Rapid-curing, aqueous, intumescent fireproofing composition having a high level of application layer thickness on surfaces at any inclination

Abstract

The present invention relates to the use of an aqueous binder comprising a binder based on an aqueous polymer latex of a film-forming carboxylated polymer and a branched polyetheramine polyol having substantially tertiary amino groups in an intumescent fireproofing composition, in particular for coating components, such as supports, construction components, or space-enclosing surfaces such as walls, ceilings, floors, etc. In addition to the aqueous binder, the aqueous intumescent fireproofing composition contains, as the second component, an intumescent compound mixture and further additives. The invention also relates to a coating made of the fireproofing composition, and to a substrate coated with the coating. The fireproofing coating according to the invention is characterised by particularly rapid curing, even in the case of a high level of layer thickness.

Description

[0001] Fast-curing, water-based, intumescent fire protection composition with high application layer thickness on surfaces of any inclination.

[0002] The present invention relates to the use of an aqueous binder comprising a binder based on an aqueous polymer latex of a film-forming carboxylated polymer, a branched polyetheramine polyol having essentially tertiary amino groups in an intumescent fire protection composition, in particular for coating components such as supports, structural components or room-enclosing surfaces such as walls, ceilings, floors, etc. In addition to the aqueous binder, the aqueous intumescent fire protection composition contains, as a second component, an intumescent compound mixture and further additives. The invention further relates to a coating produced from the fire protection composition and to a substrate coated with the coating. The fire protection coating according to the invention is characterized by particularly rapid curing, even in high layer thicknesses.

[0003] Intumescent compounds are typically applied to the surface of building components to form coatings to protect them from fire or against excessive heat, such as those resulting from a fire. Steel structures have become an integral part of modern architecture, even though they have one significant disadvantage compared to reinforced concrete construction. Above approximately 500°C, the load-bearing capacity of steel drops by 50%, meaning the steel loses its stability and load-bearing capacity. Depending on the fire load, such as direct fire exposure (approximately 1000°C), this temperature can be reached after just 5-10 minutes, which often leads to a loss of load-bearing capacity of the structure.The objective of fire protection, particularly steel fire protection, is to delay the time until a steel structure loses its load-bearing capacity in the event of a fire for as long as possible in order to save human lives and valuable goods.

[0004] The building regulations of many countries stipulate corresponding fire resistance times for certain steel structures. These are defined by so-called F classes such as F 30, F 60, F 90 (fire resistance classes according to DIN 4102-2) or American classes according to ASTM, etc. According to DIN 4102-2, for example, F 30 means that a load-bearing steel structure must withstand fire for at least 30 minutes in the event of a fire under standard conditions. This is usually achieved by delaying the heating rate of the steel, e.g., by enclosing the steel components with non-combustible materials such as plasterboard, or by coating the steel structure with intumescent coatings. These are coatings whose components expand in the event of a fire, forming a solid, microporous carbon foam.This creates a fine-pored, thick layer of carbon foam, the so-called ash crust. Depending on its composition, this layer has strong thermal insulation properties, increases the distance between the flame and the steel surface, and thus delays the heating of the component, so that the critical temperature of approximately 500°C is reached after 30, 60, 90, 120, or up to 240 minutes at the earliest. The thickness of the coating applied, or rather the resulting ash crust, is always crucial for the achievable fire resistance. Closed profiles, such as pipes, require approximately twice the amount of ash compared to open profiles, such as beams with a double-T profile, for comparable solidity.In order to comply with the required fire resistance times, the coatings must have a certain thickness and be able to form a voluminous and thus well-insulating ash crust when exposed to heat, which remains mechanically stable over the period of fire exposure.

[0005] Various systems already exist for this purpose, with a large proportion of the products available on the market being based on aqueous dispersions.

[0006] Patent WO2019 / 099372 A1 describes aqueous fire protection compositions based on polymeric binders with at least one coalescing agent and one or more additives from the group of intumescent additives, anti-vibration additives, and sound-decoupling additives. The polymeric binder is provided in a first component and the coagulant in a second component. The additive(s) can be contained in the first component, the second component, or both the first and second components. When the two components are applied directly or simultaneously to a substrate to be coated, a coating is formed within 30 seconds of application that is adhesive, stable, water-resistant, and non-sticky.

[0007] In publicly accessible facilities such as sports stadiums, skyscrapers, airports, train stations or administrative buildings, but also in private areas, an aesthetic top coat is increasingly being dispensed with, among other things for cost reasons, so that fire protection coatings must increasingly also meet aesthetic aspects and therefore have to have good to very good surface properties.

[0008] The compositions disclosed in WO2019 / 099372 A1 exhibit rapid curing with respect to intumescent coatings and allow for high coating thicknesses. However, the corresponding compositions exhibit disadvantages with regard to the stability of the ash crust in the event of a fire and with regard to their surface quality. To improve the stability of the ash crust in the event of a fire, the proportion of intumescent additives in the composition is typically increased, and more than 50 wt.% based on the total weight of the composition is usually used. However, the resulting high solids content leads to an increase in the surface roughness of the resulting cured coating with increasing solids content, especially when the composition was applied by hand or spray. As the surface roughness increases, the gloss of the cured coating decreases.For the purposes of the present invention, the combination of surface roughness and gloss is collectively referred to as a surface property. Low surface roughness and high gloss therefore correspond to very good surface properties.

[0009] The application of the fire protection coating as a two-component system (A+B) disclosed in WO 2019 / 099372 A1 brings with it several disadvantages. For example, the handling of two-component spray equipment on construction sites is generally complex, and therefore one-component solutions are preferred by users. Furthermore, the separation of the binder composition and coagulant in the two individual aqueous components leads to an increased water content in the combined mixture. This results in extended drying times, even if the curing of the binder composition itself is very rapid. Binder compositions with the highest possible solids content and the lowest possible water content are advantageous.

[0010] There is a need for a composition that demonstrates good processability despite a high solids content of 50 wt.% and more based on the total weight of the composition. The coating produced from the composition should also exhibit good fire resistance and good to very good surface properties, particularly low surface roughness and attractive gloss properties.

[0011] The object of the present invention was to provide aqueous fire protection compositions that overcome the disadvantages of the prior art. In particular, there is a need for fire protection compositions that offer sufficiently rapid curing even at high layer thicknesses, in order to provide sufficient functional layer thicknesses with as few work steps as possible.

[0012] The object underlying the invention is achieved by the use of an aqueous binder of a

[0013] (a) aqueous polymer latex of a film-forming carboxylated polymer;

[0014] (b) 0.05 to 7.5 wt.%, based on the dry weight of the carboxylated polymer, of a branched polyetheramine polyol, dissolved in the aqueous phase of the polymer latex, wherein at least 90% of all amino groups in the branched polyetheramine polyol are tertiary amine groups and wherein the aqueous polymer latex of the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M, wherein the monomer composition M consists of

[0015] I) 70% by weight consists of 99.95% by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1 selected from C1-C20 alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C1-C20 alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 C atoms, C5-C20 cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms, vinyl esters of C1-C20 alkanoic acids, vinyl aromatic monomers, C2-C6 monoolefins and butadiene;

[0016] 0.05 wt.% to 10 wt.%, based on the total weight of the monomer composition M, of one or more monoethylenically unsaturated monomers M2 selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms; ill) 0 wt.% to 20 wt.%, based on the total weight of the monomer composition M, of one or more non-ionic monomers M3 different from the monomers M1, in an aqueous intumescent fire protection composition.

[0017] The fire protection composition contains the aqueous binder as the first component and an intumescent compound mixture as the second component as well as further additives, whereby the additives can be contained in both the first and the second component or in both.

[0018] Advantageous embodiments arise from the subclaims, which can optionally be combined with one another.

[0019] In particular, it has been found that the branched polyetheramine polyols, as defined herein, reduce or eliminate the dependence of the drying properties of fire-protection coatings based on aqueous polymer latexes of film-forming carboxylated polymers on the application temperature. Therefore, binders comprising a combination of a branched polyetheramine polyol, as defined herein, and an aqueous polymer latex of a film-forming carboxylated polymer can be used to produce fire-protection compositions that exhibit drying behavior that is virtually independent of the application temperature and therefore offer accelerated drying at typical building component temperatures. The fire-protection coating according to the invention is further characterized by particularly rapid curing, even in high layer thicknesses.

[0020] A general disadvantage of such water-based systems, especially when used for fire protection coatings that require wet film thicknesses of 3 mm or more, is the purely physical drying of the coating compound.

[0021] The drying rate of a water-based fire protection coating, especially for structural shells, is highly dependent on the weather conditions, particularly the humidity, temperature, and wind speed during coating application. For example, if the drying rate is too slow, e.g., due to low temperature and / or high humidity, sudden rain can damage the coating. In contrast, a fast drying rate, e.g., under elevated temperature and / or low humidity conditions, can lead to short open times, which can cause problems when applying the coating under these conditions. Therefore, there is a need to control the drying rate of a fire protection coating, which is less dependent on weather conditions.A disadvantage of such physically curing fire protection compositions based on aqueous dispersions is their insufficient resistance to driving rain prior to curing. The term "precipitation" refers to heavy rain, whose droplets, depending on the droplet size and wind speed, can cause damage to the uncured coating composition in insufficiently cured surface areas.

[0022] By using the binders according to the invention, a faster curing is achieved and thus the required earlier driving rain resistance can be achieved and thus an intact coating can be ensured which nevertheless has sufficient water vapor permeability and thus allows the necessary drying over the entire layer thickness and thus results in a cured dry coating which ensures the desired fire protection and thus the essential requirements for the fire protection properties of the fire protection composition.

[0023] The aqueous binders according to the invention are particularly suitable for modifying the curing rate of the fire protection compositions.

[0024] Particularly advantageously, the fire protection composition produced with the binder according to the invention is adjusted to a pH value in the range from 7.5 to 9.0, preferably 8.0 - 8.5, with ammonia or an amino alcohol which is readily volatile at ambient temperature, such as ethanolamine.

[0025] The fire protection compositions according to the invention produced with the binder according to the invention are also stable over longer periods, e.g., more than 14 days, and do not tend to form agglomerates during storage.

[0026] A further aspect of the present invention relates to the use of the aqueous binder as defined herein as a binder or co-binder in water-based fire protection compositions.

[0027] The invention further relates to a coating made from the fire protection composition and a substrate coated with the coating.

[0028] Another aspect of the present invention relates to a method for producing a coating on a surface, comprising applying the fire protection composition as defined herein to the surface and allowing the composition to cure to produce the coating.

[0029] Here and throughout the description, the prefixes C n -C m used in connection with compounds or molecular units, each indicates a range for the number of possible carbon atoms that a molecular unit or compound can have. The term "Ci-C n-Alkyl" refers to a group of linear or branched saturated hydrocarbon radicals having 1 to n carbon atoms. For example, the term Ci-C2o-alkyl I refers to a group of linear or branched saturated hydrocarbon radicals having 1 to 20 carbon atoms. Similarly, the term C5-C2o-alkyl I refers to a group of linear or branched saturated hydrocarbon radicals having 5 to 20 carbon atoms, while the term Ci-C4-alkyl refers to a group of linear or branched saturated hydrocarbon radicals having 1 to 4 carbon atoms.Beispiele für Alkyl schließen Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, 2-Butyl, 2-Methylpropyl (Isopropyl), 1, 1-Dimethylethyl (tert- Butyl), Pentyl, 1 -Methylbutyl ein, sind aber nicht darauf beschränkt, 2-Methylbutyl, 3-Methylbutyl, 2,2-Dimethylpropyl, 1 -Ethylpropyl, 1,1 -Dimethylpropyl, 1 ,2-Dimethylpropyl, 1 -Methylpentyl, 2- Methylpentyl, 3-Methylpentyl, 4- Methylpentyl, 1,1 -Dimethylbutyl, 1 ,2-Dimethylbutyl, 1 ,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3- Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2- Trimethylpropyl, 1-Ethyl-1-methylpropyl, 1- Ethyl-2-methylpropyl, Hexyl, Heptyl, Octyl, 2-Ethylhexyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Heneicosyl , Docosyl und ihre Isomere. Ci-C4-Alkyl bedeutet beispielsweise Methyl, Ethyl, Propyl, 1 -Methylethyl, Butyl, 1 -Methylpropyl, 2-Methylpropyl oder 1,1- Dimethylethyl.

[0030] Here and throughout this description, the term "(meth)acrylic" encompasses both acrylic and methacrylic groups. Therefore, the term "(meth)acrylate" includes both acrylate and methacrylate.

[0031] Here and throughout this specification, the terms "polymer latex" and "polymer dispersion" are used synonymously and mean an aqueous polymer composition of a water-insoluble polymer, wherein the polymer is in the form of finely dispersed polymer particles. Typically, the polymer latex is obtainable by emulsion polymerization (also referred to as primary latex), but it can also be obtained by emulsifying a polymer in an aqueous phase (secondary latex).

[0032] Here and throughout this specification, the term "polyetheramine polyol" means a polymer having amine groups, ether groups and hydroxyl groups.

[0033] Here and throughout this specification, the term "pphm" is the abbreviation for "parts per hundred monomers" and is the weight percentage based on the total weight of monomers in the particular composition.

[0034] Here and throughout the specification, the range "x to y wt%" is a synonym for the range "x wt% to y wt%." Likewise, the range "x to y mol%" is a synonym for the range "x mol% to y mol%." For clarification, this also applies to ranges given in "mol / kg," "mg KOH / g," "g / mol," "pphm," "°C," and the like. According to the invention, the binder composition contains an aqueous polymer latex composed of a carboxylated polymer and at least one branched polyetheramine polyol. The branched polyetheramine polyol is dissolved in the aqueous phase of the polymer latex. Therefore, the polyetheramine polyol is water-soluble, at least to some extent.

[0035] The water solubility of the branched polyetheramine polyol is preferably at least 5 g / l, more preferably at least 10 g / l, especially at least 50 g / l, especially 100 g / l, at 20°C. In particular, the branched polyetheramine polyol is completely miscible with water at 20°C.

[0036] In the branched polyetheramine polyol dissolved in the aqueous phase of the polymer latex, substantially all of the amino groups are tertiary amine groups. In this context, the term "substantially" means that at least 90%, preferably at least 95%, more preferably more than 98%, and even more preferably more than 99% of the amino groups in the branched polyetheramine polyol are tertiary amine groups. In particular, the branched polyetheramine polyol has no detectable amounts of secondary and primary amino groups. Thus, in the branched polyetheramine polyol dissolved in the aqueous phase of the polymer latex, all of the amino groups in the branched polyetheramine polyol are tertiary amine groups. These are often branched.

[0037] Polyetheramine polyol contains, on average, less than 0.5 mol / kg of secondary and primary amino groups, if present. In particular, the polyetheramine polyol contains, on average, less than 0.2 mol / kg, in particular less than 0.1 mol / kg of secondary and primary amino groups, if present.

[0038] The branched polyetheramine polyol often contains an average of 4 to 8.2 mol / kg of tertiary amino groups. In particular, the polyetheramine polyol contains an average of 5 to 8.0 mol / kg of tertiary amino groups, especially 5 to 7.9 mol / kg.

[0039] The amine number of polyetheramine polyol is preferably in the range of 100 to 700 mg KOH / g, most preferably in the range of 200 to 500 mg KOH / g, determined according to the method described in DIN EN ISO 9702:1998. In addition to determining the total amine group content, this method allows the determination of the tertiary amine group content, the secondary amine group content, and the primary amine group content.

[0040] In addition to the amino groups, the polyetheramine polyol contains hydroxyl groups. The OH number of the polyetheramine polyol is often at least 100 mg KOH / g, e.g., 100 to 800 mg KOH / g, in particular at least 200 mg KOH / g, e.g., 200 to 700 mg KOH / g, in particular at least 250 mg KOH / g, e.g., 250 to 650 mg KOH / g, determined according to DIN 53240, Part 2. The number of hydroxyl groups per molecule depends on the number-average molecular weight of the branched polyetheramine polyol and the degree of branching. The branched polyetheramine polyol frequently contains on average (number average) at least four, particularly preferably at least six, and particularly preferably at least ten hydroxyl groups per molecule. The number of terminal or pendant functional groups is, in principle, unlimited. The branched polyetheramine polyol preferably contains on average (number average) at most 500, in particular at most 200 terminal hydroxyl groups per molecule.

[0041] The number-average molecular weight Mn of branched polyetheramine polyols is often in the range of 500 to 55,000 g / mol, in particular in the range of 1,000 to 40,000 g / mol, determined by gel permeation chromatography using hexafluoroisopropanol as the mobile phase and polymethyl methacrylate as the standard. The weight-average molecular weight Mw of polyetheramine polyols is often in the range of 1,000 to 300,000 g / mol, in particular in the range of 2,000 to 200,000 g / mol, and especially in the range of 5,000 to 150,000 g / mol, determined by gel permeation chromatography using hexafluoroisopropanol as the mobile phase and polymethyl methacrylate as the standard. The polydispersity, ie the ratio Mw / Mn, of the polyetheramine polyol is often in the range of 1.1 to 25, in particular in the range of 1.5 to 20.

[0042] The dynamic viscosity of the branched polyetheramine polyol is often in the range of 5 to 200 Pas, determined at 23°C according to ASTM D7042, in particular in the range of 8 to 150 Pas.

[0043] The term "branched" describes that the polyetheramine polyol does not have a linear structure, but rather has a significant number of branching points within the polymer backbone, resulting in a branched polymer chain. Such branching points can be tri- or tetrasubstituted carbon atoms and / or tertiary amino groups. The branching points are, in particular, the tertiary amino groups.

[0044] The Hazen color number of the polyetheramine polyol is preferably in the range of 100 to 600 (APHA), determined according to DIN ISO 6271.

[0045] The polyetheramine polyol is often amorphous and can therefore exhibit a glass transition. The glass transition temperature of the polyetheramine polyol preferably does not exceed 50°C, more preferably does not exceed 30°C, and even more preferably does not exceed 10°C, as determined by differential scanning calorimetry (DSC), as described below. The glass transition temperature of the polyetheramine polyol is preferably in the range of -55 to 30°C and more preferably in the range of -55 to 10°C, as determined by DSC. Branched polyetheramine polyols and their preparation are known, for example from DE3206459, EP441198, WC2009 / 047269, WO 2014 / 012812, which disclose branched polyetheramine polyols based on a polycondensation product of at least one trialkanolamine.

[0046] In one embodiment of the present invention, the branched polyetheramine polyol is obtainable by polycondensation of at least one trialkanolamine or by polycondensation of a mixture of at least one trialkanolamine with an aliphatic or cycloaliphatic polyol. Trialkanolamines for this purpose are preferably selected from tri-C2-C8 alkanolamines, where the alkanol groups in the trialkanolamine may be different or identical, with the alkanol groups preferably being identical. The trialkanolamines are particularly preferably selected from tri-C2-C4 alkanolamines, where the alkanol groups are identical.

[0047] Particularly preferred trialkanolamines are triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine and triisobutanolamine and mixtures thereof.

[0048] Suitable aliphatic or cycloaliphatic polyols include, for example, aliphatic diols, aliphatic polyols with more than two hydroxyl groups, cycloaliphatic diols, and cycloaliphatic polyols with more than two hydroxyl groups. Aliphatic diols and aliphatic polyols containing more than two hydroxyl groups are preferred. Examples of aliphatic diols are C2-C20 diols, such as ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and their structural isomers. Further examples of aliphatic diols are polyether diols of the general formula HO-((CH2) n -O) m-H, where n is independently 1 to 10, preferably 2 to 4, and m is in the range from 2 to 100. The polyether diols are preferably selected from polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. Examples of polyols having more than 2 hydroxyl groups are glycerol, pentaerythritol, trimethylolpropane, sorbitol, and the like. The polyols can also be alkoxylated, in particular ethoxylated or propoxylated, e.g., ethoxylated glycerol, propoxylated glycerol, ethylated pentaerythritol, propoxylated pentaerythritol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated sorbitol, and propoxylated sorbitol. Typically, the degree of alkoxylation, i.e., the number-average alkylene oxide content, will not exceed 100 and is frequently in the range from 2 to 50.

[0049] Preferably, the polyetheramine polyol is obtainable by polycondensation, wherein the monomers contain up to at least 50 wt.%, preferably at least 70 wt.%, particularly preferably at least 80 wt.%, based on the total amount of monomer, of compounds selected from trialkanolamines. The polyetheramine polyol is preferably obtainable by polycondensation of monomers containing 50 to 100 mol% of compounds selected from trialkanolamines and 0 to 50 mol% of compounds selected from aliphatic or cycloaliphatic polyols, preferably containing 70 to 100 mol% of compounds selected from trialkanolamines and 0 to 30 mol% of compounds selected from aliphatic or cycloaliphatic polyols, particularly preferably containing 80 to 100 mol% of compounds selected from trialkanolamines and 0 to 20 mol% of compounds selected from aliphatic or cycloaliphatic polyols, where "mol%" is based on the total amount of monomers.

[0050] In a particular embodiment, the polyetheramine polyol is obtainable by polycondensation, wherein the monomers consist only of monomers selected from trialkanolamines. The trialkanolamine is preferably selected from tri-C2-C4 alkanolamines. Preferred tri-C2-C4 alkanolamines are selected from triethanolamine, triisopropanolamine, and tri-n-propanolamine.

[0051] The mixture of at least one trialkanolamine with an aliphatic or cycloaliphatic polyol is preferably selected from mixtures of at least one trialkanolamine selected from the group consisting of tri-C2-C4 alkanolamines and an aliphatic or cycloaliphatic C2-C8 polyol.

[0052] Particularly preferably, polyetheramine polyols are obtainable by polycondensation of either triethanolamine or triisopropanolamine, or a mixture of triethanolamine and triisopropanolamine. In this embodiment, at least one further polyol, in particular at least one further diol, may optionally be present.

[0053] The polycondensation can be carried out with or without the presence of a catalyst. Suitable catalysts include, but are not limited to, phosphoric acid (H3PO4), phosphorous acid (H3PO3), or hypophosphoric acid (H3PO2), which can be applied in bulk or as an aqueous solution. Preferably, the catalyst is added in an amount of 0.001 to 10 mol%, preferably 0.005 to 7 mol%, more preferably 0.01 to 5 mol%, based on the amount of trialkanolamine.

[0054] The polycondensation can be carried out using a solvent. Examples of solvents that can be used to carry out the process according to the invention are aromatic and / or (cyclo)aliphatic hydrocarbons and their mixtures, halogenated hydrocarbons, ketones, esters, and ethers. Preference is given to aromatic hydrocarbons, (cyclo)aliphatic hydrocarbons, alkyl esters of alkanoic acids, ketones, alkoxylated alkyl esters of alkanoic acids, and mixtures thereof. Particular preference is given to monoalkylated or polyalkylated benzenes and naphthalenes, ketones, alkyl esters of alkanoic acids and alkoxylated alkyl esters of alkanoic acids, and mixtures thereof. The polycondensation is preferably carried out without the use of a solvent.

[0055] The polycondensation can be carried out such that the temperature during the polycondensation does not exceed 250°C and preferably 230°C. For example, the polycondensation is carried out at temperatures in the range of 150 to 230°C, preferably 180 to 215°C. More preferably, the temperature during the polycondensation does not exceed 215°C and especially does not exceed 210°C.

[0056] The polycondensation can be carried out at a pressure in the range of 0.02 to 20 bar. Preferably, the polycondensation is carried out at atmospheric pressure. The polycondensation is preferably followed by removal or blowing off of residual monomers, for example by distillation at atmospheric pressure or at reduced pressure, for example, in the range of 0.1 to 0.5 bar.

[0057] Water or other volatile products released during polycondensation can be removed from the reaction mixture to accelerate the reaction. Preferably, water or other volatile products released during polycondensation are removed, for example, by distillation and optionally under reduced pressure. The removal of water or other low-molecular-weight reaction by-products can also be assisted by passing a gas stream that is largely inert under the reaction conditions (stripping), such as nitrogen or a noble gas such as helium, neon, or argon, through the reaction mixture.

[0058] The branched polyetheramine polyols described herein are typically stable at room temperature for extended periods, such as at least 10 weeks. In particular, the polyetheramine polyols are stable without exhibiting turbidity, precipitation, and / or significant increases in viscosity.

[0059] The polycondensation can be terminated in various ways. For example, the temperature can be lowered to a range where the reaction stops and the polycondensation product is storage-stable. This is generally below 100°C, preferably below 60°C, more preferably below 40°C, and most preferably at room temperature. Another possibility is to deactivate the catalyst by adding a basic component, for example a Lewis base or an organic or inorganic base.

[0060] The polycondensation can be carried out in stirred-tank reactors or stirred-tank cascades. The process can be carried out batchwise, semi-continuously, or continuously. Polycondensation products of trialkanolamines and polycocondensation products of trialkanolamines as described herein are preferably used as polyetheramine polyols without chemical modification or derivatization.

[0061] Instead of a non-derivatized polycondensation product, a polycondensation product of trialkanolamines or a derivative of a polycocondensation product of a trialkanolamine can also be used.

[0062] Derivatives of such polycondensation and polycocondensation products of trialkanolamines include products obtained by alkoxylation of the hydroxyl end groups of the underivatized polycondensation and polycocondensation products. It is also possible to modify the underivatized polycondensation or polycocondensation products with hydrophobic or hydrophilic groups. Hydrophobization or hydrophilization can be achieved by reacting a portion of the hydroxyl end groups with selected reactants. The amino groups of the polycondensation and polycocondensation products can also be quaternized using alkylating agents to obtain permanently cationically modified polymers. Derivatives of such polycondensation and polycocondensation products of trialkanolamines are described, for example, in US2011 / 0168045, W02009 / 060060 and W02009 / 1112379, to which reference is made.Preferred derivatization products within the meaning of the invention are alkoxylated polycondensation and polycocondensation products.

[0063] The polyetheramine polyol typically dissolves readily in a variety of solvents, such as water, alcohols such as methanol, ethanol, n-butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.

[0064] The aqueous binder composition typically contains the branched polyetheramine polyol in an amount of 0.01 to 10 wt.%, in particular 0.05 to 7.5 wt.%, in particular 0.1 to 5 wt.%, based on the dry mass of the weight of the carboxylated polymer of the aqueous polymer latex.

[0065] The aqueous binder composition of the invention also contains an aqueous polymer latex of a film-forming carboxylated polymer.

[0066] The term "film-forming" in the context of the polymer latex refers to the ability of the carboxylated polymer of the polymer latex to form a film on surfaces upon drying under application conditions. The polymer often has a film-forming temperature of 50°C or less, especially 30°C or less. The film-forming temperature can be lowered, for example, by adding film-forming aids such as plasticizers and / or solvents.

[0067] The film-forming ability of the latex polymer under application conditions depends on its glass transition temperature. Generally, the carboxylated polymer of aqueous polymer dispersions has a glass transition temperature Tg in the range of -50 to -+60°C, particularly -40 to +50°C, and especially in the range of -30 to +30°C. The glass transition temperature can be determined using the DSC method (Differential Scanning Calorimetry, 20 K / min, center point measurement) according to [ ].

[0068] DIN 53765:1994-03 or ISO 1 1357-2, preferably with sample preparation according to DIN EN ISO 16805:2005. In the case of a multiphase polymer containing two or more polymers or polymer phases with different glass transition temperatures, the glass transition temperatures of the individual polymer phases may be outside the ranges specified here. However, the weight-average glass transition temperature Tg (av) is calculated using the equation:

[0069] Tg(av) = (T g (1)*wi + T g (2)*w2+ ... + T g (n)*f n ).

[0070] It is often in the range of -50 to -+60°C, especially from -40 to +50°C, especially in the range of -30 to +30°C. In the equation, T g (1 ), T g (2) to T g (n) the individual glass transition temperatures in K of the individual polymers 1, 2 to n, while wi, W2 to w n indicate the proportion in weight percent of the individual polymers 1, 2 to n. For example, an aqueous latex of a multi-stage polymer containing 20 wt.% of a first polymer phase 1 with a T g of -10°C and 80 wt.% of a second polymer phase 2 with a T g of +40°C have a weight-average T g (av) = 34°C. If the polymer of the aqueous polymer dispersions contains polymers with different T g , the difference between the lowest T g and the highest T gas high as, for example, 100°C, for example from 10 to 100°C. Preferably, the polymer dispersed in the aqueous polymer dispersion has only a T g or, if there are polymers with different T g contains the maximum difference of the lowest T g and the highest T g 50K, especially not exceeding 20K.

[0071] According to Fox (TG Fox, Bull. Am. Phys. Soc. 1956, Vol. 1, page 123) and Ullmann's Encyclopedia of Industrial Chemistry (Vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980), a good approximation of the glass transition temperature of not more than slightly cross-linked copolymers is:

[0072] 1 / Tg (Fox) = xi / Tgi + x2 / Tg2+ ....+ X n / day n , where xi, X2, ... Xn are the mass fractions of the monomers 1, 2, .... n and Tgi, Tg2,..., Tg n. The glass transition temperatures are given in degrees Kelvin for the polymers synthesized from only one of the monomers 1, 2, .... n. The Tg values ​​for the homopolymers of most monomers are known and can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. A21, page 169, Verlag Chemie, Weinheim, 1992; other sources for glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1st ed., J. Wiley, New York 1966, 2nd ed. J. Wiley, New York 1975, and 3rd ed. J. Wiley, New York 1989.

[0073] In the case of a multi-stage polymer containing two polymers or polymer phases with different glass transition temperatures, the glass transition temperature of one phase is typically above 40°C, preferably at least 60°C, as determined by DSC as described herein. According to Fox, the glass transition temperature of the other phase is typically below 40°C, preferably at most 30°C, as determined by DSC as described herein.

[0074] In the case of a multi-stage polymer containing 2 polymers or polymer phases with different glass transition temperatures, the polymer preferably contains 95 to

[0075] 40 wt.%, based on the total weight of the polymer, of the polymer having the lower glass transition temperature, which is usually below 40°C, and 5 to 60 wt.%, based on the total weight of the polymer, of the polymer having the higher glass transition temperature, which is usually above 40°C.

[0076] The term "carboxylated polymer" means that the latex polymer contains carboxyl groups bonded to the polymer backbone. Typically, the carboxyl groups are incorporated into the polymer by polymerizing ethylenically unsaturated monomers containing one or more carboxyl groups. Such monomers are typically selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms. Examples of such monomers include acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid, and fumaric acid.

[0077] The carboxylated polymer of the film-forming polymer latex is typically obtainable by radical copolymerization of a monomer M, which forms the carboxylated monomer latex. These monomers M, also referred to as monomer composition M, contain at least one monoethylenically unsaturated monomer having at least one carboxyl group, selected, for example, from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and at least one further neutral ethylenically unsaturated monomer that is essentially water-insoluble, i.e., that has a solubility in deionized water of at most 50 g / l at 20°C. Typically, the monomer composition comprises 0.05 to 10 wt. %, based on the total weight of the monomers contained in the monomer composition.

[0078] In particular, the monomer composition M consists essentially of a) one or more ethylenically unsaturated monomers M1 which have a solubility in deionized water of at most 50 g / l at 20°C and which are in particular selected Ci-C2o-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms, di-Ci-C2o-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 C atoms, C5-C2o-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms, vinyl esters of Ci-C2o-alkanoic acids, vinyl aromatic monomers, C2-C6 monoolefins and butadiene; b) one or more monoethylenically unsaturated monomers M2 selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 C atoms; c) optionally one or more nonionic monomers M3 different from monomers M1.

[0079] The term "consisting essentially of" in this context means that the total amount of the monomers M1, M2 and M3 constitutes at least 95% by weight, in particular at least 99% by weight or 100% by weight of the total amount of monomers of the monomer composition.

[0080] Examples of monomers M1 include, but are not limited to

[0081] Ci-C2o-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms, such as Ci-C2o-alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, Ci2 / Ci4-alkyl acrylate and stearyl acrylate, Ci-C2o-alkyl esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert. -butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, Ci2 / Ci4-alkyl methacrylate and stearyl methacrylate;

[0082] Di-Ci-C2o-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 C atoms, such as di-Ci-C2o-alkyl esters of itaconic acid, di-Ci-C2o-alkyl esters of citraconic acid, di-Ci-C2o-alkyl esters of maleic acid and di-Ci-C2o-alkyl esters of fumaric acid,

[0083] C5-C2o-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms, C5-C20-cycloalkyl esters of acrylic acid and C5-C2o-cycloalkyl esters of methacrylic acid, vinyl esters of C1-C2o-alkanoic acids, vinyl aromatic monomers such as monovinyl-substituted aromatic hydrocarbons such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and alpha-methylstyrene, C2-C6-monoolefins and butadiene.

[0084] In a preferred embodiment, the monomers M1 are a mixture of at least one monomer M1a selected from C1-C20 alkyl esters of acrylic acid and C5-C20 alkyl esters of methacrylic acid; and at least one monomer M1b selected from vinylaromatic monomers and C1-C4 alkyl esters of methacrylic acid, and mixtures thereof. Suitable monomers M1a are:

[0085] Ci-C2o-alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, Ci2 / Ci4-alkyl acrylate and stearyl acrylate; C5-C2o-alkyl esters of methacrylic acid, such as n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C12 / C14-alkyl imethacrylate and stearyl imethacrylate; and mixtures thereof.

[0086] Suitable monomers M1b are

[0087] C1-C4 alkyl esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate, particularly preferably methyl methacrylate;

[0088] Vinyl aromatic monomers, in particular monovinyl-substituted aromatic hydrocarbons such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and alpha-methylstyrene, particularly preferably styrene; and mixtures thereof.

[0089] The monomers M1 a are preferably selected from C2-C10-alkyl esters of acrylic acid, in particular from ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate.

[0090] The monomers M1b are preferably selected from vinyl aromatic monomers and Ci-C4 alkyl esters of methacrylic acid and mixtures thereof, in particular from styrene, methyl methacrylate.

[0091] In the mixtures of the monomers M1a and M1b, the relative amount of M1a and M1b can vary in particular from 10:1 to 1:10, in particular from 5:1 to 1:5, in particular from 3:1 to 1:3.

[0092] Examples of monomers M2 include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid, and fumaric acid. Monocarboxylic acids are preferred. Acrylic acid, methacrylic acid, and mixtures thereof are particularly preferred.

[0093] Particularly preferably, the monomer M2 is selected from methacrylic acid or a mixture of acrylic acid and methacrylic acid.

[0094] Examples of monomers M3 include, but are not limited to, primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms (monomers M3.1), such as acrylamide and methacrylamide;

[0095] N-Ci-Cio-alkylamides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms (monomers M3.2), in particular N-Ci-Cio-alkylamides of acrylic acid or methacrylic acid, such as N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide and N-butylmethacrylamide; monoethylenically unsaturated monomers with urea or keto groups (monomers M3.3), such as 2-(2-oxo-imidazolidin-1-yl)ethyl(meth)acrylate, 2-ureido(meth)acrylate, N-[2-(2-oxooxazolidin-3-yl)ethyl]methacrylate, acetoacetoxyethylacrylate, acetoacetoxypropylmethacrylate, acetoacetoxybutylmethacrylate, 2-(acetoacetoxy)ethylmethacrylate, diacetoneacrylamide (DAAM) and diacetonemethacrylamide;

[0096] Hydroxyalkyl esters of monoethylenically unsaturated Ca-Ce monocarboxylic acids (monomers M3.4), in particular hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid, hereinafter also referred to as hydroxyalkyl. (Meth)acrylates, in particular hydroxy-Ca-C alkyl esters of acrylic acid and hydroxy-C2-C4 alkyl esters of methacrylic acid, such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, etc.

[0097] Monoethylenically unsaturated monomers containing at least one tri-Ci-C4 alkoxysilane group (monomers M3.5), such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane, and mixtures thereof. The amount of the aforementioned monomers M3.5 will often be in the range of 0.01 to 1 pphm.

[0098] The M3 monomers may also contain small amounts of polyethylenically unsaturated monomers (monomers M3.6), i.e., monomers with at least two non-conjugated ethylenically unsaturated double bonds. The amounts of the above-mentioned M3.6 monomers will generally not exceed 1 pphm. Suitable M3.6 monomers include:

[0099] Diesters of monoethylenically unsaturated Ca-Ce monocarboxylic acids with saturated aliphatic or cycloaliphatic diols, in particular diesters of acrylic acid or methacrylic acid, such as the diacrylates and dimethacrylates of ethylene glycol (1,2-ethanediol), propylene glycol (1,2-propanediol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol) or 1,2-cyclohexanediol;

[0100] Monoesters of monoethylenically unsaturated Ca-Ce monocarboxylic acids with monoethylenically unsaturated aliphatic or cycloaliphatic monohydroxy compounds, such as the acrylates and methacrylates of vinyl alcohol (ethanol), allyl alcohol (2-propen-1-ol), 2-cyclohexen-1-ol or norbornenol and divinyl aromatic compounds, such as 1,3-divinylbenzene, 1,4-divinylbenzene and mixtures thereof.

[0101] In a particular embodiment of the invention, the monomers M contain no monomers M3.6 or no more than 0.1 pphm of the monomers M3.6. Among the monomers M3, hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of acrylic acid are preferred, methacrylic acid, in particular hydroxy-C2-C4-alkyl esters of acrylic acid and hydroxy-C2-C4-alkyl esters of methacrylic acid, acrylamide, methacrylamide, and mixtures thereof.

[0102] The carboxylated polymer is preferably obtainable by polymerizing a monomer composition M, wherein the monomer composition M essentially consists of a) 70 to 99.95 wt.%, in particular 80 to 99.9 wt.%, especially 90 to 99.8 wt.%, based on the total weight of the monomers of the monomer composition M, of one or more monoethylenically unsaturated monomers M1 as defined herein, b) 0.05 to 10 wt.%, in particular 0.1 to 8 wt.%, in particular 0.2 to 5 wt.%, based on the total weight of the monomers of the monomer composition M, of one or more monoethylenically unsaturated monomers M2 as defined herein, c) 0 to 20 wt.%, in particular 0 to 10 wt.%, in particular 0 to 5 wt.%, based on the total weight of the monomers of the monomer composition M, of one or more non-ionic monomers M3 as defined herein, which are different from the monomers M1.

[0103] The carboxylated polymer is particularly obtainable by polymerization of a monomer composition

[0104] M, wherein the monomer composition M consists of a) one or more ethylenically unsaturated monomers M1 which are selected from the group consisting of at least one monomer M1a selected from C1-C20 alkyl esters of acrylic acid and C5-C20 alkyl esters of methacrylic acid; and at least one monomer M1b selected from vinylaromatic monomers and C1-C4 alkyl esters of methacrylic acid and mixtures thereof, b) one or more monoethylenically unsaturated monomers M2 selected from the group consisting of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 C atoms; c) optionally one or more nonionic monomers M3 which are different from monomers M1.

[0105] In a preferred embodiment, the film-forming carboxylated polymer is obtainable by polymerizing a monomer composition M, wherein the monomer composition M consists essentially of a) 70 to 99.95 wt. %, in particular 80 to 99.9 wt. %, in particular 90 to 99.8 wt. %, based on the total weight of the monomers of the monomer composition M, of one or more monoethylenically unsaturated monomers M1 selected from the group consisting of at least one monomer M1a selected from C1-C20 alkyl esters of acrylic acid and C5-C20 alkyl esters of methacrylic acid; and at least one monomer M1b selected from vinylaromatic monomers and C1-C4 alkyl esters of methacrylic acid and mixtures thereof b) 0.05 to 10 wt. %, in particular 0.1 to 8 wt. %, in particular 0.2 to 5 wt.-%, based on the total weight of the monomers of the monomer composition M, of one or more monoethylenically unsaturated monomers M2 as defined herein, c) 0 to 20 wt.%, in particular 0 to 10 wt.%, in particular 0 to 5 wt.%, based on the total weight of the monomers of the monomer composition M, of one or more non-ionic monomers M3 as defined herein, which are different from the monomers M1.

[0106] In the aqueous carboxylated polymer latex, the dispersed polymers are present in the form of polymer particles. The polymer particles typically have an average diameter in the range of 50 to 500 nm, in particular in the range of 60 to 400 nm, and especially in the range of 80 to 300 nm. The average particle diameter, as referred to herein, refers to the Z-average particle diameter as determined by photon correlation spectroscopy (PCS), also known as quasielastic light scattering (QELS) or dynamic light scattering (DLS). The measurement method is described in ISO 13321:1996. The determination can be performed using a HPPS (High Performance Particle Sizer). For this purpose, a sample of the aqueous polymer latex is diluted and the dilution is analyzed. In the context of DLS, the aqueous dilution can have a polymer concentration in the range of 0.001 to 0.5 wt.%, depending on the particle size.For most purposes, a suitable concentration is 0.01 wt%. However, higher or lower concentrations can be used to achieve an optimal signal-to-noise ratio. Dilution can be achieved by adding the polymer latex to water or an aqueous solution of a surfactant to avoid flocculation. Typically, dilution is achieved by using a 0.1 wt% aqueous solution of a non-ionic emulsifier, e.g., an ethoxylated Cie / Cis alkanol (degree of ethoxylation 18), as the diluent. Measurement configuration: Malvern HPPS, automated, with continuous-flow cuvette and Gilson autosampler. Parameters: Measurement temperature 20.0°C; measurement time 120 seconds (6 cycles of 20 seconds); scattering angle 173°; dependent on particle size. Laser wavelength 633 nm (HeNe); Refractive index of the medium 1.332 (aqueous); viscosity 0.9546 mPa-s. The measurement results in a mean value of the second-order cumulant analysis (mean of fits), ieZ-mean. The "mean of fits" is an average, intensity-weighted hydrodynamic particle diameter in nm.

[0107] Preferably, the polymers in the polymer dispersion have a narrow particle size distribution. The particle size distribution is characterized by the polydispersity index, which is a dimensionless number calculated from a simple two-parameter fit to the correlation data from the cumulant analysis. The calculation is typically performed as described in ISO 13321:1996. Often, the PDI will be less than 0.2.

[0108] The polymer latex of the carboxylated polymer is usually obtainable by aqueous radical emulsion polymerization, in particular by radical aqueous emulsion polymerization, of the monomers M forming the carboxylated monomer latex, analogously to known processes of radical emulsion polymerization technology. The conditions required for carrying out the radical emulsion polymerization of the monomers M are sufficiently familiar to the person skilled in the art, for example from the prior art cited at the beginning and from "Emulsion Polymerization" in Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 ff. (1987); D.C. Blackley, in High Polymer Latices, vol. 1, pages 35 ff. (1966); H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, pages 246 ff. (1972); D.Diederich, Chemistry in Our Time 24, pages 135 to 142 (1990); Emulsion Polymerization, Interscience Publishers, New York (1965); DE-A 40 03422 and Dispersions of Synthetic High Polymers, F. Hölscher, Springer-Verlag, Berlin (1969)].

[0109] Radically initiated aqueous emulsion polymerization is triggered by a radical polymerization initiator (radical initiator). These can generally be peroxides or azo compounds. Redox initiator systems are also suitable. Peroxides that can be used include, in principle, inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or dialkali metal or ammonium salts of peroxodisulfuric acid, for example, the mono- and disodium, potassium, or ammonium salts, or organic peroxides such as alkyl hydroperoxides, e.g., tert-butyl hydroperoxide, p-menthyl hydroperoxide, or cumyl hydroperoxide, as well as dialkyl or diaryl peroxides, such as di-tert-butyl or dicumyl peroxide. The azo compounds used are mainly 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(amidinopropyl)dihydrochloride (AIBA, equivalent to V-50 from Wako Chemicals).The peroxides mentioned above, as well as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides such as sorbose, glucose, fructose and / or dihydroxyacetone, are essentially suitable as oxidizing agents for redox initiator systems.

[0110] Preferred free-radical initiators are inorganic peroxides, especially peroxodisulfates, and redox initiator systems. Generally, the amount of free-radical initiator used, based on the total amount of monomers M, is 0.01 to 5 ppm by weight, preferably 0.1 to 3 ppm by weight.

[0111] The amount of radical initiator required for the emulsion polymerization M in the process according to the invention can be introduced entirely into the polymerization vessel. However, it is also possible to add no or only a portion of the radical initiator, for example, adding no more than 30% by weight, in particular no more than 20% by weight, based on the total amount of radical initiator required, to the aqueous polymerization medium and then, under polymerization conditions during the radical emulsion polymerization of the monomers M, to add the entire amount or any remaining amount, depending on consumption, discontinuously in one or more portions or continuously at a constant or varying flow rate.Preferably, the free-radical emulsion polymerization of the monomers forming the carboxylated polymer latex is carried out by a so-called feed process, which means that at least 90%, in particular at least 95%, or the entire amount of the monomers are polymerized and added to the polymerization reaction under polymerization conditions during a metering period P. The duration of the period P can depend on the production plant and vary from, for example, 20 minutes to 12 hours. Frequently, the duration of the period P will be in the range of 0.5 h to 5 h, in particular from 1 h to 4 h.

[0112] The term "polymerization conditions" generally refers to temperatures and pressures under which radically initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. These depend in particular on the radical initiator used. Advantageously, the type and amount of radical initiator, polymerization temperature, and polymerization pressure are selected such that a sufficient amount of initiating radicals is always present to initiate or maintain the polymerization reaction. It may be expedient to adjust the polymerization conditions and initially charge at least a portion of the radical initiator to the polymerization vessel before commencing metering of the monomers M.

[0113] It has proven advantageous to carry out the free-radical emulsion polymerization in the presence of seed latex. A seed latex is a polymer latex present in the aqueous polymerization medium before the metering of the monomers M begins. The seed latex can help to better adjust the particle size of the final polymer latex obtained in the free-radical emulsion polymerization according to the invention.

[0114] In principle, any polymer latex can serve as seed latex. Preferred for the purposes of the invention are seed latices in which the particle size of the polymer particles is comparatively small. In particular, the Z-average particle diameter of the polymer particles of the seed latex, determined by dynamic light scattering at 20°C (see below), is preferably in the range from 10 to 80 nm, in particular from 10 to 50 nm. The polymer particles of the seed latex preferably consist of ethylenically unsaturated monomers which contain at least 95% by weight, based on the total weight of the monomers forming the seed latex, of one or more monomers M1a and / or M1b as defined above. The polymer particles of the seed latex contain in particular at least 95% by weight, based on the total weight of the monomers forming the seed latex.

[0115] Typically, the seed latex is initially introduced into the polymerization vessel before the metering of the monomers M begins. In particular, the seed latex is introduced into the polymerization vessel, and the polymerization conditions are then adjusted, e.g., by heating the mixture to the polymerization temperature. It may be advantageous to add at least a portion of the free-radical initiator to the polymerization vessel before the metering of the monomers M begins. However, it is also possible to meter the monomers and the free-radical polymerization initiator in parallel with the polymerization vessel.

[0116] The amount of seed latex, calculated as solids, can frequently be in the range from 0.1 to 10 wt. %, in particular 0.5 to 5 wt. %, based on the total weight of the monomers M to be polymerized. The free-radical aqueous emulsion polymerization according to the invention can be carried out at temperatures in the range from 0 to 170°C. Temperatures employed are generally in the range from 50 to 120°C, frequently from 60 to 120°C, and often from 70 to 110°C. The free-radical aqueous emulsion polymerization according to the invention can be carried out at a pressure of less than, equal to, or more than 1 atm (atmospheric pressure), and thus the polymerization temperature can exceed 100°C and be up to 170°C.

[0117] The polymerization of the monomers is usually carried out at ambient pressure, but it can also be carried out under elevated pressure. The pressure can be 1.2, 1.5, 2, 5, 10, 15 bar (absolute), or even higher. If emulsion polymerizations are carried out under vacuum, pressures of 950 mbar, frequently 900 mbar, and often 850 mbar (absolute) are reached.

[0118] Advantageously, the radical aqueous emulsion polymerization according to the invention is carried out at ambient pressure (approx. 1 atm) with exclusion of oxygen, for example under an inert gas atmosphere, for example under nitrogen or argon.

[0119] The polymerization of the monomers M can optionally be carried out in the presence of chain transfer agents. Chain transfer agents are understood to be compounds that transfer free radicals and reduce the molecular weight of the molecules or control chain growth during polymerization. Examples of chain transfer agents are aliphatic and / or araliphatic halogen compounds, for example n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, for example ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol,

[0120] 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol,

[0121] 3-Methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomeric compounds, n-octanethiol and its isomeric compounds, n-nonanethiol and its isomeric compounds, n-decanethiol and its isomeric compounds, n-undecanethiol and its isomeric compounds, n-dodecanethiol and its isomeric compounds, n-tridecanethiol and its isomeric compounds, substituted thiols, for example 2-Hydroxyethanethiol, aromatic thiols such as benzenethiol, ortho-, meta- or para-methylbenzenethiol, alkyl esters of mercaptoacetic acid (thioglycolic acid) such as 2-ethylhexyl thioglycolate, alkyl esters of mercaptopropionic acid such as octyl mercaptopropionate, and other sulfur compounds described in Polymer Handbook, 3rd edition, 1989, J.Brandrup and EHimmergut, John Wiley & Sons, Section II, pages 133 to 141, but also aliphatic and / or aromatic aldehydes, such as acetaldehyde, propionaldehyde and / or benzaldehyde, unsaturated fatty acids, such as oleic acid, dienes with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane, or hydrocarbons with easily abstracted hydrogen atoms, for example toluene. Alternatively, mixtures of the aforementioned chain transfer agents can be used which do not interfere with each other. The total amount of chain transfer agents optionally used in the process according to the invention, based on the total amount of monomers M, will generally not exceed 1% by weight. However, it is possible that during a certain period of the polymerization reaction the amount of chain transfer agent added to the polymerization reaction exceeds 1% by weight, based on the total amount of monomers already added to the polymerization reaction.

[0122] The radical emulsion polymerization according to the invention is usually carried out in an aqueous polymerization medium which, in addition to water, contains at least one surface-active substance (surfactant) to stabilize the emulsion of the monomers and the polymer particles.

[0123] The surfactant can be selected from emulsifiers and protective colloids. In contrast to emulsifiers, protective colloids are polymeric compounds with molecular weights above 2000 Daltons, while emulsifiers typically have lower molecular weights. The surfactants can be anionic or nonionic, or mixtures of nonionic and anionic surfactants.

[0124] Anionic surfactants typically carry at least one anionic group selected from phosphate, phosphonate, sulfate, and sulfonate groups. Anionic surfactants that carry at least one anionic group are typically used in the form of their alkali metal salts, especially their sodium salts, or in the form of their ammonium salts. Preferred anionic surfactants are anionic emulsifiers, especially those that carry at least one sulfate or sulfonate group.

[0125] Examples of anionic emulsifiers which carry at least one sulfate or sulfonate group are, for example, the salts, in particular the alkali and ammonium salts, of alkyl sulfates, in particular of C8-C22 alkyl sulfates, the salts, in particular the alkali and ammonium salts, of sulfuric acid monoesters of ethoxylated alkanols, in particular of sulfuric acid monoesters of ethoxylated C8-C22 alkanols, preferably with an ethoxylation degree (EO level) in the range from 2 to 40, the salts, in particular the alkali and ammonium salts, of sulfuric acid monoesters of ethoxylated alkylphenols, in particular of sulfuric acid monoesters of ethoxylated C4-C18-alkylphenols (EO content preferably 3 to 40), the salts, in particular the alkali and ammonium salts, of alkylsulfonic acids, in particular of C8-C22 Alkylsulfonic acids, the salts, in particular the alkali and ammonium salts, of dialkyl esters, in particular C4-Ci8-alkyl esters of sulfosuccinic acid, the salts,in particular the alkali metal and ammonium salts of alkylbenzenesulfonic acids, especially C4-C22-alkylbenzenesulfonic acids, and the salts, especially the alkali metal and ammonium salts, of mono- or disulfonated, alkyl-substituted diphenyl ethers, for example bis(phenylsulfonic acid) ethers, which carry a C4-C24 alkyl group on one or both aromatics. The latter are generally known, for example from US Pat. No. 4,269,749, and are commercially available, for example as Dowfax® 2A1 (Dow Chemical Company). Mixtures of the aforementioned salts are also suitable.

[0126] Preferred anionic surfactants are anionic emulsifiers selected from the following groups: the salts, in particular the alkali and ammonium salts, of alkyl sulfates, in particular of C8-C22 alkyl sulfates, the salts, in particular the alkali metal salts, of sulfuric acid monoesters of ethoxylated alkanols, in particular of sulfuric acid monoesters of ethoxylated C8-C22 alkanols, preferably with an ethoxylation degree (EO level) in the range from 2 to 40, of sulfuric acid monoesters of ethoxylated alkylphenols, in particular of sulfuric acid monoesters of ethoxylated C4-C18-alkylphenols (EO content preferably 3 to 40), of alkylbenzenesulfonic acids, in particular of C4-C22 alkylbenzenesulfonic acids, and of mono- or disulfonated, alkyl-substituted diphenyl ethers, for example of Bis(phenylsulfonic acid) ethers which carry a C4-C24 alkyl group on one or both aromatic rings.

[0127] Examples of anionic emulsifiers carrying a phosphate or phosphonate group include, but are not limited to, the following salts selected from the following groups: the salts, in particular the alkali metal and ammonium salts, of mono- and dialkyl phosphates, in particular C8-C22 alkyl phosphates, the salts, in particular the alkali metal and ammonium salts, of phosphoric acid half-esters of C2-C3 alkoxylated alkanols, preferably with a degree of alkoxylation in the range from 2 to 40, in particular in the range from 3 to 30, e.g. phosphoric acid monoesters of ethoxylated C8-C22 alkanols, preferably with a degree of ethoxylation (EO level) in the range from 2 to 40, phosphoric acid monoesters of propoxylated C8-C22 alkanols, preferably with a degree of propoxylation (PO level).) in the range from 2 to 40 and phosphoric acid half esters of ethoxylated-co-propoxylated C8-C22 alkanols, preferably with a degree of ethoxylation (EO level) in the range from 1 to 20 and a degree of propoxylation from 1 to 20, the salts, in particular the alkali metal and ammonium salts, of phosphoric acid monoesters of ethoxylated alkylphenols, in particular phosphoric acid monoesters of ethoxylated C4-Cis-alkylphenols (EO content preferably 3 to 40), the salts, in particular the alkali metal and ammonium salts, of alkylphosphonic acids, in particular C8-C22 alkylphosphonic acids and the salts, in particular the alkali metal and ammonium salts, of alkylbenzenephosphonic acids, in particular C8-C22 alkylbenzenephosphonic acids.

[0128] Further suitable anionic surfactants can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208. The surfactant preferably comprises at least one anionic emulsifier carrying at least one sulfate or sulfonate group. This can be the only type of anionic emulsifier. However, mixtures of at least one anionic emulsifier carrying at least one sulfate or sulfonate group and at least one anionic emulsifier carrying at least one phosphate or phosphonate group can also be used. In such mixtures, the amount of at least one anionic emulsifier carrying at least one sulfate or sulfonate group is preferably at least 50% by weight, based on the total weight of the anionic surfactants used in the process according to the invention.In particular, the amount of anionic emulsifiers carrying at least one phosphate or phosphonate group must not exceed 20% by weight, based on the total weight of the anionic surfactants used in the process according to the invention.

[0129] In addition to the aforementioned anionic surfactants, the surfactant may also contain one or more nonionic surface-active substances, which are particularly selected from nonionic emulsifiers. Suitable nonionic emulsifiers include, for example, araliphatic or aliphatic nonionic emulsifiers, for example, ethoxylated mono-, di-, and trialkylphenols (EO level: 3 to 50, alkyl radical: C4-C10), ethoxylates of long-chain alcohols (EO level: 3 to 100, alkyl radical: Cs-Cc), and polyethylene oxide / polypropylene oxide homo- and copolymers. These can contain the alkylene oxide units randomly distributed or polymerized in the form of blocks. EO / PO block copolymers are very suitable examples.Preference is given to ethoxylates of long-chain alkanols, in particular those having an average degree of ethoxylation of 5 to 100 in the alkyl radical Cs-Cao and, among these, particularly preferably those having a linear C12-C20 alkyl radical and an average degree of ethoxylation of 10 to 50, as well as ethoxylated monoalkylphenols.

[0130] In a particular embodiment of the invention, the surfactants used in the process according to the invention contain less than 20% by weight, in particular at most 10% by weight, of non-ionic surfactants, based on the total amount of surfactants used in the process of the present invention and in particular contain no non-ionic surfactant. In another embodiment of the invention, the surfactants used in the process of the present invention comprise at least one anionic surfactant and at least one non-ionic surfactant, the ratio of anionic surfactants to non-ionic surfactants usually being in the range from 0.5:1 to 10:1, in particular 1:1 to 5:1.

[0131] Preferably, the surfactant will be used in an amount such that the amount of surfactant is in the range from 0.2 to 5% by weight, in particular in the range from 0.5 to 3% by weight, based on the monomers M.

[0132] The aqueous reaction medium during the polymerization may in principle also contain minor amounts (usually at most 5 wt. %) of water-soluble organic solvents, for example methanol, ethanol, isopropanol, butanols, pentanoic acid, but also acetone, etc. However, the process according to the invention is preferably carried out in the absence of such solvents. It is often advantageous if the aqueous polymer dispersion obtained after completion of the polymerization of the monomers M is subjected to a post-treatment to reduce the residual monomer content. This post-treatment is carried out either chemically, e.g., by completing the polymerization reaction with a more effective free-radical initiator system (so-called post-polymerization), and / or physically, e.g., by stripping the aqueous polymer dispersion with steam or inert gas.Corresponding chemical and physical processes are familiar to the person skilled in the art - see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and DE-A 19847115. The combination of chemical and physical post-treatment has the advantage that it removes not only the unreacted ethylenically unsaturated monomers but also other disruptive volatile organic components (VOCs) from the aqueous polymer dispersion.

[0133] The polymer latex of the carboxylated polymer is obtainable, for example, by a single-stage or multi-stage emulsion polymerization, in particular an aqueous radical emulsion polymerization, of a monomer composition M. The term "multi-stage" is well understood in the context of aqueous emulsion polymerization and means that the relative concentration of the monomers in the monomer composition M added to the polymerization reaction is changed at least once during the aqueous emulsion polymerization. Such a process leads to at least two polymer populations of different monomer compositions in the polymer particles of the latex. For example, it will be possible to change the monomer composition such that the multi-stage latex polymer contains populations with different glass transition temperatures or a glass transition temperature (T g) gradient. It is also possible to change the monomer composition so that the multi-stage latex polymer has populations with different concentrations of polymerized acidic monomers, such as monomers M2, or a concentration gradient of monomers M2. During the addition of the monomers M, the type of monomers and / or their quantitative ratio can be changed continuously or stepwise. The polymerization reaction remains constant. For example, it is possible for the ratio of monomers M1 and M2 to increase or decrease during the addition.

[0134] Preferably, the aqueous polymer latex of the carboxylated polymer is prepared by a radical aqueous emulsion polymerization according to the so-called feed process, wherein during the feed of the monomer composition M at least 90% of the monomer composition M polymers to be polymerized are metered in under polymerization conditions during a metering time P of the polymerization reaction, and wherein the composition of the part of the monomer composition M which is metered in under polymerization conditions of the polymerization reaction is changed at least once during the metering time.

[0135] In a particular embodiment, the content of monomers M2 in the monomer composition M, i.e. the relative amount of monomers M2 to the weight of the monomer composition M fed to the polymerization reaction, is increased to a higher level for one or more limited time periods P(n). After each of these time periods, the relative amount of monomers M2 is reduced. During each of the periods P(n), the relative amount of monomers M2 to the total amount of monomers fed during this period is at least 0.5 pphm higher, in particular at least 1.0 pphm higher, than the level outside the periods. In particular, the amount of monomers M2 fed during the periods P(n) is 0.5 to 80 pphm, in particular 1.0 to 50 pphm higher, than the average amount of monomers M2 fed outside the periods P(n).

[0136] Here and throughout the description, and particularly in this embodiment, the term pphm (parts per hundred monomers) is used as a synonym for the relative amount of a particular monomer to the total amount of monomer composition M in wt.%. For example, x pphm of monomer M2 means x wt.% of monomers M2, based on the total amount of monomers of monomer composition M. An increase of y pphm means that the relative amount of a particular monomer is increased by y wt.%, based on the total weight of monomers of monomer composition M.

[0137] In this particular embodiment, there may be a single period P(n) during which the weight level of the monomers M2 is increased. However, there may also be more than one period P(n). The total number of periods P(n) is not particularly limited and may be up to 20 or even more. For practical reasons, the total number of periods P(n) will generally not exceed 10 and in particular will be from 1 to 6. In this particular embodiment, the content of monomers M2 in the monomer composition M outside the periods P(n), i.e., the content of monomers M2 before and after each period P(n), may be the same or vary slightly. The fluctuation in the content of monomers M2 outside the periods P(n) is normally no more than 1 pphm, in particular no more than 0.5 pphm. The values ​​given here refer to the mean values ​​during the periods P(n) and outside the periods P(n).Preferably, the content of monomers M2 within the periods P(n) is in the range from 1.5 to 85 ppm, in particular 2 to 50 ppm.

[0138] In this particular embodiment, the period(s) P(n) in which the concentration of the acidic monomers M2 is increased may lie entirely within the period P or at the end of the period P. In this particular embodiment, it is important that the first period P(n) does not begin before at least 5% of the monomers M, in particular at least 10% of the monomers M subjected to the emulsion polymerization, have been metered into the polymerization reaction. During this period(s) P(n), the weight ratio of the acidic monomers M2 to the total amount of the other monomers M1 + M3 in the monomer composition metered into the polymerization reaction is often at least 0.02:1, in particular at least 0.03:1. Before each such period P(n), the ratio of the acidic monomers M2 to the total amount of the other monomers M1 + M3 should be less than 0.03:1, in particular less than 0.02:1.Likewise, at the end of each period P(n), the ratio of the acidic monomers M2 to the total amount of the other monomers M1 + M3 should be reduced to less than 0.03:1, in particular less than 0.02:1.

[0139] Preferably, the content of monomers M2 in the monomer composition and likewise the weight ratio of the acidic monomers M2 to the total amount of the other monomers M1 + M3 in the monomer composition M that is metered into the polymerization reaction can be manipulated. For example, a single feed line can be used to meter the monomers M into the polymerization reaction. By increasing the concentration of the monomers M2 in the single feed line of monomers M or by lowering the total concentrations of the monomers M1 + M3 or by both measures, the ratio of the acidic monomers M2 to the total amount of the other monomers M1 + M3 can be reduced or increased. A portion of the monomers M2, e.g. at least 20%, in particular at least 30%.

[0140] It can be seen that the total duration of all periods P(n) is shorter than the duration of period P required for metering the total amount of monomers M into the polymerization reaction. Frequently, the total duration of all periods P(n) does not exceed 50%, in particular 40% and in particular 30% of the duration of period P. Frequently, the total duration of all periods P(n) is at least 0.2%, in particular at least 0.5% and in particular at least 1% of the duration of period P. In particular, the ratio of the total duration of all periods P(n) to the duration of period P is from 0.002:1 to 0.5:1, in particular from 0.005:1 to 0.30:1. Frequently, the total duration of all periods P(n) is from 30 seconds to 60 minutes. The duration of an individual period P(n) is of minor importance and can be a few seconds, e.g. 10 seconds, and up to 60 minutes or more. The duration of a period P may depend on the production plant and may be, for example,The time can vary from 20 minutes to 12 hours. It will often be in the range of 0.5 hours to 5 hours, especially from 1 hour to 4 hours.

[0141] In this particular embodiment, it is possible to add the total amount of monomers M2 contained in the monomer composition M during the at least one period P(n), i.e., during all periods P(n). However, it is not necessary to add the total amount of monomers M2 during the at least one period P(n). Rather, it is preferred that outside of the periods P(n), the monomer composition added to the polymerization reaction still contains one or more monomers M2. Frequently, at least 20% of the monomers M2 contained in the monomer composition M, in particular at least 30% of the monomers M2 contained in the monomer composition M, are added to the polymerization reaction during the at least one period P(n).

[0142] The concentration of the polymer latex contained in the aqueous binder composition is often in the range of 10 to 70 wt%, in particular in the range of 30 to 69 wt%, in particular in the range of 40 to 68 wt% by weight, based on the total weight of the binder composition.

[0143] The aqueous binder composition typically consists of the aqueous polymer latex of a film-forming carboxylated polymer, as described herein, and the branched polyetheramine polyol, as described herein, and water. However, the aqueous binder composition may optionally contain other components such as dispersants, biocides, wetting agents, defoamers, rheology additives, and / or fillers.

[0144] Preferred embodiments of the aqueous binder composition contained in the water-based fire protection compositions are those mentioned above. In addition to the binder composition according to the invention, the fire protection compositions preferably also contain at least one pigment and / or at least one filler. However, fire protection compositions that do not contain a pigment or filler are also part of the invention.

[0145] Pigments in the sense of the present invention are practically insoluble, finely dispersed, organic or preferably inorganic colorants as defined by the German standard DIN 55944. The composition preferably contains at least one inorganic pigment. Preference is given to inorganic pigments, for example

[0146] White pigments such as titanium dioxide (Cl Pigment White 6), zinc white, zinc borate, pigment-grade zinc oxide, zinc sulfide, lithopone; lead white; furthermore, white fillers such as barium sulfate and CaCOa, which are also referred to as inorganic white pigments in the context of the present invention,

[0147] Black pigments, such as iron oxide black (Cl Pigment Black 11), iron manganese black, spinel black

[0148] (Cl Pigment Black 7), soot or lamp black,

[0149] Color pigments such as chromium oxide, hydrated chromium oxide green; chrome green (Cl Pigment Green 48); cobalt green (Cl Pigment Green 50); ultramarine green; cobalt blue (Cl Pigment Blue 28 and 36); ultramarine blue, iron blue (Cl Pigment Blue 27), manganese blue, ultramarine violet, cobalt violet, manganese violet, Fe3O4, iron oxide red (Cl Pigment Red 101); cadmium sulfoselenide (Cl Pigment Red 108); molybdate red (Cl Pigment Red 104); ultramarine blue,

[0150] Iron oxide brown, mixed brown, spinel and corundum phases (Cl Pigment Brown 24, 29 and 31), chrome orange; iron oxide yellow (Cl Pigment Yellow 42); nickel titanium yellow (Cl Pigment Yellow 53; Cl Pigment Yellow 157 and 164); chrome titanium yellow; cadmium sulfide and cadmium zinc sulfide (Cl Pigment Yellow 37 and 35); chrome yellow (Cl Pigment Yellow 34), zinc yellow, alkaline earth chromates; Naples yellow; bismuth vanadate (Cl Pigment Yellow 184);

[0151] Preferred inorganic pigments are selected from inorganic white pigments, in particular titanium dioxide, barium sulfate and CaCOa.

[0152] The compositions may also contain mixtures of two or more different pigments, in which case it is preferred that at least one pigment is inorganic. The pigments are typically in particulate form, i.e., in the form of particles. Pigments may be selected from raw pigments, i.e., untreated, such as synthesized pigments. The pigment particles may be of regular or irregular shape, for example, the particles may have a substantially spherical or needle shape.

[0153] In one embodiment of the present invention, the pigment has a pronounced uneven ratio of length to diameter with an average particle length (median, d50) in the range from 1 to 50 pm, preferably in the range from 2 to 20 pm and particularly preferably in the range from 5 to 15 pm and a ratio of the particle length to the smallest diameter of at least 2:1, preferably 10:1 to 20:1 and particularly preferably greater than 20:1. In one embodiment of the present invention, the pigment is in spherical or substantially spherical form, ie the ratio of the longest diameter to the smallest diameter is in the range from 1.0 to 2.0, preferably up to 1.5. In one embodiment of the present invention, the pigment has an average particle diameter (median, d50) in the range from 20 to 50 pm, preferably in the range from 50 to 20 pm and particularly preferably up to a maximum of 5 pm, measured e.g.using a Coulter counter or a Hegman meter.

[0154] Examples of suitable fillers are aluminosilicates such as feldspars, silicates such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates such as calcium sulfate, silicon dioxide, attapulgite, or also glass spheres, hollow glass spheres, glass powder, expanded open- or closed-cell glass powder, perlite, basalt, pumice, etc. Finely divided fillers are naturally preferred in the coating compositions according to the invention. The fillers can be used in the form of individual components. In practice, however, filler mixtures have proven particularly effective, for example calcium carbonate / kaolin, calcium carbonate / talc. The fillers also include matting agents, which can significantly impair the surface gloss if desired.Examples of matting agents include inorganic silicates, such as the Syloid® brands from WR Grace & Company and the Acematt® brands from Evonik GmbH. Organic matting agents are available from BYK-Chemie GmbH under the Ceraflour® and Ceramat® brands, and from Deuteron GmbH under the Deuteron MK® brand.

[0155] The proportion of pigments and fillers in coating materials can be described in a conventional manner using the pigment volume concentration (PVC). The PVC describes the ratio of the volume of pigments (VP) and fillers (VF) to the total volume, consisting of the volumes of binder (VB), pigments (VP), and fillers (VF), in a dried coating in percent: PVC = (VP + VF) x 100 / (VP + VF + VB).

[0156] The compositions typically have a pigment volume concentration (PVC) of at least 5, in particular at least 10. Preferably, the PVC will not exceed a value of 60, in particular 40, and is in particular in the range from 5 to 60 or 5 to 40. However, the inventive effects of the polymer dispersions are also evident in coatings which typically have a pigment / filler content of less than 5 wt.%, based on the coating composition, and accordingly have a PVC of less than 5.

[0157] The aqueous fire-protection coating compositions according to the invention produced with the binder according to the invention may also contain conventional auxiliaries. The conventional auxiliaries depend, as is known, on the type of coating and include, but are not limited to:

[0158] Rheology modifiers, wetting or dispersing agents, film-forming agents, flow agents, biocides, defoamers, and at least one intumescent filler combination containing at least melamine (blowing agent), ammonium polyphosphate (acid donor), and polyalcohol (carbon source). These intumescent filler combinations are well known, for example, from "Die Aktuelle-Wochenschau der GDCh - Bauen und Chemie 32 / 2011," Rene Gries, "Fire Protection - an Interesting, Diverse Application Area of ​​Construction Chemistry," and are commercially available, for example, as Charmor™ PM40 (Perstorp AB, SE-284 80 Perstorp, Sweden), Melafine® (OCI NV Amsterdam, NL), or Exolit® AP 462 (Clariant, Muttenz, Switzerland).

[0159] Suitable rheology modifiers include associative thickener polymers and non-associative rheology modifiers. Suitable associative thickener polymers include anionic associated thickeners such as hydrophobically modified acrylate thickeners, also known as HASE thickeners, and nonionic associative thickeners, also known as NiSAT-type associative thickeners, including hydrophobically modified polyethylene oxide urethane rheology modifiers, also known as HEUR or PUR thickeners, or hydrophobically modified polyethylene oxides, also known as HMPE. Suitable non-associative rheology modifiers include cellulose-based thickeners, especially hydroxyethylcellulose, but also thickeners based on acrylate emulsions (ASE). Non-associative cellulose-based thickeners are preferred.The amount of thickener polymer depends on the desired viscosity profile and is often in the range of 0.05 to 2.5 wt.%, in particular 0.1 to 2 wt.% thickener, and especially 0.15 to 1.5 wt.%, based on the coating composition. Inorganic thickeners are also suitable, such as attapulgite, a hydrated magnesium aluminosilicate and a major member of the Fuller's Earth family (clay minerals) with the ideal formula: 3MgO - 1.5Al2O3 - 8SiO2 - 9H2O. Fuller's Earth is known as any clay material that can decolorize oil or other liquids without the use of aggressive chemical treatment. Fuller's Earth typically consists of palygorskite (attapulgite) or bentonite. The highly thixotropic behavior of these attapulgites ensures improved syneresis control and reduced settling tendency without negatively affecting the leveling and film build-up of the coating agent.

[0160] Suitable wetting or dispersing agents are, for example, sodium polyphosphates, potassium polyphosphates or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers or polyphosphonates.

[0161] Solvents and plasticizers are suitable as film-forming aids. Unlike solvents, plasticizers have low volatility and preferably have a boiling point of more than 250°C at 1013 mbar. Solvents have higher volatility than plasticizers and preferably have a boiling point of less than 250°C at 1013 mbar. Suitable film-forming aids include, for example, white spirit, pine oil, propylene glycol, ethylene glycol, butyl glycol, butyl glycol acetate, butyl glycol diacetate, butyl diglycol, butyl carbitol, 1-methoxy-2-propanol, 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate (Texanol®) and the glycol ethers and esters, commercially available, for example, from BASF SE under the names Solvenon® and Lusolvan® and from Dow under the trade name Dowanol®. The amount is preferably <10 wt.% and particularly preferably <5 wt.%, based on the total formulation. Formulation is also possible entirely without solvent.Further formulation ingredients for aqueous coatings are described in detail in M. Schwartz and R. Baumstark "Water-based acrylates for decorative coatings", Curt R. Vincentz Verlag, Hanover, 2001, pp. 191-212 (ISBN 3-87870-726-6). For a better understanding of the invention, the following explanations of the terminology used herein are considered useful. For the purposes of the invention:

[0162] "chemical intumescence" the formation of a voluminous, insulating ash layer by matched compounds that react with each other when exposed to heat;

[0163] "physical intumescence" means the formation of a voluminous insulating layer by expansion of a gas-releasing compound without a chemical reaction having taken place between two compounds, whereby the volume of the compound increases by several times its original volume;

[0164] "insulating layer forming" or "intumescent" means that in the event of a fire a solid microporous carbon foam is formed, so that the forming fine-pored and thick foam layer, the so-called ash crust, insulates a substrate against heat; a "carbon supplier" is an organic compound that leaves a carbon framework due to incomplete combustion and does not burn completely to carbon dioxide and water (carbonization); these compounds are also called "carbon framework formers"; an "acid former" is a compound that, under the influence of heat, i.e. above about

[0165] 150 °C, for example by decomposition, forms a non-volatile acid and thereby acts as a catalyst for carbonization; furthermore, it can contribute to reducing the viscosity of the melt of the binder; the term "dehydrogenation catalyst" is used as an equivalent; a "blowing agent" is a compound that decomposes at elevated temperature with the evolution of inert, i.e. non-combustible gases and, if appropriate, expands the plasticized binder composition into a foam (intumescence); this term is also used synonymously with "gas former"; an "ash crust stabilizer" is a so-called skeleton-forming compound that stabilizes the carbon skeleton (ash crust) formed from the interaction of carbon formation from the carbon source and the gas from the blowing agent, and fixes the foam structure formed.The basic mechanism of action is that the forming, actually very soft, carbon layers are mechanically strengthened by inorganic compounds. The addition of such an ash crust stabilizer contributes to a significant stabilization of the intumescent crust in the event of a fire, as these additives increase the mechanical strength of the intumescent layer and / or prevent dripping.

[0166] A further embodiment of the present invention providing the aforementioned properties are methods for producing a fire protection coating on a surface comprising

[0167] (a) applying the fire protection composition of the invention to the surface, and (b) allowing the composition to dry to produce the coating.

[0168] The composition can be applied to surfaces and / or substrates to be coated in a conventional manner, such as by applying the paint with a brush or roller, by spraying, by dipping, by rolling, or by doctor blade coating. The coating of surfaces and / or substrates is carried out by first coating the surface and / or substrate with a composition according to the invention, and then subjecting the aqueous fire protection composition to a drying step.

[0169] The substrate can be coated with a suitable primer prior to coating. This may be intended to improve the adhesion of the fire protection composition according to the invention to the substrate and / or to apply an additional corrosion-inhibiting intermediate layer.

[0170] The composition can be applied to surfaces such as metal, asphalt, concrete, fiberboard, stone, ceramic, minerals, wood, plastic, polymer, and glass. The composition can be applied to interior or exterior surfaces, such as an architectural surface such as a roof, wall, floor, or ceiling. The composition can also be applied to architectural structural components or parts of the building services, for example, and not limited to, beams, joists, cable ducts, ventilation pipes, water or electrical lines, or cladding. Preferably, the composition can be applied to statically loaded structural components in buildings. The application can take place both indoors and outdoors.

[0171] The branched polyetheramine polyols described herein have a superior effect on the curing and / or hardening behavior of polymer binders, such as film-forming carboxylated polymers. In particular, the branched polyetheramine polyols accelerate the film formation process, resulting in accelerated curing of the binder, which overall accelerates the curing of the fire protection composition of the invention. Physically curing aqueous fire protection coatings can thus be applied in higher layer thicknesses, with less labor, and can be overcoated with additional coatings after a shorter waiting time.

[0172] From EP 3910034A1, it is known that the fire protection composition can only protect the component to which it is applied from fire or against the effects of extreme heat in the event of a fire if the fire protection composition forms an insulating layer after curing, the so-called fire protection coating. To ensure adequate fire protection, the solids content of the fire protection composition according to the invention is at least 50 wt.% based on the total weight of the fire protection composition. The term "solids content" within the meaning of the present invention describes the proportion of compounds in the composition that are solid at room temperature. Excluded from this are any binders that are solid at room temperature, which may be present in the fire protection composition. The solids content of the fire protection composition can thus be calculated from the filler content of the composition.The solids content is preferably in a range from 50% to 85% by weight, preferably in a range from 55% to 80% by weight, more preferably in a range from 60% to 78% by weight. The second component of the intumescent fire protection composition comprises at least one intumescent fire protection additive, wherein the intumescent fire protection additive can comprise either a single compound or a mixture of several compounds.

[0173] Intumescent fire protection additives are those that act by forming an inflated, insulating layer of flame-retardant material under the influence of heat, which protects the substrate from overheating and thus significantly delays the change in the mechanical and static properties of load-bearing components due to the influence of heat.

[0174] The formation of a voluminous, insulating layer, namely an ash layer, can be achieved through the chemical reaction of a mixture of appropriately matched compounds that react with each other upon exposure to heat. Such systems are known to those skilled in the art under the term chemical intumescence and can be used according to the invention. Alternatively, the voluminous, insulating layer can be formed by physical intumescence. Both systems can be used individually or together in combination according to the invention.

[0175] For the formation of an intumescent layer through chemical intumescence, at least three components are generally required as an intumescent fire protection additive: a carbon source, a dehydration catalyst (=acid generator), and a gas generator (=blowing agent), which are often contained in a binder. When exposed to heat, the binder softens and the fire protection additives are released, allowing them to react with each other and expand in the case of chemical intumescence. Through thermal decomposition, the dehydration catalyst converts the acid into the carbon source, which serves as a catalyst for the carbonization of the carbon source. At the same time, the gas generator thermally decomposes to form inert gases, which cause the carbonized (charred) material and, if necessary, the softened binder to expand, forming a voluminous, insulating foam.

[0176] In a further embodiment of the invention, in which the insulating layer is formed by chemical intumescence, the intumescent additive comprises at least one carbon framework former (=carbon supplier) if the binder cannot be used as such, at least one acid former, at least one gas former, and at least one inorganic framework former. The components of the additive are selected in particular so that they can develop synergism, with some of the compounds being able to fulfill multiple functions. It is well known to those skilled in the art that the weight ratio of the four main components of the intumescent additive composition, carbon framework former: acid former: gas former: inorganic framework former, should be 0.7-1.3:2.7-3:0.7-1.3:0.7-1, preferably 1:3:1:1.

[0177] An example of a fire protection coating that utilizes chemical intumescence is the commercially available product "Hilti Fire Finish 120+ CFP-SP WB." Compounds based on pentaerythritol, such as monopentaerythritol, are preferred as carbon framework formers, which also exhibit high storage stability in water-based dispersions. Furthermore, the free hydroxide groups can be protected by additional substituents. Examples include pentaerythritol tetraacetate, pentaerythritol tetraacrylate, and pentaerythritol tetrabenzoate.

[0178] The polymer that serves as a binder can also function as a carbon supplier in the event of a fire, so that the addition of an additional carbon supplier is not always necessary.

[0179] Suitable acid generators or dehydrogenation catalysts, which also exhibit high storage stability in water-based dispersions, are the compounds commonly used in intumescent fire protection formulations and known to those skilled in the art, in particular a salt or ester of an inorganic, non-volatile acid selected from sulfuric acid, phosphoric acid, or boric acid. Coated phosphorus-containing compounds are primarily used, and their range is very broad, as they span several phosphorus oxidation states, such as phosphines, phosphine oxides, phosphonium compounds, phosphates, elemental red phosphorus, phosphites, and phosphates.Examples of phosphoric acid compounds include: monoammonium phosphate, diammonium phosphate, ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine resin phosphates, potassium phosphate, polyol phosphates such as pentaerythritol phosphate, glycerol phosphate, sorbitol phosphate, mannitol phosphate, dulcitol phosphate, neopentyl glycol phosphate, ethylene glycol phosphate, dipentaerythritol phosphate, and the like. A polyphosphate or an ammonium polyphosphate is preferably used as the phosphoric acid compound. Melamine resin phosphates are understood to mean compounds such as reaction products of Lamelite C (melamine-formaldehyde resin) with phosphoric acid. Examples of sulfuric acid compounds include: ammonium sulfate, ammonium sulfamate, nitroaniline bisulfate, 4-nitroaniline-2-sulfonic acid, and 4,4-dinitrosulfanilamide, and the like. Examples of boric acid compounds include melamine borate.

[0180] However, to simultaneously increase the storage stability of the water-based dispersion, coated and / or encapsulated acid generators are ideally suited for the present composition. Examples include the commercially available products Exolit® AP 462, Exolit® AP 750, Exolit® AP435, FR Gros® C70, FR Gros® 486, FR Gros® 584, and Exflam® APP 205 from Clariant, Budenheim, and Wellchem. These products each feature a coating, for example, melamine, silicone, or epoxy.

[0181] Suitable gas generators or blowing agents are the compounds commonly used in flame retardants and known to those skilled in the art, such as cyanuric acid or isocyanic acid and their derivatives, melamine and their derivatives. These include cyanamide, dicyanamide, dicyandiamide, guanidine and its salts, biguanide, melamine cyanurate, cyanic acid salts, cyanic acid esters and amides, hexamethoxymethylmelamine, dimelamine pyrophosphate, melamine polyphosphate, and melamine phosphate. Hexamethoxymethylmelamine or melamine (cyanuric acid amide) is preferably used. Also suitable are components whose mode of action is not limited to a single function, such as melamine polyphosphate, which acts both as an acid generator and as a gas generator. Further examples are described in GB 2007689 A1, EP 139401 A1, and US-3969291 A1.

[0182] In one embodiment of the invention in which the insulating layer is formed by physical intumescence, the intumescent additive comprises at least one thermally expandable compound, such as a graphite intercalation compound, also known as expandable graphite. Upon exposure to heat, the binder softens, allowing the fire protection additive to expand.

[0183] Examples of suitable expandable graphite include known intercalation compounds of sulfuric acid, nitric acid, acetic acid, Lewis acids, and / or other strong acids in graphite. These are also referred to as graphite salts. Expandable graphites that release SO2, SO3, CO2, H2O, NO, and / or NO2 upon expansion at temperatures of, for example, 120 to 350°C are preferred. The expandable graphite can, for example, be in the form of platelets with a maximum diameter in the range of 0.1 to 5 mm. This diameter is preferably in the range of 0.5 to 3 mm. Expandable graphites suitable for the present invention are commercially available.

[0184] An example of physical intumescence can be found in the over-the-counter product "Hilti FIRESTOP SEALANT FS-ONE MAX." Its effectiveness is often tested according to the specifications of ASTM E119-22, "Standard Test Methods for Fire Tests of Building Construction and Materials." For specific test conditions and product requirements, please refer to this standard.

[0185] In a further embodiment of the invention, the insulating layer is formed by both chemical and physical intumescence.

[0186] The binder according to the invention is preferably contained in the fire protection composition in a proportion of 20 to 45 wt.%, preferably 25 to 40 wt.%, based on the total weight of the fire protection composition.

[0187] The proportion of intumescent additive is in a range from 45% by weight to 80% by weight, preferably in a range from 50% by weight to 80% by weight, more preferably in a range from 55% to 75% by weight and even more preferably in a range from 57% to 70% by weight of intumescent additive.

[0188] Since the ash crust formed in a fire is generally too unstable and, depending on its density and structure, can be blown away by air currents, which negatively impacts the insulating effect of the fire protection coating, at least one ash crust stabilizer is preferably added to the fire protection additives listed above. The basic principle is that the inherently very soft carbon layers that form are mechanically strengthened by inorganic compounds. The addition of such an ash crust stabilizer contributes significantly to the stabilization of the intumescent crust in a fire, as these additives increase the mechanical strength of the intumescent layer and / or prevent it from dripping off.

[0189] Suitable ash crust stabilizers or framework formers are the compounds commonly used in fire protection formulations and known to the person skilled in the art, for example, expandable graphite and particulate metals such as aluminum, magnesium, iron, and zinc. The particulate metal can be in the form of a powder, platelets, flakes, fibers, filaments, and / or whiskers, with the particulate metal in the form of powder, platelets, or flakes having a particle size of <50 μm, preferably from 0.5 to 10 μm. When using the particulate metal in the form of fibers, filaments, and / or whiskers, a thickness of 0.5 to 10 μm and a length of 10 to 50 μm is preferred.Alternatively or additionally, an oxide or a compound of a metal from the group comprising aluminum, magnesium, iron, or zinc can be used as an ash crust stabilizer, in particular iron oxide, preferably iron trioxide, titanium dioxide, a borate, such as zinc borate, and / or a glass frit made of low-melting glasses with a melting temperature of preferably at or above 400°C, phosphate or sulfate glasses, melamine polyzinc sulfates, ferroglasses, or calcium borosilicates. The addition of such an ash crust stabilizer contributes to a significant stabilization of the ash crust in the event of a fire, since these additives increase the mechanical strength of the intumescent layer and / or prevent it from dripping off. Examples of such additives can also be found in US 4442157 A, US 3562197 A, GB 755551 A, and EP 138546 A1. In addition, ash crust stabilizers such as melamine phosphate or melamine borate can be included.

[0190] The following additional additives may be added to the composition according to the invention.

[0191] Compounds such as phosphate esters and halogen-containing compounds such as tri-(2-chloroisopropyl) phosphate (TCPP), tris(2-ethylhexyl) phosphate, dimethylpropanephosphonate, triethyl phosphate, and the like are added as flame retardants. Some such compounds are described, for example, in S. V. Levchik, E. D. Weil, Polym. Int. 2004, 53, 1901-1929. The flame retardants can preferably be present in the composition in an amount of 3 to 6 wt.%.

[0192] According to the invention, the fire protection composition comprises at least one leveling agent. The term leveling agent in the sense of the present invention describes a compound by means of which the viscosity of the composition is reduced. The inventive addition of a leveling agent enables the use of very high solids contents in the composition without impairing the surface properties, in particular the surface roughness, of a coating produced from the corresponding composition. Optionally, leveling is achieved by increasing the surface tension through the leveling agent. Preferably, silicone-based compounds (PDMS polydimethylsiloxane modified), fluorocarbon-based compounds (modified fluorocarbons), acrylate-based compounds (polyacrylates), or carbohydrate-based products are used as leveling agents.Examples include the commercially available products BYK 3760, Modaflow AQ3000, Modaflow AQ3025, and Afcone 3034. The leveling agents may preferably be present in the composition in an amount of 0.1% to 2.0% by weight, preferably 0.3% to 1.5% by weight, based on the total weight of the composition.

[0193] Additional additives such as thickeners, rheology additives, and fillers can be added to the composition and significantly improve the storage stability of the formulation. Suitable thickeners and rheology additives are helpful in improving the hold-up (the layer thickness that can be applied with one application process) in the composition. These additives also help to significantly improve storage stability. Rheology additives such as anti-settling agents, anti-sagging agents, and thixotropic agents are preferably methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, hydrophobically modified hydroxyethyl cellulose, alkali-swellable emulsions, hydrophobically modified ethoxylated urethane copolymers, hydrophobically modified cellulose ethers, hectorite clay, or attapulgite. Furthermore, organic low-shear thickeners are capable of significantly increasing hold-up.Suitable associative thickener polymers include anionic associated thickeners such as hydrophobically modified acrylate thickeners, also known as HASE thickeners. Examples of commercially available thickeners are Natrosol® 250HHR, Aquaion® 9M31 F, Benton® Gel 1002v, Natrosol® Plus 330, Acrysol® TT-615, Acrysol® ASC-60ER, Attagel® 50, Rheovis® HS 1162, or Rheovis® PU 1191.

[0194] The fire retardant composition may also contain common additives, such as solvents such as xylene or toluene, or Texanol. The use of Texanol, due to its comparatively high boiling point, is helpful in lowering the evaporation point. Furthermore, the addition of a solvent is very suitable for improving the product's sprayability, since, as is well known, the viscosity of the formulation is reduced by the addition of solvent.

[0195] The composition according to the invention can be formulated as a two- or multi-component system. It is preferably formulated as a ready-to-use one-component system.

[0196] The composition can be applied to the substrate, particularly a metallic substrate, by spraying it using a multi-component or single-component spray device. The composition is preferably applied using an airless spraying method.

[0197] The composition according to the invention is particularly suitable as a coating, in particular as a fire protection coating, preferably as a sprayable coating for metallic and non-metallic substrates. The substrates are not limited and include components, in particular steel components and wooden components, but also individual cables, cable bundles, cable trays and cable ducts or other lines. The present invention therefore further provides a coating produced from the fire protection composition according to the invention, as well as a substrate comprising a coating according to the invention or a fire protection composition according to the invention. The invention also further provides the use of the composition according to the invention for producing coatings with improved surface properties.

[0198] The following examples serve to further illustrate the invention.

[0199] Examples of implementation

[0200] Abbreviations:

[0201] • GPC Gel Permeation Chromatography

[0202] • HFIP Hexafluoroisopropanol

[0203] • Mn number average molecular weight

[0204] • Mw weight average molecular weight

[0205] • PD polydispersity, defined as PD = Mw / Mn

[0206] • PEI Polyethylenimine

[0207] • PMMAPolymethylmethacrylate

[0208] • PS particle size

[0209] • PDI polydispersity index of particle size distribution

[0210] Dynamic DLS light scattering

[0211] • s / s solid polymer additive based on solid polymer latex

[0212] • rpm revolutions per minute

[0213] Materials

[0214] • Polystyrene seed latex S1 : Polystyrene seed latex with a solids content of 33 wt.% and a volume-average particle diameter of 10 to 50 nm.

[0215] • Emulsifier E1 : Sodium dodecylsulfonate - 15% w / w aqueous solution.

[0216] • Polyethylenimine PEI1 : Lupasol FG from BASF SE - average molecular weight 600 g / mol

[0217] analysis

[0218] 1. The solids content was determined by drying a defined amount of the aqueous polymer dispersion (approx. 2 g) in an aluminum crucible with an inner diameter of approximately 5 cm at 120°C in a drying oven until constant weight was reached (approx. 2 hours). Two separate measurements were performed. The value given in the example is the mean of the two measurements.

[0219] 2. The particle diameter of the polymer latex was determined by dynamic light scattering of an aqueous polymer dispersion diluted with deionized water to 0.001 to 0.5 wt.% at 22°C using a High Performance Particle Sizer (HPPS) from Malvern Instruments, England. The cumulative Z-average diameter calculated from the measured autocorrelation function (ISO standard 13321) is reported.

[0220] 3. The glass transition temperature was determined by the DSC method (differential scanning calorimetry, 20 K / min, center point measurement, DIN 53765:1994-03) using a DSC instrument (Q 2000 series from TA Instruments).

[0221] 4. The molecular weight was determined by GPC using a refractometer as the detector. HFIP was used as the mobile phase, and PMMA was used as the standard for molecular weight determination.

[0222] 5. The OH number of the polyetheramine polyol was determined according to DIN 53240, Part 2.

[0223] 6. The dynamic viscosity of the polyetheramine polyol was measured at 23°C and a shear rate of 100 s 1 determined according to ASTM D7042.

[0224] 7. The amine number was determined according to a standard protocol as per DIN EN ISO 9702:1998.

[0225] As can be seen from Table 1 below, the use of the additive according to the invention in the specified fire protection composition achieves an improvement in the curing rate by a factor of approximately 1.6 - 1.75.

[0226] Production example 1 (latex dispersion A / styrene acrylate):

[0227] In a 2 l glass vessel with anchor stirrer, heating and cooling devices as well as various inlets, at room temperature and atmospheric pressure (1 atm = 1.013 bar absolute)

[0228] 160.40 g of deionized water were added and heated to an internal temperature of 85 °C while stirring (150 rpm).

[0229] During heating before reaching 85°C, 8.33 g of a polystyrene seed latex with a solids content of 30% and a diameter of 29 nm is already introduced.

[0230] The following inflows are used:

[0231] Inlet 1 :

[0232] 189.79 g deionized water

[0233] 14.84 g 32% solution of a sodium fatty alcohol sulfate in water

[0234] 16.96 g 28% solution of sodium laurylpolyethoxysulfate in water

[0235] 21.25 g 20% ​​solution of a fatty alcohol ethoxylate in water

[0236] 7.5 g acrylic acid

[0237] 198.8 g n-butyl acrylate

[0238] 78.60 g 2-ethylhexyl acrylate

[0239] 214.1 g styrene 1.0 g 3-methacryloxypropyltrimethoxysilane

[0240] Inlet 2:

[0241] 28.57 g of a 7 wt.% aqueous solution of sodium peroxodisulfate

[0242] 2.9 g of feed 2 are added all at once and stirred for 4 minutes. At the same time, 11 g of feed 1 are added over a period of 5 minutes. Feed 1 and feed 2 are started simultaneously and added over a period of 120 minutes while stirring at 85°C. The mixture is then post-polymerized for a further 30 minutes at 85°C, after which 15 g of a 10% solution of t-butyl hydroperoxide in water and 19 g of a 13.1% solution of acetone bisulfite in water are added. The reaction product is adjusted to pH 8 with sodium hydroxide solution (10%). A dispersion with a particle size of 170 nm and a solids content of 50% is obtained.

[0243] Production example 2 (latex dispersion B / pure acrylate)

[0244] A polymerization reactor equipped with a temperature control module and a dosing module is fed as follows:

[0245] Template 1 :

[0246] 406.56 g deionized water

[0247] 23.60 g seed latex S1

[0248] Feed 1 is prepared in the first addition vessel using the following components:

[0249] Inlet 1 :

[0250] 431.90 g deionized water

[0251] 86.67 g emulsifier E1

[0252] 6.50 g 2-ethylhexyl thioglycolate

[0253] 689.70 g methyl methacrylate

[0254] 583.10 g 2-ethylhexyl acrylate

[0255] 16.90 g acrylic acid

[0256] 10.40 g methacrylic acid

[0257] Feed 2 is prepared in the second addition vessel using the following mixture:

[0258] Inlet 2:

[0259] 55.71 g of a 7 wt.% aqueous solution of sodium peroxodisulfate

[0260] The initial mixture 1 is heated (polymerization temperature: 85°C, stirring speed: 150 rpm). Feeds 1 and 2 are started simultaneously and fed continuously over 3 hours. After feeds 1 and 2 have been added, 76.8 g of distilled water are added to the reactor, and the reaction mixture is stirred for an additional 20 minutes. After the post-polymerization is complete, 7.8 g of a 10% aqueous solution of tert-butyl hydroperoxide and 28.9 g of a 4.5% aqueous solution of acetone bisulfite are added over 1 hour. The resulting dispersion is then cooled to room temperature, adjusted to pH 8.4 with 30.4 g of 10% aqueous ammonia, and diluted with 108.3 g of distilled water.

[0261] 2570.6 g of the corresponding aqueous dispersion are obtained. A dispersion with a particle size of 159 nm and a solids content of 51.4% is obtained.

[0262] Preparation Example 3: Synthesis of polytriethanolamine from triethanolamine

[0263] A four-necked flask equipped with a stirrer, distillation bridge, gas inlet tube, and internal thermometer was charged with 2500 g of TEA and 70.78 g of 50 wt% aqueous H3PO2. The resulting mixture was heated to 200°C under nitrogen. The reaction mixture was stirred at 200°C for 25 hours, with the condensate formed during the reaction being removed via the distillation bridge using a moderate stream of N2 as a stripping gas. Towards the end of the specified reaction time, the temperature was lowered to 140°C, and residual low-molecular-weight products were removed at a pressure of 100 mbar.

[0264] Then, the reaction mixture was cooled to ambient temperature and the polytriethanolamine polyol was obtained.

[0265] Mn = 3960 g / mol; Mw = 39600 g / mol; Mw / Mn = 15.1

[0266] OH number: 284 mg KOH / g; total amine number: 426 mg KOH / g

[0267] Tertiary amine number: 426 mg KOH / g

[0268] Dynamic viscosity at 23°C: 9100 mPa'S 1 / 100 sec

[0269] The amount of secondary and primary amino groups was below the detection limit of 2 mg KOH / g, confirming that all amino groups present were tertiary amino groups.

[0270] Example 1: Binder composition of Latex Disp. A + polyetheramine polyol

[0271] The binder composition of Example 1 is prepared by mixing the polymer latex of Preparation Example

[0272] 1 is mixed with 2 wt.% (s / s) of the polyetheramine polyol according to the invention - obtained according to Preparation Example 3.

[0273] Example 2: Binder composition of Latex Disp. B + polyetheramine polyol

[0274] The binder composition of Example 2 is prepared by mixing the polymer latex of Preparation Example

[0275] 2 is mixed with 2 wt.% (s / s) of the polyetheramine polyol according to the invention - obtained according to Preparation Example 3.

[0276] Comparison example 1: Binder composition of Latex Disp. A + Polyethylenimine

[0277] The binder composition of Comparative Example 1 is prepared by mixing the polymer latex of Preparation Example 1 with 2 wt.% (s / s) polyethyleneimine PEI (Lupasol FG). Comparative Example 2: Binder composition of Latex Disp. B + Polyethylenimine

[0278] The binder composition of Comparative Example 2 is prepared by mixing the polymer latex of Preparation Example 2 with 2 wt% (s / s) of polyethyleneimine PEI (Lupasol FG).

[0279] To produce the fire protection compositions A and B according to the invention, the components listed in Table 4 below are mixed together. They are compared to an aqueous fire protection coating with PEI as a curing accelerator. Table 1 : Components of fire protection compositions (BSZ) in wt. %

Claims

Claims 1 . Use of a polymer comprising a (a) aqueous polymer latex of a film-forming carboxylated polymer; (b) 0.05 to 7.5 wt.% based on the dry weight of the carboxylated polymer of a branched polyetheramine polyol, dissolved in the aqueous phase of the polymer latex, wherein at least 90% of all amino groups in the branched polyetheramine polyol are tertiary amine groups and wherein the aqueous polymer latex of the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M, wherein the monomer composition M comprises, I) 70% by weight to 99.95% by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1 selected from C1-C20 alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C1-C20 alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 C atoms, C5-C20 cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms, vinyl esters of C1-C20 alkanoic acids, vinyl aromatic monomers, C2-C6 monoolefins and butadiene; II) 0.05 wt.% to 10 wt.%, based on the total weight of the monomer composition M, of one or more monoethylenically unsaturated monomers M2 selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms; ill) 0 wt.% to 20 wt.%, based on the total weight of the monomer composition M, of one or more non-ionic monomers M3 different from the monomers M1, as an aqueous binder for fire protection coatings.

2. Use of a polymer as an aqueous binder according to claim 1, characterized in that the fire protection coating is an aqueous intumescent fire protection composition containing an intumescent compound mixture and further additives.

3. Use of a polymer as an aqueous binder according to one of claims 1 or 2, characterized in that the intumescent compound mixture contains at least one carbon supplier, an acid generator, a gas generator and optionally an inorganic framework former.

4. Use of a polymer as an aqueous binder according to one of claims 1 to 3, characterized in that the weight ratio of carbon supplier : acid generator : gas generator : inorganic framework former is 0.7-1.3 : 2.7-3 : 0.7-1.3 : 0.7-1.

5. Use of a polymer as an aqueous binder according to one of claims 1 to 4, characterized in that the intumescent compound mixture comprises at least one thermally expandable compound.

6. Use of a polymer as an aqueous binder according to one of claims 1 to 5, characterized in that the fire protection coating contains at least one pigment and / or at least one filler.

7. Use of a polymer as an aqueous binder according to one of claims 1 to 6, characterized in that the proportion of the binder is 20 wt.% to 45 wt.%, based on the total weight of the fire protection composition.

8. Use of a polymer as an aqueous binder according to one of claims 1 to 7, characterized in that the fire protection composition is formulated as a one-, two- or multi-component system.

9. Use of a polymer as an aqueous binder according to any one of claims 1 to 8 as a co-binder in an aqueous intumescent fire protection composition.

10. Use of a polymer as an aqueous binder according to any one of claims 1 to 9 for the production of fire protection coatings with accelerated curing rate.

11. Use of a polymer as an aqueous binder according to any one of claims 1 to 10 in an insulating layer for coating components.

12. Use of a polymer as an aqueous binder according to any one of claims 1 to 11 in an insulating layer for coating components to improve fire protection.

13. Use of a branched polyetheramine polyol according to claim 1 in a fire protection coating.

14. Use of a branched polyetheramine polyol according to claim 1 in an aqueous intumescent fire protection composition.

15. A substrate partially or completely coated with an insulating layer containing the polymer as aqueous binder according to any one of claims 1 to 14.

16. A method for producing a coating on a surface, comprising applying the fire protection composition containing the polymer as an aqueous binder according to any one of claims 1 to 14 to the surface of a substrate and allowing the composition to cure to produce the coating.

17. Aqueous intumescent fire protection composition containing a polymer as aqueous binder according to claim 1, as well as an intumescent additive composition and further additives.

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