Aqueous polyurethane dispersion

Abstract

The present invention relates to aqueous polyurethane dispersion comprising water and a polyurethane, wherein the polyurethane is obtained by reacting at least components (A)-(E): (A) one or more aromatic polyester polyol and optionally one or more polycarbonate polyol, wherein said aromatic polyester polyol and polycarbonate polyol have a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, (B) one or more polyether polyol with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, wherein the amount of said polyether polyol (B), based on the total weight of (A) and (B), is at least 45.0% by weight, (C) one or more diisocyanate with formula Y(NCO)2, wherein Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon group or Y is a C6-C15 divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group, (D) one or more non-ionic hydroxy-functional polyether with an ethylene oxide content of at least 50% by weight, and (E) one or more ionic isocyanate-reactive compounds comprising sulfonate (-SO3 -) groups in the salt form, wherein the number average molecular weight of the components (A), (B) and (D) are determined with the method as described in the description, wherein the components (A), (B), (C), (D) and (E) are distinct.

Description

[0001] 2024PF30056 - Foreign Countries

[0002] 1

[0003] AQUEOUS POLYURETHANE DISPERSION

[0004] Field of the invention

[0005]

[0001] The present invention relates to aqueous polyurethane dispersion, which is especially suitable for waterproofing coating applications. The present invention also relates to a coating composition comprising such an aqueous polyurethane dispersion. The present invention further relates to a one-component coating system comprising such a coating composition, as well as to articles comprising a substrate that is at least partially coated with a coating obtained by curing such a coating composition. The present invention further relates to the use of such a coating composition for waterproof building, including exterior walls, exterior roofs, bathrooms, kitchens and basements.

[0006] Background

[0007]

[0002] Waterproofing coatings play a crucial role in protecting various structures from water damage, particularly in exposed roof applications. In recent years, there has been a growing demand for high-performance, environmentally friendly waterproofing solutions.

[0008]

[0003] Existing waterproofing coating solutions in the market include solvent-based polyurethane systems. However, these solvent-based materials emit high levels of volatile organic compounds (VOCs) into the environment during application and curing. This poses significant challenges in terms of environmental impact and potential health risks to construction workers and end-users.

[0009]

[0004] CN-A-113136020 discloses a waterborne polyurethane dispersion for waterproofing coatings. This invention incorporates amino functionalized alkoxy silane and amino boric acid (ester) as building blocks in the polyurethane structure. While this approach offers certain advantages, there remains a need for further improvement, particularly in further reducing water absorption rates. Moreover, the incorporation of amino functionalized alkoxy silanes as building blocks in polyurethane formulations presents significant challenges.

[0010] Primarily, these compounds may compromise storage stability due to their susceptibility to hydrolysis and subsequent crosslinking, processes that are pH dependent. This pH sensitivity is particularly problematic when applying the polyurethane to mineral substrates or concrete, where pH control is inherently difficult. Furthermore, amino boric acid (ester) offers only marginal improvements in water absorption rates. Additionally, the high cost associated with amino boric acid (ester) further diminishes its viability as a practical solution in this context.

[0011]

[0005] Therefore, there exists a need for aqueous polyurethane dispersions that exhibit good dispersion stability upon CaCh addition, and which is capable of providing coatings with2024PF30056 - Foreign Countries

[0012] 2

[0013] excellent mechanical properties (in particular tensile strength and elongation at break), excellent flexibility at low temperatures, low water absorption, and superior heat, acid, and alkali resistance. Furthermore, this improved formulation should achieve these performance characteristics without relying on amino functionalized alkoxy silane and amino boric acid (ester) as building blocks for the polyurethane, thus overcoming the limitations associated with these components.

[0014] Summary of the invention

[0015]

[0006] The invention relates to aqueous polyurethane dispersions comprising water and a polyurethane, wherein the polyurethane is obtained by reacting at least components (A)-(E): (A) one or more aromatic polyester polyol and optionally one or more polycarbonate polyol, wherein said aromatic polyester polyol and polycarbonate polyol have a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, (B) one or more polyether polyol with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, wherein the amount of said poly ether polyol (B), based on the total weight of (A) and (B), is at least 45.0% by weight,

[0016] (C) one or more diisocyanate with formula Y(NCO)2, wherein Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon group or Y is a Ce-Cis divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group,

[0017] (D) one or more non-ionic hydroxy -functional polyether with an ethylene oxide content of at least 50% by weight, and

[0018] (E) one or more ionic isocyanate-reactive compounds comprising sulfonate (-SO3 ) groups in the salt form,

[0019] wherein the components (A), (B), (C), (D) and (E) are distinct.

[0020]

[0007] The invention further relates to a coating composition comprising the dispersion according to the invention.

[0021]

[0008] The invention further relates to one-component system comprising the dispersion according to the invention.

[0022] Detailed Description of the invention

[0023]

[0009] The specification provides definitions for certain technical terms used in the specification and / or the claims. Any other technical term used in the specification and / or the claims that is not defined in the specification has the meaning attributed to it by one of ordinary skill in the art.2024PF30056 - Foreign Countries

[0024] 3

[0025]

[0010] For all upper and lower boundaries of any parameters given herein, the boundary value is included in each range for each parameter. All combinations of minimum and maximum values of the parameters described herein may be used to define the parameter ranges for various embodiments and preferences of the invention.

[0026] [OH] In the context of the present invention, a polyurethane is a polymer obtained by polymerization of one or more polyols and one or more polyisocyanates, but it also includes those in which also monoamines and / or diamines are used as formation components, possibly as chain extenders. The polyurethanes that can be used in the present invention include polyurethanes as well as polyurethane-polyureas. Preferably the polyurethane present in the waterborne coating composition of the present invention is a polyurethane-polyurea. Methods for preparing polyurethanes are known in the art and are described in for example the Polyurethane Handbook 2nd Edition, a Carl Hanser publication, 1994, by G. Oertel.

[0027]

[0012] The present invention is directed to aqueous polyurethane dispersions comprising water and a polyurethane, wherein the polyurethane is obtained by reacting at least components (A)-(E):

[0028] (A) one or more aromatic polyester polyol and optionally one or more polycarbonate polyol, wherein said aromatic polyester polyol and polycarbonate polyol have a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, (B) one or more polyether polyol with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, wherein the amount of said polyether polyol (B), based on the total weight of (A) and (B), is at least 45.0% by weight,

[0029] (C) one or more diisocyanate with formula Y(NCO)2, wherein Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon group or Y is a Ce-Cis divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group,

[0030] (D) one or more non-ionic hydroxy -functional polyether with an ethylene oxide content of at least 50% by weight, and

[0031] (E) one or more ionic isocyanate-reactive compounds comprising sulfonate (-SO3 ) groups in the salt form,

[0032] wherein the components (A), (B), (C), (D) and (E) are distinct.

[0033]

[0013] It has surprisingly been found that the aqueous polyurethane dispersions according to the invention dispersion exhibit good dispersion stability upon CaCh addition, and are capable of providing coatings with excellent mechanical properties (in particular tensile strength and elongation at break), excellent flexibility at low temperatures, low water absorption (even below 5%), and superior heat, acid, and alkali resistance, without relying on amino2024PF30056 - Foreign Countries

[0034] 4

[0035] functionalized alkoxy silane and amino boric acid (ester) as building blocks for the polyurethane. An additional advantage of the present invention is that one-component systems comprising a coating composition according to the present invention are capable of providing coatings with excellent mechanical properties (in particular tensile strength and elongation at break, excellent flexibility at low temperatures, low water absorption, and superior heat, acid, and alkali resistance, through curing under atmospheric conditions, without the need to increase the temperature to, for example, 40 °C.

[0036]

[0014] The concept of hydroxy functionality is familiar to the skilled person. It indicates the number of reactive OH groups (hydroxyl groups) that are present on average per molecule. The term “hydroxy functionality” refers to the average number of reactive hydroxyl groups, -OH, present per molecule of the -OH functional material that is being described. In the production of a polyurethane, the hydroxyl groups react with isocyanate groups, -NCO, that are attached to an isocyanate compound. The term "hydroxyl number" or “hydroxyl value” refers to the number of reactive hydroxyl groups available for reaction, and is expressed as the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of the polyol (DIN EN ISO 4629-2). The term "equivalent weight" refers to the weight of a compound divided by its valence. For a polyol, the equivalent weight is the weight of the polyol that will combine with an isocyanate group, and may be calculated by dividing the number average molecular weight of the polyol by its functionality. The equivalent weight of a polyol may also be calculated by dividing 56,100 by the hydroxyl number of the polyol: Equivalent Weight (g / eq) = (56.1xlOOO) / OH number.

[0037] Component (A)

[0038]

[0015] Component (A) is one or more aromatic polyester polyol and optionally one or more polycarbonate polyol, wherein said aromatic polyester polyol and polycarbonate polyol have a number average molecular weight, determined as described further herein, of from 500 to 4000 g / mol, and a hydroxy functionality from 1.9 to 2.1, preferably a hydroxy functionality of 2.0. Preferably, the amount of the one or more aromatic polyester polyol is at least 10% by weight, more preferably at least 15% by weight, even more preferably at least 20% by weight, even more preferably at least 25% by weight, even more preferably at least 30% by weight, even more preferably at least 35% by weight, even more preferably at least 40% by weight, even more preferably at least 45% by weight, even more preferably at least 50% by weight, even more preferably at least 55% by weight, even more preferably at least 60% by weight, even more preferably at least 65% by weight, even more preferably at least 70% by weight, even more preferably at least 75% by weight, even more preferably at least 80% by weight, even2024PF30056 - Foreign Countries

[0039] 5

[0040] more preferably at least 85% by weight, even more preferably at least 90% by weight, relative to the total amount of component (A). Most preferably, the amount of the one or more aromatic polyester polyol is 100% by weight, relative to the total amount of component (A), i.e., component (A) is one or more aromatic polyester polyol.

[0041]

[0016] Suitable aromatic polyester polyols are polyester polyols which can be prepared in a known manner from aromatic di- or poly-carboxylic acids, such as, for example, terephthalic acid, isophthalic acid, o-phthalic acid, or trimellitic acid, as well as acid anhydrides, such as o-phthalic anhydride, isophthalic anhydride, trimellitic anhydride, or terephthalic anhydride, or any mixture of at least two thereof with polyhydric alcohols, such as, for example, ethanediol, di-, tri-, tetra-ethylene glycol, 1,2-propanediol, di-, tri-, tetra-propylene glycol, 1,3-propanediol, 2-methyl-l,3-propanediol, 1,4-butanediol, 1,3 -butanediol, 2,3 -butanediol, 1,5-pentanediol, 3-methyl-l,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-l,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylol cyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol or mixtures thereof, optionally with the concomitant use of higher-functional polyols, such as trimethylolpropane, glycerol or pentaerythritol. Suitable polyhydric alcohols for the preparation of the polyester polyols are also cycloaliphatic and / or aromatic di- and polyhydroxyl compounds. Instead of the free poly carboxylic acid it is also possible to use for the preparation of the aromatic polyester polyols the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof. Preferably, the aromatic polyester polyol (A) is prepared from one or more aromatic dicarboxylic acids and / or the corresponding aromatic dicarboxylic anhydride with one or more diols. Preferred aromatic dicarboxylic acids and corresponding aromatic dicarboxylic anhydrides are selected from the group consisting of phthalic acid, phthalic anhydride, terephthalic acid, terephthalic anhydride, isophthalic acid, isophthalic anhydride and any mixture of at least two thereof. More preferred aromatic dicarboxylic acids and corresponding aromatic dicarboxylic anhydrides are selected from the group consisting of phthalic acid, phthalic anhydride, isophthalic acid, isophthalic anhydride and any mixture of at least two thereof. Even more preferred aromatic dicarboxylic acids and corresponding aromatic dicarboxylic anhydrides are phthalic acid and phthalic anhydride. Preferred diols are selected from the group consisting of di ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-l,3-propanediol, 1,4-butanediol, 1,3 -butanediol, 2,3 butanediol, 1,5-pentanediol, 3-methyl-l,5-pentanediol, 1,6-hexanediol, neopentylglycol and any mixture of at least two thereof. More preferred diols are selected from the group consisting of 1,6-hexanediol, neopentylglycol and any mixture thereof. Most preferred diols are 1,6-hexanediol and mixtures of 1,6-hexanediol and neopentylglycol.2024PF30056 - Foreign Countries

[0042] 6

[0043]

[0017] Suitable polycarbonate polyols are those which can be prepared by reacting diols such as 1,3-propanediol, 1,4-butanediol, 3-methyl-l,5- pentanediol and / or 1,6-hexanediol with diaryl carbonates, such as diphenyl carbonate, dialkyl carbonates, such as dimethyl carbonate, or phosgene or any mixture of at least two thereof. Preference is given to polycarbonate polyols that have been prepared by reacting 1,6-hexanediol with dimethyl carbonate.

[0044]

[0018] The amount of component (A) used to prepare the polyurethane is preferably from 4.0 to 45.0% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0045] Component (B)

[0046]

[0019] Component (B) is one or more polyether polyol with a number average molecular weight, determined as described further herein, of from 500 to 4000 g / mol, and a hydroxy functionality from 1.9 to 2.1, preferably a hydroxy functionality of 2.0.

[0047]

[0020] Preferably, component (B) comprises one or more polytetrahydrofuran (also known as poly(tetram ethylene ether) glycol) and optionally one or more polypropylene glycol. More preferably, component (B) consists of one or more polytetrahydrofuran and optionally one or more polypropylene glycol. The amount of polytetrahydrofuran, based on the total weight of (B), is preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight. This may advantageously result in further lowering of the water absorption rate and also in an increased tensile strength. Most preferably, component (B) consists of one or more polytetrahydrofuran.

[0048]

[0021] The amount of component (B) used to prepare the polyurethane is preferably from 40.0 to 80.0% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0049]

[0022] The amount of the one or more polyether polyol (B), based on the total weight of the components (A) and (B), is at least 45.0% by weight, preferably at least 48.0% by weight, more preferably at least 50.0% by weight. Accordingly, the combined amount of aromatic polyester polyols and, if used, polycarbonate polyols, based on the total weight of components (A) and (B), is at most 55.0% by weight, preferably at most 52.0% by weight, more preferably at most 50.0% by weight.

[0050]

[0023] Preferably, the combined amount of component (A) and component (B), based on the total amount of isocyanate-reactive components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated, is at least 80.0% by weight, more preferably at least 85.0% by weight, even more preferably at least 90.0% by weight.2024PF30056 - Foreign Countries

[0051] 7

[0052] Component (C)

[0053]

[0024] Component (C) is one or more diisocyanate with formula Y(NCO)2, wherein Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon group or Y is a Ce-Cis divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group. Preferably, the one or more diisocyanates (C) are selected from the group consisting of 1,5-pentamethylenediisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexane-1,4-diisocyanate, 1,3- and l,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate (HMDI) and any mixture of two or more thereof, preferably the one or more diisocyanates (C) are selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and any mixture of two or more thereof. The di cyclohexylmethane diisocyanate is preferably 4,4’ -di cyclohexylmethane diisocyanate (4,4’-H12MDI). Even more preferably, the one or more diisocyanates (C) are selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and any mixture thereof. Even more preferably, the diisocyanate (C) is 1,6-hexamethylene diisocyanate (HDI).

[0054]

[0025] The amount of component (C) used to prepare the polyurethane is preferably from 8.0 to 25.0% by weight, more preferably from 9.0 to 20.0% by weight, even more preferably from 10.0 to 15.0% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0055] Component (D)

[0056]

[0026] Component (D) is one or more non-ionic hydrophilic hydroxy functional polyether with an ethylene oxide content of at least 50% by weight. Preferably, component (D) comprises polyethylene oxide groups composed of at least 5 ethylene oxide repeating units, preferably of at least 10, more preferably of at least 15 ethylene oxide repeating units and preferably at most 120, more preferably at most 80 and even more preferably at most 40 ethylene oxide repeating units. More preferred components (D) are polyalkylene glycols having from 10 to 60 and preferably from 15 to 30 ethylene oxide repeating units. The polyalkylene glycols having from 10 to 60 ethylene oxide repeating units and preferably from 15 to 30 ethylene oxide repeating units are preferably selected from the group consisting of ethylene oxide polymers, copolymers of ethylene oxide and propylene oxide and any mixtures of two or more thereof. More preferably, the polyalkylene glycols having from 10 to 60 ethylene oxide repeating units and preferably from 15 to 30 ethylene oxide repeating units are copolymers of ethylene oxide and propylene oxide.2024PF30056 - Foreign Countries

[0057] 8

[0058]

[0027] The number average molecular weight of component (D) is preferably at least 350 g / mol, more preferably at least 1000 g / mol and preferably at most 4500 g / mol.

[0059]

[0028] The hydroxy functionality of component (D) is preferably from 0.9 to 2.1, more preferably from 0.9 to 1.1.

[0060]

[0029] The amount of component (D) used to prepare the polyurethane is preferably from 0.1 to 6.0% by weight, more preferably from 0.1 to 4.0% by weight, even more preferably from 0.1 to 2.0% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0061] Component (E)

[0062]

[0030] Component (E) is one or more isocyanate-reactive compounds comprising sulfonate (-SOf) groups in the salt form. Preferably, the sulfonate containing component (E) is a diaminosulfonate corresponding to the following general formula:

[0063] H2N-A-NH-B-SO3-Cat+wherein A and B represent aliphatic hydrocarbon radicals (i.e., aliphatic hydrocarbon groups) having from 2 to 6 carbon atoms, preferably ethylene radicals (i.e., ethylene groups), and Cat+represents an optionally substituted ammonium cation or preferably a sodium or potassium cation, more preferably sodium cation. A very suitable sulfonate containing compound is the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid.

[0064]

[0031] The amount of component (E) used to prepare the polyurethane is preferably from 1.0 to 2.5% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0065]

[0032] Components (D) and (E) are hydrophilizing components which enable the polyurethane to be stably dispersed in water. The combined amount of component (D) and component (E) is preferably at most 6.0% by weight, more preferably at most 5.0% by weight, even more preferably at most 4.5% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0066]

[0033] The polyurethane is preferably the reaction product formed through a reaction between at least components (A), (B), (C), (D) and (E), and (F) and / or (G), wherein the components (A), (B), (C), (D), (E), (F) and (G) are distinct. More preferably, the polyurethane is the reaction product formed through a reaction between components (A), (B), (C), (D) and (E), and (F) and / or (G), wherein the components (A), (B), (C), (D), (E), (F) and (G) are distinct.2024PF30056 - Foreign Countries

[0067] 9

[0068] Component (F)

[0069]

[0034] Component (F) is one or more diol having a molar mass of from 32 to 400 g / mol. Suitable examples of diols having a molar mass of from 32 to 400 g / mol are ethylene glycol, diethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol and neopentylglycol.

[0070] Preferred diols having a molar mass of from 32 to 400 g / mol are 1,6-hexanediol and / or neopentylglycol.

[0071]

[0035] The amount of component (F) used to prepare the polyurethane is preferably from 0.1 to 4.0% by weight, more preferably from 0.1 to 3.0% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0072] Component (G)

[0073]

[0036] Component (G) is one or more amine functional chain extender. The one or more amine functional chain extenders are preferably selected from the group consisting of compounds with a NH2 and / or NH functionality of 2, preferably selected from the group consisting of hydrazine, 1,2-ethanediamine, 1,4-butanediamine, 2-methyl-l,5- pentanediamine, 1,6- hexamethylene-diamine, 1,4-hexamethylenediamine, isophorone diamine (i.e. 3-aminomethyl-3,5,5-trimethylcyclohexylamine), 1,3- bis(aminomethyl)cyclohexane, xylylenediamine, piperazine, 2, 5 -dimethylpiperazine, 1,3- diamino-2-propanol, N-(2-hydroxyethyl)-ethylene diamine, N,N-bis(2 -hydroxy ethyl)-ethylene diamine and any mixture of two or more thereof.

[0074]

[0037] The amount of component (G) used to prepare the polyurethane is preferably from 0.1 to 3.0% by weight, more preferably from 0.1 to 2.0% by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

[0075]

[0038] The polyurethane present in the aqueous polyurethane dispersion of the present invention preferably has a weight average molecular weight Mwof at least 80,000, preferably of at least 100,000 Dalton, more preferably of at least 120,000 Dalton, and preferably of at most 1,000,000 Dalton, whereby the Mwis determined with the method as described further herein.

[0076]

[0039] The aqueous dispersion according to the present invention preferably further comprises one or more antioxidants in an amount of preferably from 0.25 to 5.0% by weight, more preferably from 0.25 to 4.5% by weight, more preferably from 0.5 to 4.0% by weight, even more preferably from 0.8 to 3.5% by weight, based on the amount of polyurethane present in the dispersion. The one or more antioxidants are preferably selected from the group consisting of2024PF30056 - Foreign Countries

[0077] 10

[0078] hindered phenols, benzofuranones, hydroxyamines, phosphites, sulfur compounds, preferably the one or more antioxidants are hindered phenols, preferably selected from the group consisting of ethylene bis(oxyethylene) bis(3-tert-butyl-4-hydroxy-5-(methylhydrocinnamate), tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy hydrocinnamate)]methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, N,N’-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), C7-C9 branched alkyl esters of 3, 5 -di -tert-butyl -4-hydroxyhydrocinnamic acid, reaction product of N-phenylbenzene amine with 2,4,4-trimethylpentene, and any mixture of two or more thereof.

[0079]

[0040] The aqueous polyurethane dispersion according to the invention preferably has a solid content of at least 40% by weight and preferably of at most 60% by weight, more preferably of at most 55% by weight.

[0080]

[0041] The present invention further provides a process for the preparation of the aqueous polyurethane dispersions according to the invention, characterized in that, in a first step, some or all of components (A), (B), (C) and (D) (and optionally components (F) and / or (G)), optionally in the presence of a solvent that is miscible with water but inert towards isocyanate groups, are placed in a reactor and heated to temperatures in the range from 50 to 120 degrees centigrade, and then any of constituents (A), (B), (C), (D), (F) or (G) that were not added at the beginning of the reaction are metered in, in a second step the chain extension with component (E) is carried out at temperatures of from 15 to 60 degrees centigrade and, before, during or after the chain extension, conversion into the aqueous phase is carried out and the solvent optionally used is removed.

[0081]

[0042] The present invention further relates to a coating composition comprising the dispersion as described herein above as a binder.

[0082]

[0043] Said coating composition preferably comprises from 0.5 to 1% by weight of dispersant and wetting agent, from 0.4 to 1% by weight of defoamer, from 30 to 50% by weight of pigment (preferably barium sulfate and / or titanium oxide), from 0.05 to 0.1% by weight of pH regulator, from 0.01 to 0.1% by weight of stabilizer, from 35 to 55% by weight of aqueous polyurethane dispersion as described and / or claimed herein, from 0.5 to 7% by weight of coalescent, from 0.1 to 0.7% by weight of thickener and from 5 to 20% by weight of water, wherein the amounts are given based on the coating composition.

[0083]

[0044] The coating composition of the invention preferably comprises the polyurethane (solid) as described herein above in an amount of from 10.0 to 30.0% by weight, more preferably from 12.0 to 28.0% by weight, even more preferably from 15.0 to 25.0% by weight, based on the total weight of the coating composition. The coating composition according to the invention2024PF30056 - Foreign Countries

[0084] 11

[0085] preferably has a solid content of at least 45% by weight, more preferably of at least 50% by weight and preferably of at most 70% by weight, more preferably of at most 65% by weight.

[0086]

[0045] The coating composition is preferably a one-component system. A one-component coating system can be cured by water and / or solvent evaporation, while for a two-component system a compound comprising the aqueous polyurethane dispersion and a curing agent are mixed just prior to application to be cured during application.

[0087]

[0046] The present invention further relates to the use of the coating composition as described above for waterproof coating, particularly for exterior walls, exterior roofs, bathrooms, kitchens, and basements.

[0088]

[0047] The present invention further relates to an article comprising a substrate, optionally at least partly coated with a primer, that is at least partly coated with a coating obtained by curing the coating composition as described herein above. The substrate is preferably a building material, in particular an exterior wall, an exterior roof, building material or furniture for bathrooms, building material or furniture for kitchens or building material or furniture for basements.

[0089]

[0048] The present invention further relates to a process for preparing a coated substrate, comprising at least the following steps:

[0090] (1) Providing a substrate,

[0091] (2) Optionally priming at least a portion of the substrate with a primer composition to obtain an at least partly primed substrate,

[0092] (3) Applying the coating composition as described herein to at least a portion of the substrate, or to at least a portion of the at least partly primed substrate,

[0093] (4) Optionally applying a cover on the coating composition,

[0094] (5) Curing the coating composition applied in step (3), preferably under atmospheric conditions, to obtain the coated substrate.

[0095]

[0049] The substrate is preferably a building material used in exterior walls, exterior roofs, or in bathrooms, kitchens, or basements, either as structural elements or furniture. The substrate is usually engineered stone, wood, (artificial) marble, terrazzo, ceramic, metals, mineral materials, plastics, rubber, concrete, composite sheet, most preferably the substrate is concrete.

[0096]

[0050] The coating composition as described herein is preferably applied in a dry film thickness ranging from 1.0 to 1.5 mm. A cover, such as a tile, may be applied particularly when the substrate is used in bathrooms, kitchens, or basements, either as structural elements or furniture.

[0097]

[0051] In an embodiment of the invention, the substrate is an exterior wall or an exterior roof, optionally at least partly coated with a primer to obtain an at least partly primed exterior wall or2024PF30056 - Foreign Countries

[0098] 12

[0099] exterior roof, that is at least partly coated with a coating obtained by curing the coating composition as described herein above. In this embodiment, the process for preparing the coated exterior wall or the coated exterior roof preferably consists of the following steps:

[0100] (1) Providing an exterior wall or an exterior roof,

[0101] (2) Optionally priming at least a portion of the exterior wall or the exterior roof with a primer composition to obtain an at least partly primed exterior wall or at least partly primed exterior roof,

[0102] (3) Applying the coating composition as described herein to at least a portion of the exterior wall or the exterior roof, or to at least a portion of the at least partly primed exterior wall or at least partly primed exterior roof,

[0103] (4) Curing the coating composition applied in step (3), preferably under atmospheric conditions, to obtain the coated exterior wall or the coated exterior roof.

[0104]

[0052] The present invention is now illustrated by reference to the following examples. Unless otherwise specified, all parts, percentages and ratios are on a weight basis.

[0105] Measurement and Testing Methods

[0106]

[0053] Unless stated otherwise, all analytical measurements relate to measurements at temperature of 23 °C

[0107] Particle size

[0108]

[0054] Test for Z-average particle size and poly dispersity index PDI of aqueous polvurethane dispersion

[0109] Average particle size refers to Z-average size was tested using Zetasizer Nano from Malvern (Malvern Zetasizer Nano ZS). 1 drop (about 0.05 g) polyurethane dispersion (PUD) was added to 50 mL DI water. Test temperature was 23.0 ± 0.1 °C. Setting for testing material: polystyrene latex (refractive index of 1.590, absorption value of 0.010); setting for dispersant: water (temperature of 23.0 °C, viscosity of 0.9308 cps, refractive index of 1.330); and equilibrium time of 60 seconds. Type of sample cell: disposable sample cell DTS0012. Positioning method: automatic attenuation, automatic optimization of positioning. Analysis mode: general purpose (normal resolution). Test angle: 173° backscatter (NIBS default). Each sample was tested for 3 rounds with 10 times per round, the time for each test being 10 seconds. Z-average particle size and poly dispersity index were average of all tests, respectively. Z-average particle size was defined according to the standard ISO 13321 as the average particle size measured according to the principle of dynamic light scattering. The poly dispersity index represents the distribution of particle size. The closer to 0 is PDI, the narrower is the particle size distribution.2024PF30056 - Foreign Countries

[0110] 13

[0111] Solid content

[0112]

[0055] Solid content was tested with a halogen moisture analyzer from Mettler Toledo (Mettler Toledo Halogen Moisture Analyzer Excellence HS153). A piece of glass fiber filter paper was placed on a standard aluminum weighing pan. 1 gram of the tested aqueous polyurethane dispersion was dropped on the glass fiber filter paper. It was dried with a standard drying procedure at drying temperature of 120 °C with stop standard of level 5 (1 mg / 140 seconds). That is, the sample was heated at 120°C and continuously weighed. If the weight loss of the sample was less than 1 mg within 140 seconds, the test was stopped and the remaining weight percentage was recorded as the solid content.

[0113] pH

[0114]

[0056] The pH was measured at 23 °C using a PB-10 pH meter from Sartorius, Germany according to DIN ISO 976.

[0115] Viscosity

[0116]

[0057] Viscosity was tested with Brookfield viscometer DV-II+ Pro according to the standard ISO 3219:1994. 150 g of the aqueous polyurethane dispersion was weighed into a glass bottle. The viscosity was measured with a spindle having the number of S63 at a rotational speed of 30 rpm.

[0117] Number average molecular weight of hydroxy functional components

[0118]

[0058] The number average molecular weight (Mn) was determined using gel permeation chromatography (GPC). The analysis was performed with a TOSOH liquid chromatograph, and with 4 GPC TSKgel SuperHZ columns in series, which have an exclusion limit of 44,000 g / mol. The sample concentration was approximately 0.008 g / mL, and an injection volume of 20 pL was used. Tetrahydrofuran (THF) was used as the mobile phase, and the analysis was conducted at a column temperature of 40°C, using a refractive index detector. The final number average molecular weight was calculated based on polyethylene glycol standards, selecting components with a molecular weight of 200 or higher for the calculation.

[0119] Weight average molecular weight of the polyurethane

[0120]

[0059] Dimethylacetamide (DMAc) was used as the mobile phase and a series of polyester copolymer GPC column was used with 1000000 g / mol exclusion limit. Under the condition of column temperature of 60 °C, Agilent's liquid chromatography was used for detection. The final weight average molecular weight was based on polystyrene standard as the standard sample, and components with a molecular weight of 200 or higher were selected for calculation.

[0121] Hydroxyl value

[0122]

[0060] OH numbers were measured according to standard DIN EN ISO 4629-2.2024PF30056 - Foreign Countries

[0123] 14

[0124] Waterproofing coating preparation

[0125]

[0061] One-component aqueous polyurethane waterproof coating composition was comprising the following parts (amounts are given based on the total coating composition):

[0126] From 0.5% to 1% of dispersant and wetting agent, from 0.4% to 1% of defoamer, from 30% to 50% of pigment, from 0.05% to 0.1% of pH regulator, from 0.01% to 0.1% of stabilizer, from 35% to 55% of aqueous polyurethane dispersion, from 0.5% to 7% of coalescent, from 0.1% to 0.7% of thickener and from 5% to 20% of DI water.

[0127]

[0062] The preparation method of the one-component waterborne polyurethane waterproofing coating composition comprises the following steps:

[0128] Step 1) Add dispersant, wetting agent, defoamer, titanium dioxide pigment, barium sulfate pigment, pH regulator and stabilizer into DI water. And stir the mixture at 1500 - 2500 rpm for 10 - 30 min to disperse the material uniformly in DI water.

[0129] Step 2) In the system of step 1), aqueous polyurethane dispersion, coalescent were added, stirred at a 600 - 1200 rpm for 5 - 20 min until the stock solution was mixed uniformly. Then thickener was added last to adjust the viscosity (viscosity range 3000-6000 mPa-s) to obtain a one-component waterborne polyurethane waterproof coating composition.

[0130] Waterproofing application testing

[0131] Dispersion resistance to CaCh addition

[0132]

[0063] 30 ml polyurethane dispersion was added to a beaker. Then 6 mL of 0.5% CaCh aqueous solution was added to the beaker. After mixing, the mixture was left to stand for 48 h and filtered to observe for precipitation and flocculation. The test was rated as passed (“pass) when no precipitation and flocculation were observed. The test was rated as not passed (“no pass”) when precipitation and / or flocculation was observed.

[0133] Initial tensile strength and elongation at break

[0134]

[0064] Above mentioned waterproof coating composition was applied on PTFE sheet using film casting knife with dry film thickness 1 mm - 1.5 mm.

[0135] Film was cured under standard condition (temperature 23 °C ± 2 °C, humidity 50% ± 10%) for 96 h. Then the film was flipped upside down and cured under standard condition for another 72 h.

[0136] After curing, film was cut into dumbbell-shaped according to GB / T 19250-2013. Tensile strength and elongation at break was measured using ZwickRoell tensile tester with 500 mm / min pull-off speed. Test results were the average value from three specimen tests.2024PF30056 - Foreign Countries

[0137] 15

[0138] Heat resistance / Acid resistance / Alkali resistance

[0139]

[0065] Above mentioned waterproof coating composition was applied on PTFE sheet using film casting knife with dry film thickness 1 mm - 1.5 mm.

[0140] Film was cured under standard condition (temperature 23 °C ± 2 °C, humidity 50% ± 10%) for 96 h. Then the film was flipped upside down and cured under standard condition for another 72 h. Heat resistance, acid resistance and alkali resistance were tested according to GB / T 19250-2013 standard.

[0141]

[0066] Heat resistance: cured film was treated at 80 °C for 168 h. Heat treated film was dried first. Then tensile strength and elongation at break were measured according to previous method.

[0142]

[0067] Acid resistance: cured film was soaked in 2% H2SO4 solution for 168 h. Acid treated film was dried first. Then tensile strength and elongation at break were measured according to previous method.

[0143]

[0068] Alkali resistance: cured film was soaked in 0.1% NaOH solution / saturated Ca(OH)2 solution for 168 h. Alkali treated film was dried first. Then tensile strength and elongation at break were measured according to previous method.

[0144] Coating film low temperature flexibility

[0145]

[0069] Film preparation: Above mentioned waterproof coating composition was applied on PTFE sheet using film casting knife with dry film thickness 1 mm - 1.5 mm.

[0146] Film was cured under standard condition (temperature 23 °C ± 2 °C, humidity 50% ± 10%) for 96 h. Then the film was flipped upside down and cured under standard condition for another 72 h.

[0147] After curing, film was cut into specimen with size of 100 mm * 50 mm. The specimen was placed in -35 °C freezer for 1 h. The specimen was bent for 180° in 3 s. The specimen was immediately taken out to be observed for defects on the surface. The test was rated as passed (“pass) when no fracture on the coating surface was observed. The test was rated as not passed (“no pass”) when fracture(s) on the coating surface was observed.

[0148] Water absorption rate

[0149]

[0070] Water absorption rate was tested according to GB / T 19250-2013 standard.

[0150] Cured film was cut into specimen with size of 50 mm * 50 mm and the weight (ml) of the specimen was measured.

[0151] The specimen was soaked in 23 °C ± 2 °C DI water for 168 h, and DI water was wiped off from the surface. Weight of the specimen was the determined (m2).

[0152] Water absorption rate was calculated as (m2 - ml) / ml *100%2024PF30056 - Foreign Countries

[0153] 16

[0154] For the same waterproof coating, three specimens were tested and the final value was the average of three values.

[0155] Preparation of polyurethane dispersion PUD 1-PUD 17

[0156]

[0071] Raw materials and abbreviations used:

[0157] P 200 H: difunctional polyester polyol based on phthalic anhydride and 1,6-hexane diol with a number average molecular weight Mnof 2000 g / mol (OH number: 56 mg KOH / g) from Covestro AG.

[0158] HDPOL-320NH: difunctional polyester polyol based on phthalic anhydride, 1,6-hexanediol and neopentyl glycol with a number average molecular weight of 2000 g / mol (OH number: 56 mg KOH / g) from Shanghai Huide Science and Technology Co., Ltd.

[0159] HDPOL-320H: difunctional polyester polyol based on phthalic anhydride and 1,6-hexanediol with a number average molecular weight of 2000 g / mol (OH number: 56 mg KOH / g) from Shanghai Huide Science and Technology Co., Ltd.

[0160] HDPOL-310M: difunctional polyester polyol based on phthalic anhydride and 2-methyl-l,3-propanediol with a number average molecular weight of 1000 g / mol (OH number: 112 mg KOH / g) from Shanghai Huide Science and Technology Co., Ltd.

[0161] Desmophen® PE 170 HN: difunctional polyester polyol based on adipic acid, neopentyl glycol and hexanediol with an average molecular weight Mnof 1700 g / mol (OH number: 66 mg KOH / g) from Covestro AG.

[0162] Desmophen® C 2202: aliphatic polycarbonate diol of hexanediol and dimethyl carbonate with a number average molecular weight Mnof 2000 g / mol (OH number: 56 mg KOH / g) from Covestro AG.

[0163] pTHF2000: poly(tetramethylene glycol) polyetherdiol having number average molecular weight 2000 g / mol (OH number: 56 mg KOH / g) from BASF.

[0164] pTHFlOOO: poly(tetram ethylene glycol) poly etherdiol having number average molecular weight 1000 g / mol (OH number: 112 mg KOH / g) from BASF.

[0165] Desmodur® H: 1,6-hexamethylene diisocyanate, Covestro, AG.

[0166] Desmodur® I: isophorone diisocyanate, Covestro, AG.

[0167] Poly ether LB 25: monofunctional non-ionic hydrophilic poly ether polyol based on ethylene oxide / propylene oxide with an ethylene oxide content of 84% by weight, number average molecular weight of 2250 g / mol (OH number: 25 mg KOH / g) from Covestro, AG.

[0168] HDO: 1,6-hexanediol from BASF.

[0169] NPG: neopentyl glycol from BASF.2024PF30056 - Foreign Countries

[0170] 17

[0171] DABCO T 9: Stannous 2-ethylhexanoate, catalyst, from Evonik

[0172] EDA: ethylenediamine from BASF.

[0173] BA: butylamine from BASF.

[0174] IPDA: isophorone diamine from BASF.

[0175] Hydrazine hydrate: 64% aqueous solution of hydrazine from Lanxess.

[0176] Vestamin® A95: sulfonate salt AAS <Sodium 2-((2-aminoethyl)amino)ethanesulfonate, 49% aqueous solution> from Evonik.

[0177] Irganox® 1076: antioxidant from BASF.

[0178] Irgastab® IS 4276: antioxidant from BASF.

[0179] Water: water demineralized by an ion exchanger.

[0180] Preparation of PUD 1

[0181]

[0072] 312 g P 200 H, 312 g pTHF2000 and 11.67 g polyether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.77 g HDO was added into the polyol mixture under stirring. Then 91.84 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.40%. After reaction was complete, 1095.5 g acetone was added to give prepolymer-acetone solution. Then AAS solution (25.67 g AAS solution in 138.45 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 962.7 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 41%, pH 7.23, viscosity 138 mPa-s, average particle size 188 nm and Mw 290,140 Dalton.

[0182] Preparation of PUD 2

[0183]

[0073] 144 g HDPOL-320NH, 432 g pTHF2000 and 7.54 g polyether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.55 g HDO was added into the polyol mixture under stirring. Then 84.77 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.42%. After reaction was complete, 1006.3 g acetone was added to give prepolymer-acetone solution. Then AAS solution (23.70 g AAS solution in 92.41 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 665.1 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 44%, pH 6.81, viscosity 4819 mPa-s, average particle size 281 nm and Mw 223,998 Dalton.2024PF30056 - Foreign Countries

[0184] 18

[0185] Preparation of PUD 3

[0186]

[0074] 168 g HDPOL-320NH, 504 g pTHF2000 and 5.03 g poly ether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.98 g HDO was added into the polyol mixture under stirring. Then 98.9 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.44%. After reaction was complete, 1168 g acetone was added to give prepolymer-acetone solution. Then AAS solution (27.6 g AAS solution in 107.8 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 1067 g water was added into mixture to give dispersion. After acetone distillation, 7.98 g Irgastab IS 4276 was added and mixture was stirred for 5 min. A solvent-free polyurethane-polyurea dispersion was obtained with solid content 41%, pH 6.8, viscosity 576 mPa-s, average particle size 310 nm and Mw 416,754 Dalton.

[0187] Preparation of PUD 4

[0188]

[0075] 100.8 g HDPOL-320NH, 571.2 g pTHF2000 and 3.77 g poly ether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.98 g HDO and 7.97 g Irganox 1076 were added into the polyol mixture under stirring. Then 98.9 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.42%. After reaction was complete, 1166.5 g acetone was added to give prepolymer-acetone solution. Then AAS solution (27.65 g AAS solution in 107.8 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 1064.9 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 40%, pH 6.96, viscosity 762 mPa-s, average particle size 261 nm. Product was not soluble in GPC solvent DMAc.

[0189] Preparation of PUD 5

[0190]

[0076] 120.0 g HDPOL-320H, 360.0 g pTHF2000 and 6.28 g polyether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 3.75 g NPG and 5.75 g Irganox 1076 were added into the polyol mixture under stirring. Then 70.6 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.12%. After reaction was complete, 841.0 g acetone was added to give prepolymer-acetone solution. Then AAS solution (21.72 g AAS solution in 84.7 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 761.2 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 40%, pH 6.57, viscosity 713 mPa-s, average particle size 257 nm and Mw 243,840 Dalton.2024PF30056 - Foreign Countries

[0191] 19

[0192] Preparation of PUD 6

[0193]

[0077] 120.0 g HDPOL-320NH, 240.0 g pTHF2000, 120.0 g Desmophen C 2202 and 6.28 g poly ether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.13 g HDO and 5.74 g Irganox 1076 were added into the polyol mixture under stirring. Then 70.6 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.40%. After reaction was complete, 839.0 g acetone was added to give prepolymeracetone solution. Then AAS solution (21.72 g AAS solution in 84.7 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 758,8 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 41%, pH 6.81, viscosity 1552 mPa-s, average particle size 300 nm and Mw 182,092 Dalton.

[0194] Preparation of PUD 7

[0195]

[0078] 168 g HDPOL-310M, 504 g pTHF2000 and 8.7965 g polyether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.98 g HDO and 8.02 g Irganox 1076 was added into the polyol mixture under stirring. Then 98.9 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 1.50%. After reaction was complete, 1174 g acetone was added to give prepolymer-acetone solution. Then AAS solution (27.6 g AAS solution in 107.8 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 1072 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 40%, pH 6.8, viscosity 520 mPa-s, average particle size 176 nm and Mw 417,105 Dalton.

[0196] Preparation of PUD 8

[0197]

[0079] 287.55 g HDPOL-320NH and 191.70 g pTHF2000 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.13 g HDO was added into the polyol mixture under stirring. Then 70.64 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.48%. After reaction was complete, 828 g acetone was added to give prepolymer-acetone solution. Then AAS solution (28.2 g AAS solution in 106.5 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 492.6 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 48%, pH 6.96, viscosity 1900 mPa-s and average particle size 184 nm.2024PF30056 - Foreign Countries

[0198] 20

[0199] Preparation of PUD 9

[0200]

[0080] 431.3 g HDPOL-320NH and 47.9 g pTHF2000 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.13 g HDO was added into the polyol mixture under stirring. Then 70.64 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.48%. After reaction was complete, 828 g acetone was added to give prepolymer-acetone solution. Then AAS solution (28.2 g AAS solution in 106.5 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 485 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 50%, pH 6.8, viscosity 735 mPa-s and average particle size 144 nm.

[0201] Preparation of PUD 10

[0202]

[0081] 239.7 g HDPOL-320NH and 239.7 g pTHF2000 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.13 g HDO was added into the polyol mixture under stirring. Then 70.6 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.48%. After reaction was complete, 828 g acetone was added to give prepolymer-acetone solution. Then AAS solution (28.2 g AAS solution in 107 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 493 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 46%, pH 6.5, viscosity 1132 mPa-s, average particle size 185 nm and Mw of 227,741 Dalton.

[0203] Preparation of PUD 11

[0204]

[0082] 335 pTHF2000 and 72 g pTHFlOOO were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 6.14 g Irganox 1076 was added into the polyol mixture under stirring. Then 36 g HDI and 47.6 g IPDI were added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 3.20%. After reaction was complete, 872 g acetone was added to give prepolymer-acetone solution. Then AAS / EDA / BA solution (6.65 g AAS solution and 4.72 g EDA in 124 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 396 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 49%, pH 6.94, viscosity 643 mPa-s, average particle size 160 nm and Mw of 205,280 Dalton.2024PF30056 - Foreign Countries

[0205] 21

[0206] Preparation of PUD 12

[0207]

[0083] 144 g HDPOL-320NH, 432 g pTHF2000 and 12.82 g LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.55 g HDO was added into the polyol mixture under stirring. Then 84.8 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.39%. After reaction was complete, 1014 g acetone was added to give prepolymer-acetone solution. Then EDA solution (3.67 g EDA in 32.32 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 987 g water was added into mixture to give dispersion. The polymer could not be emulsified and showed phase separation.

[0208] Preparation of PUD 13

[0209]

[0084] 288 g P 200 H, 144 g pTHFlOOO and 10.77 g LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.55 g HDO was added into the polyol mixture under stirring. Then 84.8 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 3.05%. After reaction was complete, 795 g acetone was added to give prepolymer-acetone solution. Then AAS solution (23.7 g AAS solution in 127 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 402 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 36%, pH 6.31, viscosity >10000 mPa-s, average particle size 237 nm.

[0210] Preparation of PUD 14

[0211]

[0085] 108.0 g HDPOL-320H, 360.0 g pTHF2000, 252.0 g Desmophen C 2202 and 9.42 g poly ether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 5.62 g NPG and 7.67 g Irganox 1076 were added into the polyol mixture under stirring. Then 106.0 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.12%. After reaction was complete, 1261.5 g acetone was added to give prepolymer-acetone solution. Then AAS solution (32.58 g AAS solution in 127.1 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 1141.8 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 40%, pH 7.24, viscosity 1960 mPa-s, average particle size 247 nm and Mw 174,169 Dalton.

[0212] Preparation of PUD 15

[0213]

[0086] 36.0 g HDPOL-320H, 360.0 g pTHF2000, 324.0 g Desmophen C 2202 and 9.42 g poly ether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 25.62 g NPG and 7.67 g Irganox 1076 were added into the polyol mixture under stirring. Then2024PF30056 - Foreign Countries

[0214] 22

[0215] 106.0 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.12%. After reaction was complete, 1261.5 g acetone was added to give prepolymeracetone solution. Then AAS solution (32.58 g AAS solution in 127.1 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 1141.8 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 40%, pH 7.33, viscosity 1364 mPa-s, average particle size 236 nm and Mw 150,853 Dalton.

[0216] Preparation of PUD 16

[0217]

[0087] 240.0 g pTHF2000, 240.0 g Desmophen C 2202 and 6.28 g polyether LB 25 were dehydrated at 100 °C and 100 mbar for 1 hour. After cooling to 70 °C, 2.13 g HDO and 5.74 g Irganox 1076 were added into the polyol mixture under stirring. Then 70.6 g HDI was added into the mixture and reaction mixture was heated to 110 °C until NCO% reaches 2.40%. After reaction was complete, 839.0 g acetone was added to give prepolymer-acetone solution. Then AAS solution (21.72 g AAS solution in 84.7 g water) was added slowly into reaction mixture at 40 °C under stirring. The mixture was stirred under 40 °C for 15 min and 758,8 g water was added into mixture to give dispersion. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 40%, pH 7.65, viscosity 716 mPa-s, average particle size 410 nm and Mw 116,129 Dalton.

[0218] Preparation of PUD 17

[0219]

[0088] PUD 17 was prepared analogously to Example 2 of US2007249746. 539.9 g PE 170 HN, 18.2 g polyether LB 25 were heated to 65 °C. A mixture of 60.5 g HDI and 80.0 g IPDI was then added at 65 °C. In the course of 5 min, and stirring was carried out at 100 °C, until NCO% reaches 4.79%. The finished prepolymer was dissolved with 1247.6 g acetone at 50 °C, and then a solution of 46.8 g IPDA and 80.7 g acetone was added in the course of 2 min. The afterstirring time was 5 minutes. A solution of 15.9 g AAS solution, 1.6 g of hydrazine hydrate and 82.9 g of water was then added in the course of 5 min. Dispersion was carried out by addition of 550 g water. After acetone distillation, a solvent-free polyurethane-polyurea dispersion was obtained with solid content 54%, pH 7.16, viscosity 1652 mPa-s, average particle size 198 nm and Mw 145,910 Dalton.

[0220]

[0089] Tables la-lc specifies the components and its amounts applied for preparing the polyurethane dispersions PUD 1 to PUD 17.2024PF30056 - Foreign Countries

[0221] 23

[0222] Table la

[0223]

[0224] 2024PF30056 - Foreign Countries

[0225] 24

[0226] Table lb

[0227]

[0228] 2024PF30056 - Foreign Countries

[0229] 25

[0230] Table 1c

[0231]

[0232] 2024PF30056 - Foreign Countries

[0233] 26

[0234] Preparation of coating compositions based on PUD 1 to PUD 11 and PUD 14 to PUD 17.

[0235]

[0090] Raw materials and abbreviations used:

[0236] DISPERBYK-190: wetting & dispersing additive, from BYK.

[0237] Borchi® Gen 1252: wetting and dispersing agent for inorganic pigments, from Borchers.

[0238] Tego® Airex 901 W: defoamer, from Evonik.

[0239] BYKO 12: defoamer, from BYK.

[0240] NA 250 HBR: hydroxyethylcellulose, stabilizer, from Ashland.

[0241] AMP-95: pH regulator, from AUGUS

[0242] Ti-Pure® R-706: rutile titanium dioxide pigment, from Chemours.

[0243] Barium sulfate: 1250 mesh, pigment, from Shanghai Yuejiang Titanium Chemical Manufacturer CO., Ltd.

[0244] Borchi® Gel 0434: thickener, Borchers.

[0245] Diethylene glycol monohexyl ether: coalescent, from Sigma-Aldrich.

[0246] PG: propylene glycol, coalescent, from Sigma-Aldrich.

[0247] OE400: coalescent from Eastman.

[0248]

[0091] PUD 1 to PUD 11 were used for preparing coating compositions which were subsequently tested as described below. Coating compositions of PUD 12 and PUD 13 were not prepared since PUD 12 showed phase separation and PUD 13 has a too high viscosity (Comparative Examples 5 and 6 (CE 5-6)). Coating film prepared by PUD 16 showed mudcracking and respective coating properties cannot be measured. Table 2a and 2b specify the components and its amounts applied for preparing coating compositons based on polyurethane dispersions PUD 1 to PUD 11 and PUD 14 to PUD 17. Table 3 reports the initial properties of the waterproofing coating obtained from the coating compositions based on polyurethane dispersions PUD 1 to PUD 11, PUD 14, PUD 15 and PUD 17. Table 4 reports the resistance properties of the waterproofing coating obtained from the coating compositions based on polyurethane dispersions PUD 1 to PUD 11 and PUD 14, PUD 15 and PUD 17.2024PF30056 - Foreign Countries

[0249] 27

[0250] Table 2a

[0251]

[0252] 2024PF30056 - Foreign Countries

[0253] 28

[0254] Table 2b

[0255]

[0256] 2024PF30056 - Foreign Countries

[0257] 29

[0258] Table 3

[0259] < > >

[0260] >

[0261] >

[0262]

[0263] Table 4

[0264] > > > > > > > > >

[0265]

Claims

2024PF30056 - Foreign Countries30What is claimed is:

1. An aqueous polyurethane dispersion comprising water and a polyurethane, wherein the polyurethane is obtained by reacting at least components (A)-(E):(A) one or more aromatic polyester polyol and optionally one or more polycarbonate polyol, wherein said aromatic polyester polyol and polycarbonate polyol have a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1,(B) one or more polyether polyol with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, wherein the amount of said poly ether polyol (B), based on the total weight of (A) and (B), is at least 45.0% by weight,(C) one or more diisocyanate with formula Y(NCO)2, wherein Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon group or Y is a Ce-Cis divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group,(D) one or more non-ionic hydroxy -functional polyether with an ethylene oxide content of at least 50% by weight, and(E) one or more ionic isocyanate-reactive compounds comprising sulfonate (-SO3 ) groups in the salt form,wherein the number average molecular weight of the components (A), (B) and (D) are determined with the method as described in the description,wherein the components (A), (B), (C), (D) and (E) are distinct.

2. The aqueous polyurethane dispersion of claim 1, wherein the polyurethane is obtained by reacting at least components (A)-(E):(A) from 4.0 to 45.0% by weight of the one or more aromatic polyester polyol and optionally the one or more polycarbonate polyol, wherein said aromatic polyester polyol and polycarbonate polyol have a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1,(B) from 40.0 to 80.0% by weight of the one or more polyether polyol with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1,(C) from 8.0% to 25.0% by weight, preferably from 9.0 to 20.0% by weight, even more preferably from 10.0 to 15.0% by weight of the one or more diisocyanate with formula Y(NCO)2, wherein Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon2024PF30056 - Foreign Countries31group or Y is a Ce-Cis divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group,(D) from 0.1 to 6.0% by weight, preferably from 0.1 to 4.0% by weight, even more preferably from 0.1 to 2.0% by weight of the one or more non-ionic hydroxy -functional polyether with an ethylene oxide content of at least 50% by weight, and(E) from 1.0 to 2.5% by weight of the one or more ionic isocyanate-reactive compounds comprising sulfonate (-SO3 ) groups in the salt form,wherein the amounts of (A) to (E) are given relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

3. The dispersion according to claim 1 or 2, wherein the amount of the poly ether polyols (B), based on the total weight of (A) and (B), is at least 48.0% by weight, more preferably at least 50.0% by weight.

4. The dispersion according to any of claims 1 to 3, wherein the aromatic polyester polyol (A) is prepared from one or more aromatic dicarboxylic acids and / or the corresponding aromatic dicarboxylic anhydride with one or more diols and wherein the one or more aromatic dicarboxylic acids and aromatic dicarboxylic anhydrides are selected from the group consisting of phthalic acid, phthalic anhydride, terephthalic acid, terephthalic anhydride, isophthalic acid, isophthalic anhydride and any mixture of at least two thereof, more preferably the one or more aromatic dicarboxylic acids and aromatic dicarboxylic anhydrides are phthalic acid and phthalic anhydride and / or wherein the one or more diols are selected from the group consisting of diethylene glycol, 1,2- propanediol, 1,3-propanediol, 2-methyl-l,3-propanediol, 1,4-butanediol, 1,3 -butanediol, 2,3 butanediol, 1,5-pentanediol, 3-methyl-l,5-pentanediol, 1,6-hexanediol, neopentylglycol and any mixture of at least two thereof, preferably the one or more diols are selected from the group consisting of 1,6-hexanediol, neopentylglycol and any mixture thereof, more preferably the one or more diols are 1,6-hexanediol or mixtures of 1,6-hexanediol and neopentylglycol.

5. The dispersion according to any one of the preceding claims, wherein the amount of the one or more aromatic polyester polyol is at least 10% by weight, more preferably at least 15% by weight, even more preferably at least 20% by weight, even more preferably at least 25% by weight, even more preferably at least 30% by weight, even more preferably at least 35% by weight, even more preferably at least 40% by weight, even more preferably at least 45% by weight, even more preferably at least 50% by weight, even2024PF30056 - Foreign Countries32more preferably at least 55% by weight, even more preferably at least 60% by weight, even more preferably at least 65% by weight, even more preferably at least 70% by weight, even more preferably at least 75% by weight, even more preferably at least 80% by weight, even more preferably at least 85% by weight, even more preferably at least 90% by weight, relative to the total amount of component (A).

6. The dispersion according to any one of the claims 1 to 5, wherein the amount of the one or more aromatic polyester polyol is 100% by weight, relative to the total amount of component (A), i.e., component (A) is one or more aromatic polyester polyol.

7. The dispersion according to any of the preceding claims, wherein the polyether polyol (B) comprises one or more polytetrahydrofuran and optionally one or more polypropylene glycol, wherein the amount of polytetrahydrofuran, based on the total weight of (B), is preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, even more preferably the polyether polyol (B) is one or more polytetrahydrofuran.

8. The dispersion according to any one of the preceding claims, wherein the one or more diisocyanates (C) are selected from the group consisting of 1,5- pentamethylenediisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexane-l,4-diisocyanate, 1,3- and 1,4- bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate (H12MDI) and any mixture of two or more thereof, preferably the one or more diisocyanates (C) are selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and any mixture of two or more thereof, more preferably the diisocyanate (C) is 1,6-hexamethylene diisocyanate (HDI).

9. The dispersion according to any one of the preceding claims, wherein the one or more non-ionic hydroxy -functional polyether (D) have a number average molecular weight of from 350 to 4500 g / mol, preferably from 1000 to 4500 g / mol and / or the one or more non-ionic hydroxy-functional polyether (D) have a hydroxy functionality of from 0.9 to 2.1, preferably from 0.9 to 1.1.

10. The dispersion according to any one of the preceding claims, wherein the one or more non-ionic hydroxy-functional polyether (D) is selected from the group consisting of ethylene oxide polymers, copolymers of ethylene oxide and propylene oxide and any mixtures of two or more thereof, preferably the one or more non-ionic hydroxy-2024PF30056 - Foreign Countries33functional polyether (D) is one or more copolymers of ethylene oxide and propylene oxide.

11. The dispersion according to any one of the preceding claims, wherein the one or more sulfonate containing component (E) is a diaminosulfonate corresponding to the following general formula:H2N-A-NH-B-SO3-Cat+wherein A and B represent aliphatic hydrocarbon groups having from 2 to 6 carbon atoms, preferably ethylene groups, and Cat+represents an optionally substituted ammonium cation or preferably a sodium or potassium cation, more preferably sodium cation, preferably component (E) is the sodium salt of N-(2- aminoethyl)-2-aminoethanesulfonic acid.

12. The dispersion according to any one of the preceding claims, wherein the polyurethane is the reaction product formed through a reaction between at least components (A), (B), (C), (D) and (E), and (F) and / or (G),wherein component (F) is one or more diol having a molar mass of from 32 to 400 g / mol, wherein the amount of component (F) is preferably from 0.1 to 4.0%, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated, andwherein component (G) is one or more amine functional chain extender,wherein the amount of component (G) is preferably from 0.1 to 3.0 % by weight, relative to the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated,wherein the components (A), (B), (C), (D), (E), (F) and (G) are distinct.

13. The dispersion according to any one of the preceding claims, wherein the polyurethane has a weight average molecular weight Mwof at least 80,000 Dalton, preferably of at least 100,000 Dalton, more preferably of at least 120,000 Dalton, whereby the Mwis determined with the method as described in the description.

14. The dispersion according to any one of the preceding claims, wherein the combined amount of component (A) and component (B), based on the total amount of isocyanatereactive components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated, is at least 80.0% by weight, more preferably at least 85.0% by weight, even more preferably at least 90.0% by weight and / or wherein the combined amount of component (D) and component (E) is at most 6.0% by weight, preferably at most 5.0% by weight, more preferably at most 4.5% by weight, relative to2024PF30056 - Foreign Countries34the total amounts of components used to prepare the polyurethane from which the building blocks from the polyurethane are emanated.

15. The dispersion according to any one of the preceding claims, wherein the dispersion further comprises one or more antioxidants in an amount of from 0.25 to 5.0% by weight, based on the amount of polyurethane present in the dispersion.

16. A coating composition comprising the dispersion of any one of the preceding claims as a binder, wherein the coating composition comprises from 0.5 to 1% by weight of dispersant and wetting agent, from 0.4 to 1% by weight of defoamer, from 30 to 50% by weight of pigment, from 0.05 to 0.1% by weight of pH regulator, from 0.01 to 0.1% by weight of stabilizer, from 35 to 55% by weight of aqueous polyurethane dispersion according to any of claims 1 to 13, from 0.5 to 7% by weight of coalescent, from 0.1 to 0.7% by weight of thickener and from 5 to 20% by weight of water, wherein the amounts are given based on the coating composition.

17. Use of the coating composition of claim 16 for waterproof coating, in particular for exterior walls, exterior roofs, bathrooms, kitchens and basements.

18. An article comprising a substrate, optionally at least partly coated with a primer, that is at least partly coated with a coating obtained by curing the coating composition of claim 16, wherein the substrate is a building material, in particular an exterior wall, an exterior roof, building material or furniture for bathrooms, building material or furniture for kitchens or building material or furniture for basements and the substrate is preferably engineered stone, wood, (artificial) marble, terrazzo, ceramic, metals, mineral materials, plastics, rubber, concrete, composite sheet, more preferably the substrate is concrete.

Images