7 or is a diamine containing a tertiary amine function and which is bis (3-) aminopropyl) methylamine. 10. The process according to claim 8, characterized in that the mono-amine or mono-alcohol containing a tertiary amine is 2- (diethylamino) ethylamine, 3- (diethylamino) -propylamine, N, N, N '- trimethylethylenediamine, N, N, N '-trimeti? -1, 3-propanediamine, N, N, 2, 2-tetramethyl-l, 3-propylenediamine, N, -diethylethanolamine, l-dimethylamino-2-propanol, 3-dimethylamino -l-propanol, 2-dimethylamino-2-methyl-l-propanol, l-diethylamino-2-propanol, 3-diethylamino-1-propanol, 2- (diisopropylamino) ethanol, 5-diethylamino-2-pentanol, 2- (dibutylamino) -ethanol and is preferably 2- (dimethylamino) ethylamine, 3- (dimethylamino) -propylamine, N, N-mixtures thereof. The process according to claims 4-10, characterized in that the polyisocyanate in claim 4, 5 or 6 is 2,4-toluene-diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, 1,6-hexanediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, tetramethylxylene diisocyanate, N, N ', N "-tris (6-isocyanatohexyl) isocyanurate , N, N'-bis (6-isocyanatohexyl) -N- (6-isocyanatohexylamido) urea, or mixtures thereof. 12. The process according to claims 5-11, characterized in that a further polyol is present during the formation of the prepolymer, which may be a polyethoxy diol, a poly (ethoxy / propoxy) diol, a diol containing a ethoxy or (ethoxy / propoxy) pendant chain, a diol containing a carboxylic acid or a sulfonic acid or salt, or mixtures thereof. 13. The process according to claims 1-12, characterized in that the reactive hydrogen functional material for the chain extension of the tertiary functional amine polyurethane prepolymer of the claims 4-12 is a diamine such as 1,2-diamino-propane, 1,3-diaminopropane, hydrazine, 5-amino-1,3, 3-trimethylcyclohexanemethylamine, methylpentane diamine, polyethoxy diamine, polypropoxy diamine or bis (3-aminopropyl). ethylamine or a functional 5-amino-1,3,3-trimethyl-cyclohexanomethylamine N- "-idrazone, or mixtures thereof 14. The process according to the re" indications 1-13, characterized in that the relationship tertiary amino functions in the neutralizing agent of claim 4 to 13 the carboxylic acid functions in the anionic polyurethane is from 0.5 to 1.5 and preferably from 0.7 to 1.2. 15. The process according to the re: / indications 1-14, characterized in that the dispersion of anionic polyester and / or the urethane oligomer or urethane polymer or tertiary amine dispersion thereof contains additional functional groups that they can be polyacyloxy functions with a high concentration of ethoxy functions, incorporated silicone furcations, perfluorine functions, ketone functionalities, acetoacetate or aldehyde functions of pendant hydrazone c: idrazide, or mixtures thereof. 16. Dispersions obtained by the process of claims 1-15. 17. Dispersions according to claim 16, comprising customary additives such as coloring agents, pigments, agents intended to achieve a matte effect, silicones, flow agents and the like. applying a dispersion of claims 16 or 17 on a substrate such as leather, artificial leather, metal, wood, glass, plastic, paper, cardboard, textile, nonwovens, cloth, foam, etc. The present invention relates to a process for the preparation of an aqueous dispersion of an anionic polyurethane. According to the invention, a tertiary functional amine urethane oligomer or polymer acts as an acid neutralizing agent. The process of the invention comprises the steps of: Dispersing an anionic isocyanate functional polyurethane prepolymer in water in the presence of a tertiary functional amine urethane oligomer or polymer and chain extension of the anionic polyurethane prepolymer with a reactive hydrogen functional material during or after dispersion in water. In addition, the invention deals with dispersions obtained by the present process, which may comprise customary additives such as coloring agents, pigments, agents which aim to achieve a matt effect, silicones, flow agents and the like. Finally the invention relates to a coated film or substrate, which is obtained by applying the above dispersion on a substrate such as leather, artificial leather, metal, wood, glass, plastic, paper, cardboard, textile, non-woven, cloth, foam, etc.