Aqueous adhesive composition

Abstract

The present invention relates to an aqueous binder composition comprising an aqueous polymer latex of a film-forming carboxylated polymer and a branched polyetheramine polyol dissolved in the aqueous phase of the aqueous polymer latex, wherein substantially all amino groups in the branched polyetheramine polyol are tertiary amine groups. The present invention further relates to an aqueous coating composition comprising the aqueous binder composition.

Description

[0001] This invention relates to aqueous adhesive compositions comprising aqueous polymer latexes of film-forming carboxylated polymers. The invention also relates to aqueous coating compositions comprising the aqueous adhesive compositions of this invention. Background Technology

[0002] The drying rate of paints or coatings, especially those intended for outdoor use (such as masonry or wood coatings), is highly dependent on weather conditions, particularly atmospheric humidity, temperature, and wind speed during application. For example, if the drying rate is too slow (e.g., due to low temperatures and / or high humidity), sudden rainfall can damage the coating. Conversely, a fast drying rate (e.g., under high temperatures and / or low humidity conditions) can result in too short a work-in timeframe, which can cause problems when applying the coating under these conditions. Therefore, it is necessary to control the drying rate of paints or coatings (to be less dependent on weather conditions) to ensure that the paints or coatings can be applied in any weather conditions without defects.

[0003] It is well known that certain water-soluble polyamine-based additives (such as polyethyleneimine) can increase the drying speed of paint. These additives provide sufficient drying speed and low paint damage under low temperature and high humidity conditions. However, such paints generally have poor storage stability. Furthermore, such paints are difficult to use under high temperature and low humidity conditions because under these conditions, the shelf life of the paint may be shortened and the coating will dry too quickly. Moreover, these coatings tend to yellow. Therefore, professional decorators are typically offered two series of paint compositions: one series with increased drying speed when applied in cold weather conditions, and another series with normal drying speed when applied in normal or warm weather conditions.

[0004] WO 2014 / 060456 describes a waterborne coating composition comprising an anionicly stabilized polymer latex, one or more derivatized polyamines, and a volatile base. The polyamines comprise multiple primary, secondary, or combinations thereof, and are particularly alkoxylated polyethyleneimine. The derivatized polyamines reduce the curing time of the coating composition. However, the coating tends to yellow upon exposure to UV light. Furthermore, the coating dries too quickly at higher temperatures and has too short an application time.

[0005] WO 2016 / 209691 describes a latex composition comprising anionicly stable latex, at least one volatile alkali compound, and one or more water-soluble polymers with multiple amine and hydroxyl functional groups on their main chain. This water-soluble polymer is an addition product formed by reacting at least one polyfunctional amine compound with one or more polyfunctional epoxy compounds, one or more monofunctional epoxy compounds, or combinations thereof. Its application performance is unsatisfactory. Summary of the Invention

[0006] The object of this invention is to provide a water-based adhesive composition that overcomes the shortcomings of the prior art. In particular, there is a need for an adhesive composition that provides sufficiently fast drying in cold and / or humid weather conditions, but also has sufficient application time in warm and / or dry weather conditions.

[0007] Surprisingly, these objectives have been found to be achieved by aqueous adhesive compositions comprising an aqueous polymer latex of a film-forming carboxylated polymer and a branched polyetheramine polyol dissolved in the aqueous phase of the latex, wherein substantially all amino groups in the branched polyetheramine polyol are tertiary amine groups. In particular, it has been found that the branched polyetheramine polyol, as defined herein, reduces or eliminates the dependence of the drying properties of paints or coatings based on aqueous polymer latexes of film-forming carboxylated polymers on application temperature. Therefore, adhesives comprising a combination of branched polyetheramine polyols as defined herein and aqueous polymer latexes of film-forming carboxylated polymers can be used to prepare coating compositions with drying properties that are almost independent of application temperature, thus providing accelerated drying at temperatures below 20°C and sufficient application time and extended shelf life at temperatures above 20°C.

[0008] Therefore, a first aspect of the present invention relates to an aqueous adhesive composition comprising an aqueous polymer latex of a film-forming carboxylated polymer and a branched polyetheramine polyol as defined herein dissolved in an aqueous phase of the aqueous polymer latex, wherein substantially all amino groups in the branched polyetheramine polyol are tertiary amine groups.

[0009] A second aspect of the invention relates to a waterborne coating composition comprising a waterborne adhesive composition as defined herein.

[0010] A third aspect of the invention relates to the use of a waterborne adhesive composition as defined herein as an adhesive or co-adhesive in a waterborne coating composition.

[0011] Another aspect of the invention relates to a method for producing a coating on a surface, the method comprising applying an aqueous adhesive composition as defined herein and / or a coating composition as defined herein to the surface and allowing the composition to dry to produce a coating.

[0012] Another aspect of the invention relates to the use of branched polyetheramine polyols in aqueous polymer latexes of film-forming carboxylated polymers, particularly for altering the drying speed of polymer latexes and paints containing said polymer latexes, wherein substantially all amino groups in said branched polyetheramine polyols are tertiary amine groups.

[0013] The invention described herein has several advantages:

[0014] - The drying properties of the adhesive composition of the present invention are almost independent of temperature, and enable the coating to have an accelerated drying rate at temperatures below 20°C, especially below 15°C, and a sufficient application time at temperatures above 20°C, especially above 25°C.

[0015] - The adhesive composition is stable over a long period of time (e.g., more than 14 days) and does not tend to form clumps.

[0016] - The adhesive composition and the coating obtained therefrom exhibit minimal yellowing properties.

[0017] Paints made from these adhesives will remain stable over long periods (e.g., more than 14 days) and have an increased shelf life. Detailed Implementation

[0018] The prefix C used here and throughout the specification in conjunction with the compound or molecule part n -C m Each indicates a range of possible carbon atoms that a molecule or compound can have. The term "C1-C" n "Alkyl" refers to a group of straight-chain or branched saturated hydrocarbon groups having 1 to n carbon atoms. For example, the term C1-C... 20 Alkyl groups represent a group of straight-chain or branched saturated hydrocarbon groups having 1 to 20 carbon atoms. Similarly, the term C5-C... 20Alkyl groups refer to a group of straight-chain or branched saturated hydrocarbon groups having 5 to 20 carbon atoms, while the term C1-C4 alkyl refers to a group of straight-chain or branched saturated hydrocarbon groups having 1 to 4 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl The alkyl group includes 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, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, and their isomers. C1-C4-alkyl refers to, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0019] Throughout this specification and elsewhere, the term "(meth)acryloyl" includes both acryloyl and methacryloyl. Therefore, the term "(meth)acrylate" includes both acrylate and methacrylate.

[0020] Throughout this specification, the terms "polymer latex" and "polymer dispersion" are used synonymously and refer to an aqueous polymer composition of a water-insoluble polymer, wherein the polymer exists in the form of finely dispersed polymer particles. Typically, the polymer latex can be obtained by emulsion polymerization (also known as primary latex), but it can also be obtained by emulsifying the polymer in an aqueous phase (secondary latex).

[0021] Here and throughout this specification, the term "polyetheramine polyol" refers to a polymer having amine, ether, and hydroxyl groups.

[0022] Here and throughout the specification, the term “pphm” is an abbreviation for “parts per hundred monomers” and is a weight fraction based on the total weight of the monomers in the respective composition.

[0023] Throughout this specification, the range "x to y wt%" is a synonym for the range "x wt% to y wt%". Similarly, the range "x to y mol%" is a synonym for the range "x mol% to y mol%". To avoid any ambiguity, it should be emphasized that this also applies to ranges given in "mol / kg", "mg KOH / g", "g / mol", "pphm", "℃", etc.

[0024] According to the present invention, the adhesive composition comprises an aqueous polymer latex 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 at least partially water-soluble. The water solubility of the branched polyetheramine polyol at 20°C is preferably at least 5 g / L, more preferably at least 10 g / L, particularly at least 50 g / L, and especially 100 g / L. In particular, the branched polyetheramine polyol is completely miscible with water at 20°C.

[0025] In branched polyetheramine polyols dissolved in the aqueous phase of polymer latex, substantially all amino groups are tertiary amine groups. Hereinafter, the term "substantially" means that at least 90%, preferably at least 95%, more preferably greater than 98%, and even more preferably greater than 99% of the amino groups in the branched polyetheramine polyol are tertiary amine groups. In particular, the branched polyetheramine polyol contains no detectable amounts of secondary or primary amine groups. Therefore, in branched polyetheramine polyols dissolved in the aqueous phase of polymer latex, all amino groups in the branched polyetheramine polyol are tertiary amine groups. Typically, branched polyetheramine polyols contain an average of less than 0.5 mol / kg of secondary and primary amine groups (if any). Specifically, polyetheramine polyols contain an average of less than 0.2 mol / kg, particularly less than 0.1 mol / kg of secondary and primary amine groups (if any).

[0026] Typically, branched polyetheramine polyols contain an average of 4 to 8.2 mol / kg of tertiary amine groups. In particular, polyetheramine polyols contain an average of 5 to 8.0 mol / kg of tertiary amine groups, especially 5 to 7.9 mol / kg.

[0027] The amine value of the polyetheramine polyol is preferably from 100 to 700 mg KOH / g, most preferably from 200 to 500 mg KOH / g, and is determined according to the method described in DIN EN ISO 9702:1998. In addition to determining the total amine content, this method can also determine the tertiary amine content, secondary amine content, and primary amine content.

[0028] In addition to amino groups, polyetheramine polyols also contain hydroxyl groups. The OH value of polyetheramine polyols is typically at least 100 mg KOH / g, for example, 100 to 800 mg KOH / g, particularly at least 200 mg KOH / g, for example, 200 to 700 mg KOH / g, particularly at least 250 mg KOH / g, for example, 250 to 650 mg KOH / g, as determined according to Part 2 of DIN 53240. The number of hydroxyl groups per molecule depends on the number-average molecular weight and degree of branching of the branched polyetheramine polyol. Typically, branched polyetheramine polyols contain an average of at least four, more preferably at least six, and more preferably at least ten hydroxyl groups per molecule. In principle, there is no upper limit to the number of terminal or side functional groups. Preferably, the branched polyetheramine polyol contains an average of up to 500 terminal hydroxyl groups per molecule, particularly up to 200 terminal hydroxyl groups.

[0029] Number-average molar weight (M) of branched polyetheramine polyols n The weight-average molar weight (M) of polyetheramine polyols is typically 500 to 55,000 g / mol, particularly 1,000 to 40,000 g / mol, and is determined by gel permeation chromatography using hexafluoroisopropanol as the mobile phase and polymethyl methacrylate as the standard. w The polydispersity (i.e., Mw / Mn ratio) of polyetheramine polyols is typically 1,000 to 300,000 g / mol, particularly 2,000 to 200,000 g / mol, and especially 5,000 to 150,000 g / mol, determined by gel permeation chromatography using hexafluoroisopropanol as the mobile phase and polymethyl methacrylate as the standard.

[0030] The dynamic viscosity of branched polyetheramine polyols is typically 5 to 200 Pa·s, particularly 8 to 150 Pa·s, as measured at 23°C according to ASTM D7042.

[0031] The term "branching" describes a polyetheramine polyol that does not have a linear structure but instead possesses numerous branching points within the polymer backbone, resulting in a branched polymer chain. Such branching points can be tri- or tetra-substituted carbon atoms and / or tertiary amine groups. Tertiary amine groups are particularly preferred as branching points.

[0032] The Hazen color value of polyetheramine polyols is preferably 100 to 600 (APHA), as determined according to DIN ISO 6271.

[0033] Polyetheramine polyols are typically amorphous and therefore may exhibit a glass transition. The glass transition temperature of polyetheramine polyols is preferably not more than 50°C, more preferably not more than 30°C, and even more preferably not more than 10°C, as determined by differential scanning calorimetry (DSC) as described below. The glass transition temperature of polyetheramine polyols is preferably -55 to 30°C, more preferably -55 to 10°C, as determined by DSC.

[0034] Branched polyetheramine polyols and their preparation are known, for example, in DE 3206459, EP 441198, WO 2009 / 047269, and WO 2014 / 012812, which disclose branched polyetheramine polyols based on the polycondensation products of at least one trialkylolamine.

[0035] In one embodiment of the invention, branched polyetheramine polyols can be obtained by polycondensation of at least one trialkylolamine or by polycondensation of a mixture of at least one trialkylolamine with an aliphatic or alicyclic polyol. For this purpose, the trialkylolamine is preferably selected from tri-C2-C8-alkanolamines, wherein the alkyl groups in the trialkylolamine may be different or the same, wherein the alkyl groups are preferably the same. More preferably, the trialkylolamine is selected from tri-C2-C4-alkanolamines, wherein the alkyl groups are the same. Particularly preferred trialkylolamines are triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, and triisobutanolamine, and mixtures thereof.

[0036] Suitable aliphatic or alicyclic polyols are, for example, aliphatic diols, aliphatic polyols with more than two hydroxyl groups, alicyclic diols, and alicyclic polyols with more than two hydroxyl groups. Aliphatic diols and aliphatic polyols with more than two hydroxyl groups are preferred. Examples of aliphatic diols are C2-C... 20 -Diols, such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptahydrate, octanediol, and their structural isomers. Other examples of aliphatic diols are those with the general formula HO-((CH2). n -O) m The polyether glycol has -H groups, wherein n is independently 1 to 10, preferably 2 to 4, and m is 2 to 100. Preferably, the polyether glycol is selected from polyethylene glycol, polypropylene glycol, polybutane glycol, and copolymers thereof. Examples of polyols having more than two hydroxyl groups are glycerol, pentaerythritol, trimethylolpropane, sorbitol, etc. Polyols can also be alkoxylated, particularly ethoxylated or propoxylated, for example, 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 mean of the alkylene oxide moiety) will not exceed 100, and is typically 2 to 50.

[0037] Preferably, the polyetheramine polyol can be obtained by polycondensation, wherein, based on the total amount of monomers, the monomers contain at least 50% by weight, preferably at least 70% by weight, more preferably at least 80% by weight of a compound selected from trialkylolamines.

[0038] Polyetheramine polyols are preferably obtained by polycondensation of monomers comprising 50 to 100 mol% of compounds selected from trialkanolamines and 0 to 50 mol% of compounds selected from aliphatic or alicyclic polyols, preferably comprising 70 to 100 mol% of compounds selected from trialkanolamines and 0 to 30 mol% of compounds selected from aliphatic or alicyclic polyols, more preferably comprising 80 to 100 mol% of compounds selected from trialkanolamines and 0 to 20 mol% of compounds selected from aliphatic or alicyclic polyols, wherein “mol%” is based on the total amount of monomers.

[0039] In one particular embodiment, the polyetheramine polyol can be obtained by polycondensation, wherein the monomer consists only of monomers selected from trialkylolamines. The trialkylolamine is preferably selected from tri-C2-C4-alkanolamines. Preferred tri-C2-C4-alkanolamines are selected from triethanolamine, triisopropanolamine, and tri-n-propanolamine.

[0040] The mixture of at least one trialkylolamine with an aliphatic or alicyclic polyol is preferably selected from a mixture of at least one trialkylolamine and an aliphatic or alicyclic C2-C8-polyol, wherein the trialkylolamine is selected from tri-C2-C4-alkylolamines.

[0041] Polyetheramine polyols obtained by polycondensation of triethanolamine, or triisopropanolamine, or a mixture of triethanolamine and triisopropanolamine are particularly preferred. In this embodiment, at least one other polyol, particularly at least one other diol, may optionally be present.

[0042] Polycondensation can be carried out with or without a catalyst. Suitable catalysts include, but are not limited to, phosphoric acid (H3PO4), phosphorous acid (H3PO3), or hypophosphorous acid (H3PO2), which can be applied as is or in aqueous solution. Preferably, the amount of catalyst added is 0.001 to 10 mol%, more preferably 0.005 to 7 mol%, and even more preferably 0.01 to 5 mol%, based on the amount of trialkylolamine.

[0043] Polycondensation can be carried out using a solvent. Examples of solvents that can be used in the method of the present invention are aromatic and / or aliphatic (cyclic) hydrocarbons and mixtures thereof, halogenated hydrocarbons, ketones, esters, and ethers. Preferably, aromatic hydrocarbons, aliphatic hydrocarbons, alkyl esters of alkanes, ketones, alkoxylated alkyl esters of alkanes, and mixtures thereof are preferred. Particularly preferred are monoalkylated or polyalkylated benzenes and naphthalenes, ketones, alkyl esters of alkanes, alkoxylated alkyl esters of alkanes, and mixtures thereof. Polycondensation is preferably carried out without the use of a solvent.

[0044] Polycondensation can be carried out at a temperature not exceeding 250°C, preferably not exceeding 230°C. For example, the polycondensation reaction is carried out in a temperature range of 150 to 230°C, preferably 180 to 215°C. Even more preferably, the temperature during the polycondensation process does not exceed 215°C, and especially not exceeds 210°C.

[0045] Polycondensation can be carried out at pressures from 0.02 to 20 bar. Preferably, polycondensation is carried out at atmospheric pressure. After polycondensation, residual monomers are preferably removed or blown off, for example by distillation at atmospheric or reduced pressure (e.g., in the range of 0.1 to 0.5 bar).

[0046] Water or other volatile products released during the polycondensation process can be removed from the reaction mixture to accelerate the reaction. Preferably, the water or other volatile products released during the polycondensation process are removed, for example by distillation and optionally under reduced pressure. The removal of water or other low-molecular-weight reaction byproducts may also be aided by passing a stream of gas that is substantially inert under the reaction conditions (e.g., nitrogen) or a rare gas (e.g., helium, neon, or argon) through the reaction mixture (stripping).

[0047] The branched polyetheramine polyols described herein are generally 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 a significant increase in viscosity.

[0048] Polycondensation can be terminated by a variety of methods. For example, the temperature can be lowered to a range where the reaction stops and the polycondensation product is storage-stable. Typically, this is below 100°C, preferably below 60°C, more preferably below 40°C, and very preferably at room temperature. Another option is to deactivate the catalyst by adding a basic component, such as a Lewis base or an organic or inorganic base.

[0049] Polycondensation reactions can be carried out in stirred tank reactors or in a cascade of stirred tank reactors. The process can be carried out in batch, semi-batch, or continuous modes.

[0050] Preferably, the condensation products of trialkanolamines and the cocondensation products of trialkanolamines described herein are used as polyetheramine polyols without chemical modification or derivatization. However, derivatives of the condensation products of trialkanolamines or derivatives of the cocondensation products of trialkanolamines can be used instead of the underrivatized condensation products.

[0051] Derivatives of such condensation and cocondensation products of trialkanolamines include products obtained by alkoxylation of the hydroxyl end groups of underivated condensation and cocondensation products. Similarly, underivated condensation or cocondensation products can be modified with hydrophobic or hydrophilic groups. Hydrophobicity or hydrophilicity can be achieved by reacting a portion of the hydroxyl end groups with selected reactants. The amino groups of the condensation and cocondensation products can also be quaternized using alkylating agents to obtain permanently cationically modified polymers. Such derivatives of condensation and cocondensation products of trialkanolamines are described, for example, in US 2011 / 0168045, WO 2009 / 060060, and WO2009 / 1112379. For the purposes of this invention, preferred derivatized products are alkoxylated condensation and cocondensation products.

[0052] Polyetheramine polyols are generally readily soluble in a variety of solvents, such as water, alcohols (e.g., 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.

[0053] The composition of the aqueous adhesive typically contains 0.01 to 10% by weight, particularly 0.05 to 7.5% by weight, and even more particularly 0.1 to 5% by weight of branched polyetheramine polyol, based on the dry weight of the carboxylated polymer of the aqueous polymer latex.

[0054] The aqueous adhesive composition of the present invention further comprises an aqueous polymer latex of a film-forming carboxylated polymer.

[0055] In the case of polymer latex, the term "film formation" refers to the ability of the carboxylated polymer of the latex to form a film on a surface after drying under the applied conditions. This polymer typically has a film-forming temperature of up to 50°C, and particularly up to 30°C. The film-forming temperature can be lowered, for example, by adding film-forming aids such as plasticizers and solvents.

[0056] The ability of latex polymers to form films under application conditions will depend on their glass transition temperature. Typically, the glass transition temperature Ti of carboxylated polymers in aqueous polymer dispersions is... g The temperature range is -20 to +60°C, especially 0 to +50°C, and especially +5 to +40°C.

[0057] The glass transition temperature can be determined by DSC (differential scanning calorimetry, 20 K / min, midpoint measurement) according to DIN 53765:1994-03 or ISO 11357-2, wherein sample preparation is preferably performed according to DIN EN ISO 16805:2005.

[0058] In the case of multiphase polymers containing two or more polymers or polymer phases with different glass transition temperatures, the glass transition temperatures of each polymer phase may exceed the range given herein. However, the weight-average glass transition temperature T calculated by the following equation... g (av) is typically -20 to +60°C, especially 0 to +50°C, and particularly +5 to +40°C:

[0059] T g (av)=(T g (1)*w1+T g (2)*w2….T g (n)*w n )

[0060] In the equation, T g (1) T g (2) to T g (n) represents the glass transition temperatures of polymers 1, 2 to n, in K, while w1, w2 to w n This indicates the amount of each polymer 1, 2 to n, expressed as a percentage by weight. For example, a polymer containing 20% ​​by weight of T... g The first polymer phase 1 is at -10℃ and 80% by weight of T g Aqueous latex of multi-stage polymers with a second polymer phase at +40℃ has a weight-average Tg g (av) = 34℃. If the aqueous polymer dispersion contains polymers with different T... g For polymers of 's, the minimum T g and the highest T g The temperature difference can be as high as, for example, 100°C, or, for example, 10 to 100°C. Preferably, the polymer dispersed in the aqueous polymer dispersion has only one T. g Or if it contains different T g For polymers of 's, the minimum T g and the highest T g The maximum difference should not exceed 50K, and in particular, should not exceed 20K.

[0061] According to Fox (TGFox, Bull. Am. Phys. Soc. 1956, Vol. 1, p. 123) and according to Ullmann's According to *The Technischen Chemie* [Ullmann's Encyclopedia of Industrial Chemistry] (Vol. 19, p. 18, 4th edition, Verlag Chemie, Weinheim, 1980), the following are good approximations of the glass transition temperatures of copolymers with at most slight crosslinking:

[0062] 1 / Tg(Fox)=x1 / Tg1+x2 / Tg2+....x n / Tg n ,

[0063] Where x1, x2, ..., x n Let Tg1, Tg2, ..., Tn be the mass fractions of monomers 1, 2, ..., n, and Tg1, Tg2, ..., Tg2, Tg3, Tg4, Tg5, Tg6, Tg7, Tg8, Tg9, Tg1 ... gn Tg values ​​are given in Kelvin for the polymer synthesized from only one of monomers 1, 2, ..., n in each case. The Tg values ​​for homopolymers of most monomers are known and listed in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A21, p. 169, Verlag Chemie, Weinheim, 1992; other sources for the glass transition temperatures of homopolymers include, for example, J. Brandrup, E. Himmergut, Polymer Handbook, 1st edition, J. Wiley, New York 1966, 2nd edition, J. Wiley, New York 1975, and 3rd edition, J. Wiley, New York 1989.

[0064] For multi-phase polymers comprising 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 temperatures of the other phases are typically below 40°C, preferably at most 30°C, as determined by DSC as described herein.

[0065] For a multi-level polymer comprising two polymers or polymer phases with different glass transition temperatures, the polymer preferably comprises 95 to 40 wt% of a polymer with a lower glass transition temperature (which is typically below 40°C) and 5 to 60 wt% of a polymer with a higher glass transition temperature (which is typically above 40°C) based on the total weight of the polymers.

[0066] The term "carboxylated polymer" refers to a latex polymer containing carboxyl groups attached to the polymer backbone. Typically, carboxyl groups are introduced into the polymer by polymerizing an olefinically unsaturated monomer having one or more carboxyl groups. Such monomers are usually selected from monoolefinically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoolefinically unsaturated dicarboxylic acids having 4 to 6 carbon atoms. Examples of such monomers include acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, 2-propylacrylic acid, itaconic acid, and fumaric acid.

[0067] Carboxylated polymers of film-forming polymer latexes are typically obtained by free radical copolymerization of monomers M that form carboxylated monomer latexes. These monomers M (also called monomer components M) comprise at least one mono-olefinically unsaturated monomer having at least one carboxyl group, such as mono-olefinically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and mono-olefinically unsaturated dicarboxylic acids having 4 to 6 carbon atoms; and at least one other neutral olefinically unsaturated monomer that is substantially insoluble in water, i.e., its solubility in deionized water at 20°C is at most 50 g / L. Typically, based on the total weight of monomers contained in the monomer component, the monomer component comprises 0.05 to 10% by weight of one or more mono-olefinically unsaturated monomers having at least one carboxyl group.

[0068] Specifically, the monomer component M is essentially composed of the following:

[0069] a) One or more olefinically unsaturated monomers M1, whose solubility in deionized water at 20°C is at most 50 g / L, and particularly selected from C1-C of monoolefinically unsaturated monocarboxylic acids having 3 to 6 carbon atoms. 20 -alkyl esters, mono-olefinic unsaturated dicarboxylic acids having 4 to 6 carbon atoms, di-C1-C 20 -alkyl esters, C5-C monoalkenyl unsaturated monocarboxylic acids with 3 to 6 carbon atoms 20 -Cycloalkyl esters, C1-C 20 - Vinyl esters of alkyl acids, vinyl aromatic monomers, C2-C6 monoolefins and butadiene;

[0070] b) One or more mono-ene unsaturated monomers M2, selected from mono-ene unsaturated monocarboxylic acids having 3 to 6 carbon atoms and mono-ene unsaturated dicarboxylic acids having 4 to 6 carbon atoms.

[0071] c) Optionally, one or more nonionic monomers M3, which are different from monomer M1.

[0072] In this document, the term "consistent with" means that the total amount of monomers M1, M2 and M3 constitutes at least 95% of the total amount of monomers in the monomer component, particularly at least 99% by weight or 100% by weight.

[0073] Examples of single-unit M1 include, but are not limited to:

[0074] - C1-C of monoalkenyl unsaturated monocarboxylic acids with 3 to 6 carbon atoms 20 -alkyl ester,

[0075] For example

[0076] - Acrylic acid C1-C 20 -Alkyl esters, 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, C-acrylate 12 / C 14 -Alkyl esters and stearyl acrylate,

[0077] -C1-C of methacrylic acid 20 -alkyl esters, 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, C-methacrylate 12 / C 14 -Alkyl esters and stearyl methacrylate;

[0078] -Di-C1-C of monoene-bonded unsaturated dicarboxylic acids having 4 to 6 carbon atoms 20 -alkyl esters, such as the di-C1-C of itaconic acid 20 -Alkyl esters, citralic acid di-C1-C 20 -alkyl esters, di-C1-C of maleic acid 20 -Alkyl esters and fumaric acid di-C1-C 20 -alkyl ester,

[0079] -C5-C of monoalkenyl unsaturated monocarboxylic acids with 3 to 6 carbon atoms 20 -Cycloalkyl esters, C5-C of acrylic acid 20 -C5-C of cycloalkyl esters and methacrylic acid 20 - Cycloalkyl esters,

[0080] -C1-C 20 Vinyl esters of alkyl acids,

[0081] - 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 α-methylstyrene.

[0082] -C2-C6-monoolefins and butadiene.

[0083] In a preferred embodiment, monomer M1 is a mixture of the following:

[0084] - At least one monomer M1a, selected from C1-C of acrylic acid 20 -C5-C of alkyl esters and methacrylic acid 20 -alkyl esters; and

[0085] - At least one monomer M1b, which is selected from vinyl aromatic monomers and C1-C4-alkyl esters of methacrylic acid and mixtures thereof.

[0086] The suitable monomer M1a is:

[0087] - Acrylic acid C1-C 20 -Alkyl esters, 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, C-acrylate 12 / C 14 -Alkyl esters and stearyl acrylate;

[0088] -C5-C of methacrylic acid 20 -alkyl esters, such as n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C-methacrylate 12 / C 14 -Alkyl esters and stearyl methacrylate;

[0089] and its mixtures.

[0090] The suitable monomer M1b is:

[0091] - C1-C4-alkyl esters of methacrylate, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate, with methyl methacrylate being particularly preferred;

[0092] - Vinyl aromatic monomers, especially monovinyl-substituted aromatic hydrocarbons, such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and α-methylstyrene, with styrene being particularly preferred;

[0093] and its mixtures.

[0094] Preferably, monomer M1a is selected from C2-C of acrylic acid. 10 -alkyl esters, particularly those selected from ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate.

[0095] Preferably, monomer M1b is selected from vinyl aromatic monomers and C1-C4-alkyl esters of methacrylic acid and mixtures thereof, particularly from styrene and methyl methacrylate.

[0096] In a mixture of monomers M1a and M1b, the relative amounts of M1a and M1b can be particularly 10:1 to 1:10, more particularly 5:1 to 1:5, and especially 3:1 to 1:3.

[0097] Examples of monomer M2 include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropionic acid, 2-propylpropionic acid, itaconic acid, and fumaric acid. Monocarboxylic acids are preferred. Acrylic acid, methacrylic acid, and mixtures thereof are particularly preferred.

[0098] Particularly preferred is that the monomer M2 is selected from methacrylic acid or a mixture of acrylic acid and methacrylic acid.

[0099] Examples of single-unit M3 include, but are not limited to:

[0100] - Primary amides (monomer M3.1) of mono-olefinic unsaturated monocarboxylic acids having 3 to 8 carbon atoms, such as acrylamide and methacrylamide;

[0101] -N-C1-C monoalkenyl unsaturated monocarboxylic acids with 3 to 6 carbon atoms 10 Alkylamides (monomer M3.2), especially N-C1-C of acrylic acid or methacrylic acid. 10 Alkylamides, such as N-methacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, and N-butylmethacrylamide;

[0102] - Monoolefinic unsaturated monomers with urea and ketone groups (monomer M3.3), such as 2-(2-oxo-imidazolidine-1-yl)ethyl (meth)acrylate, 2-ureoyl (meth)acrylate, N-[2-(2-oxooxazolidine-3-yl)ethyl]methacrylate, acetylacetoxyethyl acrylate, acetylacetoxypropyl methacrylate, acetylacetoxybutyl methacrylate, 2-(acetylacetoxy)ethyl methacrylate, diacetone acrylamide (DAAM), and diacetone methacrylamide;

[0103] - Hydroxyalkyl esters of monoolefinically unsaturated C3-C6 monocarboxylic acids (monomers M3 and M4), especially hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid (also known as (meth)acrylate hydroxyalkyl esters), particularly hydroxy-C2-C4-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.

[0104] - A mono-olefinic unsaturated monomer (monomer M3.5) having at least one tri-C1-C4-alkoxysilyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane, and mixtures thereof. The amount of said monomer M3.5 is typically from 0.01 to 1 pphm.

[0105] Monomer M3 may also contain a small amount of a polyene-bonded unsaturated monomer (monomer M3.6), i.e., a monomer having at least two non-conjugated olefinic unsaturated double bonds. The amount of monomer M3.6 typically does not exceed 1 pphm. Examples of suitable monomer M3.6 include:

[0106] - Diesters of monoene-bonded unsaturated C3-C6 monocarboxylic acids with saturated aliphatic or alicyclic diols, especially diesters of acrylic acid or methacrylic acid, such as diacrylates of ethylene glycol (1,2-ethylene glycol), 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 and dimethacrylic acid;

[0107] - Monoesters of monoene-unsaturated C3-C6 monocarboxylic acids and monoene-unsaturated aliphatic or alicyclic monohydroxy compounds, such as acrylates and methacrylates of vinyl alcohols (vinyl alcohol), allyl alcohols (2-propen-1-ol), 2-cyclohexen-1-ol, or norbornenol, and

[0108] -Divinyl aromatic compounds, such as 1,3-divinylbenzene, 1,4-divinylbenzene and mixtures thereof.

[0109] In a particular embodiment of the invention, the monomer M does not contain monomer M3.6 or monomer M3.6 in amounts not exceeding 0.1 pphm.

[0110] In monomer M3, hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid are preferred, especially hydroxy-C2-C4-alkyl esters of acrylic acid and hydroxy-C2-C4-alkyl esters of methacrylic acid, acrylamide, methacrylamide and mixtures thereof.

[0111] Preferably, the carboxylated polymer can be obtained by polymerization of monomer component M, wherein the monomer component M is substantially composed of the following:

[0112] a) 70 to 99.95% by weight, particularly 80 to 99.9% by weight, especially 90 to 99.8% by weight, of one or more mono-olefinic unsaturated monomers M1 as defined herein, based on the total weight of monomers in monomer component M.

[0113] b) 0.05 to 10 wt%, particularly 0.1 to 8 wt%, particularly 0.2 to 5 wt%, of one or more mono-olefinic unsaturated monomers M2 as defined herein, based on the total weight of monomers in monomeric component M.

[0114] c) 0 to 20% by weight, particularly 0 to 10% by weight, especially 0 to 5% by weight, of one or more nonionic monomers M3 as defined herein (which differs from monomer M1), based on the total weight of monomers in monomer component M.

[0115] The carboxylated polymer can be obtained, in particular, by polymerization of monomer component M, wherein monomer component M comprises the following:

[0116] a) One or more olefinically unsaturated monomers M1, selected from:

[0117] - At least one monomer M1a, selected from C1-C of acrylic acid 20 -C5-C of alkyl esters and methacrylic acid 20 -alkyl esters; and

[0118] - At least one monomer M1b, selected from vinyl aromatic monomers and C1-C4-alkyl esters of methacrylic acid and mixtures thereof.

[0119] b) One or more mono-ene unsaturated monomers M2, selected from mono-ene unsaturated monocarboxylic acids having 3 to 6 carbon atoms and mono-ene unsaturated dicarboxylic acids having 4 to 6 carbon atoms.

[0120] c) Optionally, one or more nonionic monomers M3, which are different from monomer M1.

[0121] In a preferred embodiment, the film-forming carboxylated polymer can be obtained by polymerization of monomer component M, wherein said monomer component M is substantially composed of the following:

[0122] a) 70 to 99.95% by weight, particularly 80 to 99.9% by weight, especially 90 to 99.8% by weight, of one or more mono-olefinic unsaturated monomers M1, based on the total weight of monomers in monomer component M, wherein said monomer M1 is selected from:

[0123] - At least one monomer M1a, selected from C1-C acrylic acid 20 -C5-C of alkyl esters and methacrylic acid 20 -alkyl esters; and

[0124] - At least one monomer M1b, selected from vinyl aromatic monomers and C1-C4-alkyl esters of methacrylic acid and mixtures thereof.

[0125] b) 0.05 to 10 wt%, particularly 0.1 to 8 wt%, particularly 0.2 to 5 wt%, of one or more mono-olefinic unsaturated monomers M2 as defined herein, based on the total weight of monomers in monomeric component M.

[0126] c) 0 to 20% by weight, particularly 0 to 10% by weight, especially 0 to 5% by weight, of one or more nonionic monomers M3 as defined herein (which differs from monomer M1), based on the total weight of monomers in monomer component M.

[0127] In aqueous carboxylated polymer latexes, the polymer is dispersed in the form of polymer particles. The average particle size is typically 50 to 500 nm, particularly 60 to 400 nm, and especially 80 to 300 nm. The average particle size referred to herein is the Z-mean particle size determined by photon correlation spectroscopy (PCS) (also known as quasi-elastic light scattering (QELS) or dynamic light scattering (DLS)). The measurement method is described in ISO 13321:1996. It can be determined using an HPPS (High Performance Particle Size Analyzer). For this purpose, a sample of the aqueous polymer latex is diluted and the dilution is analyzed. In the case of DLS, depending on the particle size, the aqueous dilution can have a polymer concentration of 0.001 to 0.5% by weight. For most purposes, a suitable concentration would be 0.01% by weight. However, higher or lower concentrations can be used to obtain the 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 performed using an aqueous solution of 0.1 wt% nonionic emulsifier (such as ethoxylated C16 / C18 alkanols (degree of ethoxylation 18)) as the diluent. Measurement setup: HPPS from Malvern, automated, with continuous flow cuvettes and a Gilson autosampler. Parameters: Measurement temperature 20.0 °C; Measurement time 120 s (6 cycles every 20 s); Scattering angle 173°; Laser wavelength 633 nm (HeNe); Refractive index of the medium 1.332 (aqueous solution); Viscosity 0.9546 mPa·s. This measurement yields the average value (fitted average value) of the second-order cumulant analysis, i.e., the Z-mean value. The "fitted average value" is the intensity-weighted average hydrodynamic particle size in nm.

[0128] Preferably, the polymer in the polymer dispersion has a narrow particle size distribution. This particle size distribution is characterized by a polydispersity index (PDI), a dimensionless number calculated from relevant data obtained from a simple two-parameter fitted cumulative analysis. It is typically calculated according to the description in ISO 13321:1996. Typically, the PDI is less than 0.2.

[0129] The latex of the carboxylated polymer can typically be obtained by aqueous free radical emulsion polymerization of monomer M that forms the carboxylated monomer latex, particularly by free radical aqueous emulsion polymerization, using known methods similar to free radical emulsion polymerization. The conditions required for the free radical emulsion polymerization of monomer M are sufficiently familiar to those skilled in the art, for example, from the prior art cited at the beginning and from “Emulsion polymerization” in the Encyclopedia of Polymer Science and Engineering, Volume 8, page 659 and later (1987); DC. Blackley, High Polymer Latices, Volume 1, page 35 and later (1966); H. Warson, The Application of Synthetic Resin Emulsions, Chapter 5, page 246 and later (1972); D. Diederich, Chemie in unserer Zeit 24, pages 135-142 (1990); Emulsion Polymerisation, Interscience Publishers, New York (1965); DE-A-40 03 422 and Dispersionen synthetischer Hochpolymerer [Dispersions of Synthetic High Polymers], F. Springer-Verlag, Berlin (1969).

[0130] Free radical-initiated aqueous emulsion polymerization is initiated by free radical polymerization initiators (free radical initiators). These can, in principle, be peroxides or azo compounds. Redox initiator systems are also useful. In principle, the peroxides used can be inorganic peroxides, such as hydrogen peroxide or persulfate, such as monoalkali metal salts or dialkali metal salts or ammonium salts of persulfate, such as monosodium and disodium salts, monopotassium or dipotassium salts or ammonium salts; or organic peroxides, such as alkyl hydrogen peroxide, such as tert-butyl hydrogen peroxide, p-menthyl hydrogen peroxide or cumyl hydrogen peroxide, and dialkyl peroxides or diaryl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide. The azo compounds used are essentially 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and 2,2'-azobis(amidinylpropyl) dihydrochloride (AIBA, corresponding to Wako Chemicals' V-50). Suitable oxidants for redox initiator systems are essentially the peroxides specified above. Corresponding reducing agents that can be used are sulfur compounds with low oxidation states, such as alkali metal sulfites, for example, potassium sulfite and / or sodium sulfite; alkali metal bisulfites, for example, potassium bisulfite and / or sodium bisulfite; alkali metal metabisulfites, for example, potassium metabisulfite and / or sodium metabisulfite; formaldehyde bisulfite, for example, potassium formaldehyde bisulfite and / or sodium formaldehyde bisulfite; alkali metal salts, especially potassium and / or sodium salts of aliphatic sulfinic acids; and alkali metal sulfhydrides, for example, potassium hydrosulfide and / or sodium hydrosulfide; salts of polyvalent metals, for example, ferrous(II) sulfate, ferrous(II) ammonium sulfate, ferrous(II) phosphate; ethylene glycols, for example, dihydroxymaleic acid, benzoic acid, and / or ascorbic acid; and reducing sugars, for example, sorbitol, glucose, fructose, and / or dihydroxyacetone.

[0131] Preferred free radical initiators are inorganic peroxides, especially persulfates and redox initiator systems.

[0132] Typically, based on the total amount of monomer M, the amount of free radical initiator used is 0.01 to 5 pphm, preferably 0.1 to 3 pphm.

[0133] The amount of free radical initiator required for the emulsion polymerization M in the method of the present invention can be initially added entirely to the polymerization vessel. However, it is also possible to add no or only a portion of the free radical initiator, for example, no more than 30% by weight, especially no more than 20% by weight, based on the total amount of free radical initiator required in the aqueous polymerization medium, and then, under polymerization conditions, during the free radical emulsion polymerization of monomer M, add the entire amount or any remaining amount in batches or continuously at a constant or varying flow rate, depending on the consumption.

[0134] Preferably, the free radical emulsion polymerization of the monomers forming the carboxylated polymer latex is carried out by a so-called feed method, which means that at least 90%, particularly at least 95%, or all of the monomers to be polymerized are metered into the polymerization reaction under polymerization conditions within a metering time period P. The length of time period P can depend on the production equipment and can be, for example, from 20 minutes to 12 hours. Typically, the length of time period P will be from 0.5 hours to 5 hours, particularly from 1 hour to 4 hours.

[0135] The term "polymerization conditions" should generally be understood to refer to the temperatures and pressures at which free radical-initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. These conditions are particularly dependent on the free radical initiator used. Advantageously, the type and amount of free radical initiator, polymerization temperature, and polymerization pressure are chosen such that a sufficient amount of initiating free radicals is always present to initiate or sustain the polymerization reaction.

[0136] It may be appropriate to establish polymerization conditions and initially add at least a portion of the radical initiator into the polymerization vessel before starting metered addition of monomer M.

[0137] It has been found advantageous to carry out free radical emulsion polymerization in the presence of a seed latex. The seed latex is the polymer latex present in the aqueous polymerization medium prior to the metered addition of monomer M. The seed latex can help to better control the particle size or the final polymer latex obtained in the free radical emulsion polymerization of this invention.

[0138] In principle, any polymer latex can be used as a seed latex. For the purposes of this invention, a seed latex in which the polymer particles have a relatively small particle size is preferred. In particular, the Z-average particle size of the polymer particles of the seed latex, as determined by dynamic light scattering (see below) at 20°C, is preferably 10 to 80 nm, particularly 10 to 50 nm. Preferably, the polymer particles of the seed latex are made of olefinically unsaturated monomers comprising at least 95% by weight of one or more monomers M1a and / or M1b as defined above, based on the total weight of the monomers forming the seed latex. The polymer particles of the seed latex particularly comprise at least 95% by weight of at least one monomer M1b or a mixture of at least one monomer M1b and one or more monomers M1a, based on the total weight of the monomers forming the seed latex, wherein the weight ratio of monomer M1b to M1a is at least 50%.

[0139] Therefore, the seed latex is typically added to the polymerization vessel before the metered addition of monomer M begins. Specifically, the seed latex is added to the polymerization vessel, and polymerization conditions are subsequently established, for example, 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 metered addition of monomer M begins. However, it is also possible to meter the monomer and free radical polymerization initiator into the polymerization vessel in parallel.

[0140] On a solids basis, the amount of seed latex is typically 0.1 to 10% by weight, particularly 0.5 to 5% by weight, based on the total weight of the monomer M to be polymerized.

[0141] The free radical aqueous emulsion polymerization of the present invention can be carried out in a temperature range of 0 to 170°C. The temperatures used are typically 50 to 120°C, often 60 to 120°C, and frequently 70 to 110°C. The free radical aqueous emulsion polymerization of the present invention can be carried out at pressures less than, equal to, or greater than 1 atm (atmosphere), thus the polymerization temperature can exceed 100°C and can reach a maximum of 170°C. Monomer polymerization is typically carried out at ambient pressure, but can also be carried out under increased pressure. In this case, the pressure can be 1.2, 1.5, 2, 5, 10, 15 bar (absolute pressure) or even higher. If the emulsion polymerization is carried out under reduced pressure, a pressure of 950 mbar, often 900 mbar, and typically 850 mbar (absolute pressure) is established. Advantageously, the free radical aqueous emulsion polymerization of the present invention is carried out at ambient pressure (about 1 atm) with oxygen excluded, for example, in an inert gas atmosphere, such as nitrogen or argon.

[0142] The polymerization of monomer M can be carried out optionally in the presence of a chain transfer agent. A chain transfer agent should be understood as a compound that transfers free radicals and reduces molecular weight or controls chain growth during the polymerization reaction. Examples of chain transfer agents are aliphatic and / or aryliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, dichloromethane, dichloroethane, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide; and organic sulfur-containing compounds, such as primary, secondary, or tertiary aliphatic thiols, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 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 isomers, n-octanethiol and its isomers, n-nonanethiol and its isomers, n-decanethiol and its isomers, n-undecanethiol and its isomers, n-dodecanethiol and its isomers, n-tridecanethiol and its isomers; substituted thiols, such as 2-hydroxyethylthiol; aromatic thiols, such as benzenethiol, o-methylbenzenethiol, m-methylbenzenethiol or p-methylbenzenethiol; alkyl esters of mercaptoacetic acid (mercaptoacetic acid), such as 2-ethylhexyl mercaptoacetate; alkyl esters of mercaptopropionic acid, such as octyl mercaptopropionate; and in Polymer Other sulfur compounds described in Handbook, 3rd Edition, 1989, J. Brandrup and E. Himmergut, John Wiley & Sons, Chapter II, pages 133-141; and aliphatic aldehydes and / or aromatic aldehydes, such as acetaldehyde, propionaldehyde, and / or benzaldehyde; unsaturated fatty acids, such as oleic acid; dienes having non-conjugated double bonds, such as divinylmethane or vinylcyclohexane; or hydrocarbons having readily abstracted hydrogen atoms, such as toluene. Alternatively, a mixture of the aforementioned chain transfer agents that do not interfere with each other may be used. Based on the total amount of monomer M, the total amount of chain transfer agent optionally used in the method of the present invention will generally not exceed 1% by weight. However, at some point in the polymerization reaction, the amount of chain transfer agent added to the polymerization reaction may exceed 1% by weight, based on the total amount of monomer already added to the polymerization reaction.

[0143] The free radical emulsion polymerization of the present invention is typically carried out in an aqueous polymerization medium, which, in addition to water, contains at least one surfactant for stabilizing the monomer emulsion and polymer particles of the polymer latex.

[0144] Surfactants can be selected from emulsifiers and protective colloids. In contrast to emulsifiers, protective colloids should be understood as polymers with a molecular weight greater than 2000 Daltons, while emulsifiers typically have a lower molecular weight. Surfactants can be anionic, nonionic, or a mixture of nonionic and anionic surfactants.

[0145] Anionic surfactants typically have at least one anionic group, selected from phosphate, phosphonate, sulfate, and sulfonate groups. Anionic surfactants with at least one anionic group are usually used in the form of their alkali metal salts, particularly sodium or ammonium salts.

[0146] Preferred anionic surfactants are anionic emulsifiers, particularly those with at least one sulfate or sulfonate group. Similarly, anionic emulsifiers with at least one phosphate or phosphonate group can be used alone or in combination with one or more anionic emulsifiers with at least one sulfate or sulfonate group.

[0147] Examples of anionic emulsifiers having at least one sulfate or sulfonate group are, for example...

[0148] -Salts of alkyl sulfates, especially C8-C 22 -Salts of alkyl sulfates, especially alkali metal salts and ammonium salts

[0149] - Salts of sulfated monoesters of ethoxylated alkanols, especially ethoxylated C8-C 22 Salts of sulfate monoesters of alkanols (preferably with an ethoxylation degree (EO content) of 2 to 40), especially alkali metal salts and ammonium salts.

[0150] - Salts of sulfated monoesters of ethoxylated alkylphenols, especially ethoxylated C4-C 18 Salts of sulfate monoesters of alkylphenols (preferably with an EO content of 3 to 40%), especially alkali metal salts and ammonium salts.

[0151] Salts of alkyl sulfonic acids, especially C8-C 22 Salts of alkyl sulfonic acids, especially alkali metal salts and ammonium salts.

[0152] -Dialkyl ester salts of sulfosuccinic acid, especially the di-C4-C salts of sulfosuccinic acid 18 Salts of alkyl esters, especially alkali metal salts and ammonium salts.

[0153] -Salts of alkylbenzene sulfonic acids, especially C4-C 22 Salts of alkylbenzene sulfonic acids, especially alkali metal salts and ammonium salts, and

[0154] - Salts of mono- or disulfonated alkyl-substituted diphenyl ethers, especially alkali metal and ammonium salts, for example, those with C4-C on one or both aromatic rings. 24 -Alkyl bis(benzenesulfonic acid) ether salts. The latter is common knowledge, for example in US-A-4,269,749, and is commercially available, for example... 2A1 (Dow Chemical Company).

[0155] A mixture of the above salts is also suitable.

[0156] The preferred anionic surfactant is an anionic emulsifier, selected from:

[0157] -Salts of alkyl sulfates, especially C8-C 22 -Salts of alkyl sulfates, especially alkali metal salts and ammonium salts

[0158] - Salts of sulfated monoesters of ethoxylated alkanols, especially ethoxylated C8-C 22 Salts of sulfate monoesters of alkanols (preferably with an ethoxylation degree (EO content) of 2 to 40), especially alkali metal salts and ammonium salts.

[0159] - Salts of sulfated monoesters of ethoxylated alkylphenols, especially ethoxylated C4-C 18 Salts of sulfate monoesters of alkylphenols (preferably with an EO content of 3 to 40%), especially alkali metal salts and ammonium salts.

[0160] -Salts of alkylbenzene sulfonic acids, especially C4-C 22 Salts of alkylbenzene sulfonic acids, especially alkali metal salts and ammonium salts, and

[0161] - Salts of mono- or disulfonated alkyl-substituted diphenyl ethers, especially alkali metal and ammonium salts, for example, those with C4-C on one or both aromatic rings. 24 Salts of alkyl bis(benzenesulfonic acid) ethers.

[0162] Examples of anionic emulsifiers containing phosphate or phosphonate groups include, but are not limited to, salts selected from the following:

[0163] - Salts of monoalkyl and dialkyl phosphates, especially C8-C 22 Salts of alkyl phosphates, especially alkali metal salts and ammonium salts.

[0164] Salts of phosphate monoesters of -C2-C3-alkoxylated alkanols (preferably with an alkoxylation degree of 2 to 40, especially 3 to 30), particularly alkali metal salts and ammonium salts, wherein the phosphate monoester is, for example, an ethoxylated C8-C3-alkoxylated alkanol. 22 - Alkyl alcohol (preferably with an ethoxylation degree (EO content) of 2 to 40) phosphate monoesters, propoxylated C8-C22 - Alkyl alcohol (preferably propoxylation degree (PO content) of 2 to 40) phosphate monoesters and ethoxylated-copolymerized-propoxylated C8-C 22 - Phosphate monoesters of alkanols (preferably with an ethoxylation degree (EO content) of 1 to 20 and a propoxylation degree of 1 to 20),

[0165] - Salts of ethoxylated alkylphenol phosphate monoesters, especially ethoxylated C4-C 18 Salts of alkylphenol (EO content preferably 3 to 40%) phosphate monoesters, especially alkali metal salts and ammonium salts.

[0166] -Salts of alkylphosphonic acids, especially C8-C 22 Salts of alkylphosphonic acids, especially alkali metal salts and ammonium salts, and

[0167] -Salts of alkylphenylphosphonic acids, especially C4-C 22 Salts of alkylphenylphosphonic acids, especially alkali metal salts and ammonium salts.

[0168] Other suitable anionic surfactants can be found in Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 1, Macromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.

[0169] Preferably, the surfactant comprises at least one anionic emulsifier having at least one sulfate or sulfonate group. The at least one anionic emulsifier having at least one sulfate or sulfonate group can be the only type of anionic emulsifier. However, a mixture of at least one anionic emulsifier having at least one sulfate or sulfonate group and at least one anionic emulsifier having at least one phosphate or phosphonate group can also be used. In such a mixture, the amount of the at least one anionic emulsifier having at least one sulfate or sulfonate group is preferably at least 50% by weight, based on the total weight of the anionic surfactant used in the method of the present invention. In particular, the amount of the anionic emulsifier having at least one phosphate or phosphonate group does not exceed 20% by weight, based on the total weight of the anionic surfactant used in the method of the present invention.

[0170] In addition to the anionic surfactants mentioned above, surfactants may also contain one or more nonionic surfactants, particularly selected from nonionic emulsifiers. Suitable nonionic emulsifiers are, for example, aryl or aliphatic nonionic emulsifiers, such as ethoxylated monoalkylphenols, dialkylphenols, and trialkylphenols (EO content: 3 to 50, alkyl group: C4-C). 10 ), ethoxylated long-chain alcohols (EO content: 3 to 100, alkyl: C8-C) 36 ), and poly(ethylene oxide) / poly(propylene oxide) homopolymers and copolymers. These may contain epoxy alkyl units copolymerized in a random or block form. A very suitable example is an EO / PO block copolymer. Ethoxylated long-chain alkanols are preferred, especially those with alkyl groups C8-C. 30 Those with an average degree of ethoxylation of 5 to 100, of which those having a straight-chain C are particularly preferred. 12 -C 20 Alkyl groups with an average degree of ethoxylation of 10 to 50, and particularly preferred are ethoxylated monoalkylphenols.

[0171] In one specific embodiment of the invention, the surfactant used in the method of the invention comprises less than 20% by weight, particularly not more than 10% by weight, of a nonionic surfactant, based on the total amount of surfactant used in the method of the invention, and particularly does not contain any nonionic surfactant. In another embodiment of the invention, the surfactant used in the method of the invention comprises at least one anionic surfactant and at least one nonionic surfactant, the ratio of the anionic surfactant to the nonionic surfactant typically being from 0.5:1 to 10:1, particularly from 1:1 to 5:1.

[0172] Preferably, the amount of surfactant should be in the range of 0.2 to 5% by weight, particularly in the range of 0.5 to 3% by weight, based on the monomer M to be polymerized.

[0173] The aqueous reaction medium in polymerization may, in principle, contain a small amount (usually up to 5% by weight) of a water-soluble organic solvent, such as methanol, ethanol, isopropanol, butanol, pentanol, and acetone. However, preferably, the method of the present invention is carried out in the absence of such solvents.

[0174] It is generally advantageous to post-process the aqueous polymer dispersion obtained upon completion of polymerization of monomer M to reduce the residual monomer content. This post-processing can be carried out chemically, for example by using a more efficient free radical initiator system to complete the polymerization reaction (referred to as post-polymerization), and / or physically, for example by stripping the aqueous polymer dispersion with steam or an inert gas. Relevant chemical and physical methods are well known to those skilled in the art, see, for example, EP-A771328, 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 advantage of combining chemical and physical post-treatment is that it can remove not only unconverted olefinic unsaturated monomers from aqueous polymer dispersions, but also other damaging volatile organic compounds (VOCs).

[0175] Carboxylated polymer latexes can be obtained, for example, through single- or multi-stage emulsion polymerization of monomer component M, particularly aqueous free radical emulsion polymerization. In the case of aqueous emulsion polymerization, the term "multi-stage" should be understood as meaning that the relative concentration of monomers in monomer component M added to the polymerization reaction is changed at least once during the aqueous emulsion polymerization process. This process results in the production of at least two polymer groups with different monomer compositions in the polymer particles of the latex. For example, the monomer composition can be changed so that the multi-stage latex polymers are characterized by having different glass transition temperatures or glass transition temperatures (T0). g Gradient. The monomer composition can also be changed to give the multi-level latex polymer such characteristics that its groups have different concentrations of the polymerizable acidic monomer (e.g., monomer M2) or monomer M2 with a concentration gradient.

[0176] During the addition of monomer M, the type and / or relative amount of monomer can be changed continuously or gradually. However, the type and relative amount of monomer M added to the polymerization reaction can also remain constant. For example, the ratio of monomers M1 and M2 can be increased or decreased during the addition process.

[0177] Preferably, the aqueous polymer latex of the carboxylated polymer is prepared by free radical aqueous emulsion polymerization via a so-called feed method, wherein during the feeding process of monomer component M, at least 90% of the monomer component M to be polymerized is metered into the polymerization reaction under polymerization conditions during the metering time period P, and wherein the composition of a portion of the monomer component M metered into the polymerization reaction under polymerization conditions is changed at least once during the metering time period P.

[0178] In one particular embodiment, for one or more finite time periods P(n), the level of monomer M2 (i.e., the relative amount of monomer M2 by weight to monomer component M) fed into the monomer component M in the polymerization reaction is increased to a higher level. After each of the said time periods P(n), the relative amount of monomer M2 will decrease. During each time period P(n), the relative amount of monomer M2 to the total amount of monomer fed during that time period is at least 0.5 pphm higher, particularly at least 1.0 pphm higher, than the level outside that time period. Specifically, the level of monomer M2 fed during time period P(n) is 0.5 to 80 pphm higher, particularly 1.0 to 50 pphm higher, than the average level of monomer M2 fed outside time period P(n).

[0179] Throughout this specification and particularly in this embodiment, the term pphm (parts per hundred monomers) is used as a synonym for the relative amount (in weight percent) of a monomer to the total amount of monomer component M. For example, x pphm monomer M2 means x weight percent of monomer M2, based on the total amount of monomers in monomer component M. An increase of y pphm means that the relative amount of a specific monomer increases by y weight percent, based on the total weight of monomers in monomer component M.

[0180] In this particular implementation, there may be a single time period P(n) during which the weight level of monomer M2 increases. However, there may also be more than one time period P(n). There is no particular limit to the total number of time periods P(n) and it can be as high as 20 or even higher. For practical reasons, the total number of time periods P(n) is usually not more than 10, specifically 1 to 6.

[0181] In this particular embodiment, the level of monomer M2 in the monomer component M fed outside of time period P(n) (i.e., the level of monomer M2 before and after each time period P(n)) may be the same or may vary slightly. The variation in the level of monomer M2 outside of time period P(n) will generally not exceed 1 pphm, particularly not more than 0.5 pphm. The values ​​given herein refer to the average value during time period P(n) and the average value outside of time period P(n). Preferably, the level of monomer M2 in time period P(n) will be from 1.5 to 85 pphm, particularly from 2 to 50 pphm.

[0182] In this particular embodiment, one or more time periods P(n) during which the level of acidic monomer M2 increases may be entirely within said time period P or at the end of said time period P. Importantly, in this particular embodiment, the first time period P(n) is not initiated until at least 5% of monomer M, particularly at least 10% of monomer M for emulsion polymerization, is metered into the polymerization reaction.

[0183] During the one or more time periods P(n), the weight ratio of the total amount of acidic monomer M2 to other monomers M1+M3 in the monomer components metered for addition to the polymerization reaction is generally at least 0.02:1, and particularly at least 0.03:1. Prior to each of the one or more time periods P(n), the weight ratio of the total amount of acidic monomer M2 to other monomers M1+M3 should be less than 0.03:1, and particularly less than 0.02:1. Similarly, at the end of each time period P(n), the weight ratio of the total amount of acidic monomer M2 to other monomers M1+M3 should be reduced to less than 0.03:1, and particularly less than 0.02:1.

[0184] Preferably, the level of monomer M2 in the monomer component and the weight ratio of the total amount of acidic monomer M2 to other monomers M1+M3 in the monomer component M fed to the polymerization reaction can be controlled by well-known methods. For example, monomer M can be metered into the polymerization reaction using a single feed line. The ratio of the total amount of acidic monomer M2 to other monomers M1+M3 can be increased by increasing the concentration of monomer M2 in the single feed line of monomer M, or by decreasing the total concentration of monomers M1+M3, or by using both measures simultaneously. A portion of monomer M2, such as at least 20%, particularly at least 30%, such as 20 to 100% or 30 to 100% of monomer M2 contained in the monomer component M, can be metered into the polymerization reaction through a separate feed line into the polymerization reaction.

[0185] Clearly, the length of all time periods P(n) is shorter than the length of time period P required to add the full amount of monomer M to the polymerization reaction. Typically, the total length of all time periods P(n) does not exceed 50% of the length of time period P, particularly 40%, and especially 30%. Typically, the total length of all time periods P(n) is at least 0.2% of the length of time period P, particularly at least 0.5%, and especially at least 1%. Specifically, the ratio of the total length of all time periods P(n) to the length of time period P is 0.002:1 to 0.5:1, particularly 0.005:1 to 0.30:1. Typically, the total length of all time periods P(n) is from 30 seconds to 60 minutes. The length of a single time period P(n) is less important and can be a few seconds, for example 10 seconds, and up to 60 minutes or longer. The length of time period P can depend on the production equipment and can be, for example, from 20 minutes to 12 hours. Typically, it is from 0.5 hours to 5 hours, especially 1 hour to 4 hours.

[0186] In this particular embodiment, the entire amount of monomer M2 contained in monomer component M may be added to the polymerization reaction during at least one time period P(n), i.e., during all time periods P(n). However, it is not necessary to add the entire amount of monomer M2 during at least one time period P(n). Instead, it is preferable that the monomer component metered into the polymerization reaction also contains one or more monomers M2 outside of time period P(n). Typically, at least 20% of monomer M2 contained in monomer component M, and particularly at least 30% of monomer M2 contained in monomer component M, is metered into the polymerization reaction during at least one time period P(n).

[0187] The concentration of polymer latex contained in the aqueous adhesive composition is typically 10 to 70% by weight, particularly 30 to 65% by weight, especially 40 to 65% by weight, based on the total weight of the adhesive composition.

[0188] Aqueous adhesive compositions typically consist of an aqueous polymer latex of the film-forming carboxylated polymer described herein, a branched polyetheramine polyol described herein, and water. However, aqueous adhesive compositions optionally include other components, such as dispersants, biocides, and defoamers.

[0189] The present invention also relates to waterborne coating compositions comprising waterborne adhesive compositions as defined herein.

[0190] Preferred embodiments of the waterborne adhesive composition included in the waterborne coating composition are those described above.

[0191] In addition to the binder composition, the coating composition preferably also contains at least one pigment and / or at least one filler. However, coating compositions that do not contain pigments or fillers are also part of this invention.

[0192] According to the definition in German standard DIN 55944, the pigment used for the purposes of this invention is a nearly insoluble, finely dispersed organic or preferably inorganic pigment. Preferably, the composition comprises at least one inorganic pigment. Representative examples of organic pigments are:

[0193] - Monoazo pigments, such as CI pigment brown 25; CI pigment orange 5, 13, 36 and 67; CI pigment red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1, 63, 112, 146, 170, 184, 210, 245 and 251; CI pigment yellow 1, 3, 73, 74, 65, 97, 151 and 183;

[0194] -Diazo pigments, such as CI pigments Orange 16, 34 and 44; CI pigments Red 144, 166, 214 and 242; CI pigments Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;

[0195] - Anthraquinone pigments, such as CI Pigment Red 168 (CI Reduced Orange 3);

[0196] - Anthraquinone pigments, such as CI pigments yellow 147 and 177; CI pigment violet 31;

[0197] - Anthraquinone pigments, such as CI pigments yellow 147 and 177; CI pigment violet 31;

[0198] - Anthraquinone pyrimidine pigments, such as CI Pigment Yellow 108 (CI Vat Yellow 20);

[0199] - Quinacridone pigments, such as CI pigments Red 122, 202 and 206; CI pigment Violet 19;

[0200] - Quinoline ketone pigments, such as CI Pigment Yellow 138;

[0201] - Dioxazine pigments, such as CI pigments Violet 23 and 37;

[0202] - Yellow anthrone pigments, such as CI Pigment Yellow 24 (CI Vat Yellow 1);

[0203] -Indoanthraquinone pigments, such as CI Pigment Blue 60 (CI Reduced Blue 4) and 64 (CI Reduced Blue 6);

[0204] -Isoindoline pigments, such as CI pigment orange 69; CI pigment red 260; CI pigment yellow 139 and 185;

[0205] -Isoindolinone pigments, such as CI pigment orange 61; CI pigment red 257 and 260; CI pigment yellow 109, 110, 173 and 185;

[0206] -Isoanthrone violet pigments, such as CI Pigment Violet 31 (CI Reduced Violet 1);

[0207] - Metal complex pigments, such as CI pigments Yellow 117, 150 and 153; CI pigment Green 8;

[0208] - Perinone pigments, such as CI pigment Orange 43 (CI Vat Orange 7); CI pigment Red 194 (CI Vat Red 15);

[0209] - Dinaphthalene-based pigments, such as CI pigments Black 31 and 32; CI pigments Red 123, 149, 178, 179 (CI Reduce Red 23), 190 (CI Reduce Red 29) and 224; CI pigment Violet 29;

[0210] - Phthalocyanine pigments, such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16; CI Pigment Green 7 and 36;

[0211] - Piperanthonone pigments, such as CI Pigment Orange 51; CI Pigment Red 216 (CI Reduced Orange 4);

[0212] - Indigo pigments, such as CI pigments Red 88 and 181 (CI Vat Red 1); CI pigment Violet 38 (CI Vat Violet 3);

[0213] - Triarylcarbonium pigments, such as CI pigments Blue 1, 61 and 62; CI pigment Green 1; CI pigments Red 81, 81:1 and 169; CI pigments Violet 1, 2, 3 and 27; CI pigment Black 1 (aniline black);

[0214] -CI Pigment Yellow 101 (Aldehyde Yellow) and CI Pigment Brown 22.

[0215] Specific examples of preferred organic pigments are CI pigment yellow 138, CI pigment red 122, CI pigment purple 19, CI pigment blue 15:3 and 15:4, CI pigment black 7, CI pigment orange 5, 38 and 43 and CI pigment green 7.

[0216] Inorganic pigments are preferred, such as

[0217] - White pigments such as titanium dioxide (CI pigment white 6), zinc white, pigment-grade zinc oxide; zinc sulfide, zinc barium white; lead white; and white fillers such as barium sulfate and CaCO3, which are also referred to as inorganic white pigments in the context of this invention.

[0218] - Black pigments, such as iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27), and carbon black (CI Pigment Black 7);

[0219] - Colored pigments such as chromium oxide, hydrated chromium oxide green; chrome green (CI pigment green 48); cobalt green (CI pigment green 50); ultramarine green; cobalt blue (CI pigment blue 28 and 36); ultramarine blue, iron blue (CI pigment blue 27), manganese blue, ultramarine violet, cobalt violet, manganese violet, iron oxide red (CI pigment red 101); cadmium sulfide selenide (CI pigment red 108); molybdenum chrome red (CI pigment red 104); ultramarine red,

[0220] - Iron oxide brown, mixed brown, spinel phase and corundum phase (CI pigment brown 24, 29 and 31), chrome orange;

[0221] - Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); Chromium titanium yellow; Cadmium sulfide and zinc cadmium sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), Zinc yellow, Alkaline earth metal chromates; Napo yellow; Bismuth vanadate (CI Pigment Yellow 184);

[0222] - Interference pigments, such as metallic effect pigments based on coated metal sheets, pearlescent pigments based on mica sheets coated with metal oxides, and liquid crystal pigments.

[0223] Preferred inorganic pigments are selected from inorganic yellow pigments and inorganic white pigments, especially titanium dioxide, barium sulfate and CaCO3.

[0224] The composition may also contain a mixture of two or more different pigments, in which case at least one pigment is preferably inorganic. The pigments are typically in particulate form, i.e., in granular form. The pigments may be selected from coarse pigments, i.e., untreated pigments such as those in their synthetic state. The pigment particles may be regular or irregular in shape; for example, the particles may have a spherical or substantially spherical shape or a needle-like shape (needle-shaped).

[0225] In one embodiment of the invention, the pigment is spherical or substantially spherical in shape, i.e., the ratio of the longest diameter to the smallest diameter is 1.0 to 2.0, preferably up to 1.5.

[0226] In one embodiment of the invention, the pigment has an average particle size (median, d50) of 20 nm to 50 μm, preferably 50 nm to 20 μm, more preferably a maximum of 5 μm, as determined, for example, by a Coulter counter or a Hegman measuring instrument.

[0227] Examples of suitable fillers include aluminosilicates, such as feldspar; silicates, such as kaolin, talc, mica, magnesite; alkaline earth metal carbonates, such as calcium carbonate in the form of calcite or chalk, magnesium carbonate, dolomite; and alkaline earth metal sulfates, such as calcium sulfate, silica, etc. Finely crushed fillers are preferred in the coating compositions of the present invention. Fillers can be used as individual components. However, filler mixtures have been found particularly useful in practice, such as calcium carbonate / kaolin or calcium carbonate / talc. Gloss paints typically contain only small amounts of very finely crushed fillers, or none at all. Fillers also include matting agents, which can significantly impair the desired gloss level. Matting agents are typically transparent and can be organic or inorganic. Examples of matting agents are inorganic silicates, such as those from WRGrace & Company. Brands and products from Evonik GmbH Brand. Organic matting agents can be, for example, branded. and brand Acquired by BYK-Chemie GmbH and under the brand Deuteron Acquired by Deuteron GmbH.

[0228] The proportion of pigments and fillers in a coating composition can be described in a manner known per se by pigment volume concentration (PVC). PVC describes the ratio of the volume of pigment (VP) and filler (VF) to the total volume, which consists of the volumes (in percentage) of binder (VB), pigment (VP), and filler (VF) in the dried coating film: PVC = (VP + VF) x 100 / (VP + VF + VB).

[0229] The pigment volume concentration (PVC) of the composition is typically at least 5, especially at least 10. Preferably, the PVC value will not exceed 60, especially not exceed 40, and specifically is 5 to 60 or 5 to 40. However, the inventive effect of the polymer dispersion is also evident in varnishes, which typically have a pigment / filler content of less than 5% by weight based on the varnish, and correspondingly have a PVC of less than 5.

[0230] The waterborne coating composition of the present invention may also contain conventional additives. These conventional additives will depend on the type of coating in a well-known manner, and include, but are not limited to:

[0231] - Rheology modifiers,

[0232] - Wetting agents or dispersants

[0233] -Film-forming aids

[0234] - Leveling agent,

[0235] -Biocides, and

[0236] - Defoamer.

[0237] Suitable rheology modifiers include associative thickener polymers and non-associative rheology modifiers. Suitable associative thickener polymers include anionic associative thickeners, such as hydrophobically modified acrylate thickeners, also known as HASE thickeners; nonionic associative thickeners (also known as NiSAT-type associative thickeners) include hydrophobically modified polyethylene oxide polyurethane rheology modifiers (also known as HEUR or PUR thickeners), and hydrophobically modified polyethylene oxide (also known as HMPE). Suitable non-associative rheology modifiers are particularly cellulose-based thickeners, especially hydroxyethyl cellulose, and also acrylate emulsion (ASE)-based thickeners. Non-associative cellulose-based thickeners are preferred. The amount of thickener polymer will depend on the desired viscosity distribution, and the amount of thickener polymer is typically 0.05 to 2.5% by weight, particularly 0.1 to 2% by weight, especially 0.15 to 1.5% by weight, based on latex paint.

[0238] Suitable wetting or dispersing agents include, for example, sodium polyphosphate, potassium polyphosphate or ammonium polyphosphate, alkali metal salts and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers, polyphosphonates such as sodium 1-hydroxyethane-1,1-diphosphonate, and naphthalene sulfonates, especially their sodium salts.

[0239] Suitable film-forming aids are solvents and plasticizers. In contrast to solvents, plasticizers have low volatility and preferably have a boiling point above 250°C at 1013 mbar, while solvents have higher volatility than plasticizers and preferably have a boiling point below 250°C at 1013 mbar. Suitable film-forming aids include, for example, petroleum solvents, pine oil, propylene glycol, ethylene glycol, butanediol, butylene acetate, butylene diacetate, butyl diethylene glycol, butyl carbitol, 1-methoxy-2-propanol, and 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate. And glycol ethers and esters, for example, can be trade names and Purchased from BASF SE, under the product name Purchased from Dow. The amount of film-forming aid is preferably <10% by weight, more preferably <5% by weight, based on the entire formulation. The formulation may also be completely solvent-free.

[0240] Other formulation components used in water-based paints are detailed 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).

[0241] Another embodiment of the present invention is a method for forming a coating on a surface, comprising:

[0242] (a) Applying the aqueous adhesive composition and / or the coating composition described herein to a surface, and

[0243] (b) Dry the composition to produce a coating.

[0244] The composition can be applied to the surface and / or substrate to be coated in a conventional manner, such as by applying paint with a brush or roller, spraying, dipping, rolling, or stick coating. The coating of the surface and / or substrate is performed in such a manner that the surface and / or substrate are first coated with the composition of the present invention, followed by a drying step of the aqueous composition.

[0245] The composition can be applied to surfaces such as metals, asphalt, concrete, fiberboard, stone, ceramics, minerals, wood, plastics, polymers, and glass. It can be applied to interior or exterior surfaces, such as architectural surfaces like roofs, walls, floors, and ceilings. Preferably, the composition can be applied to exterior surfaces.

[0246] Another embodiment of the present invention is the use of the branched polyetheramine polyol described herein as an additive for aqueous polymer latexes used in film-forming carboxylated polymers, wherein substantially all amino groups in the branched polyetheramine polyol are tertiary amine groups.

[0247] The branched polyetheramine polyols described in this article have excellent effects on the curing and / or hardening properties of polymer adhesives (such as film-forming carboxylated polymers).

[0248] Specifically, the branched polyetheramine polyol accelerates the film-forming process at lower temperatures below 20°C, while the film-forming process is slower or at least the same at higher temperatures. Therefore, the adhesive composition of the present invention cures faster or at least the same at temperatures below 20°C compared to curing at temperatures above 20°C.

[0249] Example

[0250] abbreviation

[0251] EO (ethylene oxide)

[0252] GPC gel permeation chromatography

[0253] HFIP (Hexafluoroisopropanol)

[0254] Mn number-average molecular weight

[0255] Mw weight-average molecular weight

[0256] PD polydispersity is defined as PD = Mw / Mn

[0257] PMMA (polymethyl methacrylate)

[0258] PS particle size

[0259] PDI (Polydispersity Index) of particle size distribution

[0260] DLS Dynamic Light Scattering

[0261] s / s Solid polymer addition based on solid polymer latex

[0262] rpm (speed per minute)

[0263] Sc. Solid content

[0264] TEA Triethanolamine

[0265] TIPA triisopropanolamine

[0266] Material

[0267] Polystyrene seed latex S1: Polystyrene seed latex with a solid content of 33% by weight and a volume average particle size of 10 to 50 nm.

[0268] Emulsifier E1: Sodium dodecyl sulfonate - 15% by weight aqueous solution.

[0269] Polyethyleneimine (PEI1): BASF SE's Lupasol FG has an average molecular weight of 600 g / mol.

[0270] Biocide 1: A biocide composition containing a mixture of 1,2-benzisothiazolin-3-one (5.0%) and 2-methyl-4-isothiazolin-3-one (2.5%) - Actid MBS 2550 of Thor Specialties, Inc.

[0271] Biocide 2: A biocide composition containing a mixture of 5-chloro-2-methyl-2H-isothiazolidin-3-one and 2-methyl-2H-isothiazolidin-3-one (3:1) - Actid MV of Thor Specialties, Inc.

[0272] analyze

[0273] 1. The solid content was determined by drying a specified amount of aqueous polymer dispersion (approximately 2 g) to constant weight (approximately 2 hours) in an aluminum crucible with an inner diameter of approximately 5 cm at 120°C in a drying oven. Two separate measurements were performed. The values ​​reported in the examples are the average of the two measurements.

[0274] 2. The particle size 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% by weight using a high-performance particle size analyzer (HPPS) from Malvern Instruments, UK, at 22°C. The cumulative Z-mean diameter is reported based on the measured autocorrelation function (ISO standard 13321).

[0275] 3. The glass transition temperature was determined by DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765:1994-03) using a DSC instrument (TA Instruments Q 2000 series).

[0276] 4. Molecular weight was determined by GPC using a refractometer as the detector. The mobile phase used was HFIP, and the standard used for molecular weight determination was PMMA.

[0277] 5. The OH value of polyetheramine polyols shall be determined according to DIN 53240 Part 2.

[0278] 6. The dynamic viscosity of polyetheramine polyol is determined according to ASTM D7042 at 23°C and 100 seconds. -1 The shear rate was measured.

[0279] 7. Amine value is determined according to the standard test procedure of DIN EN ISO 9702:1998.

[0280] Preparation Example 1: Carboxylated Latex (Disp1)

[0281] The charging of the polymerization reactor equipped with a temperature control module and a quantitative feeding module is as follows:

[0282] Initial charge 1

[0283] 462.47g water

[0284] 45.5g Seed Latex S1

[0285] Initial charge 2

[0286] 8.74g of 7% sodium persulfate aqueous solution

[0287] Feed 1 is prepared in the first feeding container using the following components:

[0288] Feed / Emulsion 1

[0289] 569.1g water

[0290] 100.0g Emulsifier E1

[0291] 19.5g Acrylic Acid

[0292] 636.5g Methyl methacrylate

[0293] 750.0g n-Butyl Acrylate

[0294] Feed 2 was prepared in the second feeding container using the following components:

[0295] Feed 2

[0296] 12.0g Methacrylic Acid

[0297] 37.5g n-Butyl Acrylate

[0298] 37.5g styrene

[0299] Feed 3 is prepared in the third feeding container using the following mixture:

[0300] Feed 3

[0301] 16.97g of 7% sodium persulfate aqueous solution

[0302] Initial charge 1 is heated (polymerization temperature: 90°C, stirring speed: 150 rpm). Then initial charge 2 is added to initial charge 1, and polymerization is carried out for 5 minutes. Feed 1 and feed 3 are started simultaneously and fed continuously over 2 hours. 20 minutes after the start of feeding 1 and feed 3, feed 2 is fed into the reactor over 5 minutes.

[0303] After the addition of feeds 1 and 3, 87.2 g of distilled water was added to the reactor, and the reaction mixture was stirred for another 20 minutes. After post-polymerization, 4.8 g of ammonia (25% aqueous solution) was added to the reaction mixture, and the mixture was stirred for 5 minutes. After the neutralization step, 9.0 g of 10% tert-butyl hydroperoxide aqueous solution and 33.4 g of 4.5% acetone-bisulfite aqueous solution were added over 1 hour. The resulting dispersion was then cooled to room temperature, diluted with 104.9 g of distilled water, and finally preserved with 6.0 g of biocide 1 and 2.6 g of biocide 2. 2950.6 g of the corresponding aqueous dispersion was obtained.

[0304] Sc: 51.9%; PS / PDI(DLS)=131nm / 0.01, pH=6.0

[0305] Preparation Example 2: Dispersion Disp2

[0306] The loading of the polymerization reactor equipped with a temperature control module and a quantitative feeding module is as follows:

[0307] Initial charge 1

[0308] 406.56g water

[0309] 23.6g Seed Latex S1

[0310] Feed 1 is prepared in the first feeding container using the following components:

[0311] Feed / Emulsion 1

[0312] 431.9g water

[0313] 86.67g Emulsifier E1

[0314] 6.50g 2-Ethylhexyl mercaptoacetic acid

[0315] 689.7g Methyl methacrylate

[0316] 583.1g 2-Ethylhexyl Acrylate

[0317] 16.90g Acrylic Acid

[0318] 10.40g Methacrylic Acid

[0319] Feed 2 was prepared in the second feeding container using the following mixture:

[0320] Feed 2

[0321] 55.71g of 7% sodium persulfate aqueous solution

[0322] Initial charge 1 was heated (polymerization temperature: 85°C, stirring speed: 150 rpm). Feeds 1 and 2 were started simultaneously and fed continuously over 3 hours. After feeding both feeds 1 and 2 was complete, 76.8 g of distilled water was added to the reactor, and the reaction mixture was stirred for another 20 minutes. After post-polymerization was 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 and bisulfite were added over 1 hour. The resulting dispersion was then cooled to room temperature, neutralized with 30.4 g of 10% ammonia water, and diluted with 108.3 g of distilled water.

[0323] 2570.6g of the corresponding aqueous dispersion was obtained.

[0324] Sc: 51.4%; PS / PDI(DLS)=159nm / 0.003; pH=8.4

[0325] Preparation Example 3: Dispersion Disp3

[0326] The loading of the polymerization reactor equipped with a temperature control module and a quantitative feeding module is as follows:

[0327] Initial charge 1

[0328] 406.56g water

[0329] 23.6g Seed Latex S1

[0330] Feed 1 is prepared in the first feeding container using the following components:

[0331] Feed / Emulsion 1

[0332] 215.9g water

[0333] 43.33g Emulsifier E1

[0334] 6.50g 2-Ethylhexyl mercaptoacetic acid

[0335] 344.8g Methyl methacrylate

[0336] 291.5g 2-Ethylhexyl Acrylate

[0337] 8.45g acrylic acid

[0338] 10.4g methacrylic acid

[0339] Feed 2 was prepared in the second feeding container using the following components:

[0340] Feed 2

[0341] 215.9g water

[0342] 43.33g Emulsifier E1

[0343] 344.8g Methyl methacrylate

[0344] 291.5g 2-Ethylhexyl Acrylate

[0345] 8.45g acrylic acid

[0346] Feed 3 is prepared in the third feeding container using the following mixture:

[0347] Feed 3

[0348] 55.7g of 7% sodium persulfate aqueous solution

[0349] Initial charge 1 was heated (polymerization temperature: 85°C, stirring speed: 150 rpm). Feeds 1 and 3 were started simultaneously, continuously fed over 1.5 hours and 3 hours respectively. After feed 1 was completed, feed 2 was started immediately and carried out for 1.5 hours. After feeds 2 and 3 were completed, 76.8 g of distilled water was added to the reactor, and the reaction mixture was stirred for another 20 minutes. After post-polymerization was complete, 7.8 g of 10% tert-butyl hydroperoxide aqueous solution and 28.9 g of 4.5% acetone-bisulfite aqueous solution were added over 1 hour. The resulting dispersion was then cooled to room temperature, neutralized with 30.4 g of 10% ammonia water, and diluted with 108.3 g of distilled water.

[0350] 2570.6g of the corresponding aqueous dispersion was obtained.

[0351] Sc: 51.5%; PS / PDI(DLS)=166nm / 0.03; pH=8.4

[0352] Preparation Example 4: EO-functionalized polyethyleneimine (comparative)

[0353] In a 2L autoclave, 430g of polyethyleneimine Lupasol FG and 43g of water were heated to 80°C. The autoclave was then purged three times with nitrogen to a final pressure of 2 bar. After raising the temperature to 120°C, 369g of ethylene oxide was added in batches. After all the ethylene oxide was added, the temperature was maintained until the reactor pressure stabilized. All volatile compounds were then removed under vacuum at 90°C. 820g of product was obtained.

[0354] Preparation Example 5: Synthesis of Polytriethanolamine from Triethanolamine

[0355] 2500 g of TEA and 70.78 g of a 50% by weight aqueous solution of H3PO2 were charged into a four-necked flask equipped with a stirrer, distillation bridge, inlet tube, and internal thermometer. The resulting mixture was heated to 200 °C under nitrogen atmosphere. The reaction mixture was stirred at 200 °C for 25 hours, during which time the condensate formed during the reaction was removed by passing it through the distillation bridge using a mild stream of N2 as the stripping gas. Near the end of the indicated reaction time, the temperature was lowered to 140 °C, and residual low molecular weight products were removed under a pressure of 100 mbar.

[0356] The reaction mixture was then cooled to ambient temperature to obtain polytriethanolamine polyol.

[0357] Mn=3960g / mol; Mw=39600g / mol; Mw / Mn=15.1

[0358] OH value: 284 mg KOH / g

[0359] Total amine value: 426 mg KOH / g

[0360] Tertiary amine value: 426 mg KOH / g

[0361] Dynamic viscosity at 23°C: 9100 mPa·s 1 / 100 second

[0362] The contents of secondary and primary amine groups were below the detection limit of 2 mg KOH / g, confirming that all amino groups present were tertiary amine groups.

[0363] Preparation Example 6: Synthesis of Polytriisopropanolamine from Triisopropanolamine

[0364] 2500 g of TIPA and 29.96 g of a 50% by weight aqueous solution of H3PO2 were charged into a four-necked flask equipped with a stirrer, distillation bridge, inlet tube, and internal thermometer. The resulting mixture was heated to 200 °C under nitrogen atmosphere. The reaction mixture was stirred at 200 °C for 10 hours, during which time the condensate formed during the reaction was removed by passing it through the distillation bridge using a mild stream of N2 as the stripping gas. Near the end of the indicated reaction time, the temperature was lowered to 140 °C, and residual low molecular weight products were removed under a pressure of 100 mbar.

[0365] The reaction mixture was then cooled to ambient temperature to obtain polytriisopropanolamine polyol.

[0366] Mn=2550g / mol; Mw=6180g / mol; Mw / Mn=2.4

[0367] OH value: 498 mg KOH / g

[0368] Total amine value: 306 mg KOH / g

[0369] Tertiary amine value: 304 mg KOH / g (the content of secondary and primary amine groups is below the detection limit of 2 mg KOH / g, confirming that all amino groups present are tertiary amine groups).

[0370] Dynamic viscosity at 23°C: 102000 mPa·s 1 / 100 second

[0371] Comparative Example 1: Adhesive Composition of Latex Disp1 + Polyethyleneimine

[0372] The adhesive composition of Comparative Example 1 was prepared by mixing the polymer latex of Preparation Example 1 with 2 wt% (s / s) of polyethyleneimine PEI1 after adding a biocide.

[0373] Comparative Example 2: Adhesive Composition of Latex Disp1 + Polyethyleneimine

[0374] The adhesive composition was prepared similarly to Comparative Example 1, but the pH of the final composition was adjusted to 7 using a 25% ammonia solution before adding 2% (s / s) of polyethyleneimine (PEI1). Attempts were made to measure the pH after the addition was completed, but this was not possible due to the instability of the mixture.

[0375] Comparative Example 3: Adhesive Composition of Latex Disp1 + Polyethyleneimine

[0376] The adhesive composition was prepared similarly to Comparative Example 1, but the pH of the final composition was adjusted to 8 using a 25% ammonia solution before adding 2% (s / s) of polyethyleneimine (PEI1). Attempts were made to measure the pH after the addition was completed, but this was not possible due to the instability of the mixture.

[0377] Comparative Example 4: Adhesive Composition of Latex Disp1 + EO Functionalized PEI

[0378] The adhesive composition was prepared similarly to that of Comparative Example 1, but after the addition of the biocide, 2% (s / s) of a 25% aqueous solution of Preparation Example 4 was added. The pH after the addition was 8.56.

[0379] Example 1: Adhesive composition of latex Disp1 + polytriethanolamine

[0380] The adhesive composition was prepared similarly to that of Comparative Example 1, but after the addition of the biocide, 2% (s / s) of a 25% aqueous solution of polytriethanolamine from Preparation Example 5 was added.

[0381] Example 2: Adhesive composition of latex Disp1 + polytriethanolamine

[0382] The adhesive composition was prepared similarly to that of Example 1, but the pH of the final composition was adjusted with a 25% ammonia solution before adding 2% (s / s) of the 25% aqueous solution of Preparation Example 5 so that the pH reached 8.38 after the addition of polytriethanolamine.

[0383] Example 3: Adhesive composition of latex Disp1 + polytriethanolamine

[0384] The adhesive composition was prepared similarly to that of Example 1, but the pH of the final dispersion was adjusted with a 25% ammonia solution before adding 2% (s / s) of the 25% aqueous solution of Preparation Example 5 so that the pH reached 8.58 after the addition of polytriethanolamine.

[0385] Example 4: Adhesive composition of latex Disp2 + polytriethanolamine

[0386] Similar to Example 1, latex Disp2 was used instead of latex Disp1 to prepare the adhesive composition.

[0387] Example 5: Adhesive composition of latex Disp3 + polytriethanolamine

[0388] Similar to Example 1, latex Disp3 was used instead of latex Disp1 to prepare the adhesive composition.

[0389] Stability test

[0390] The dispersion / composition was stored at 50°C for 14 days, and the pH was measured before and after storage. Stability was visually assessed. The results are summarized in Table 1 below.

[0391] Table 1

[0392]

[0393] yellowing

[0394] Films of each adhesive composition from Example 3 and Comparative Examples 1 and 4 were cast separately, and the yellowing effect was visually analyzed.

[0395] Comparative Example 1: No membrane could be obtained due to condensation.

[0396] Comparative Example 4: Severe Yellowing of the Membrane

[0397] Example 3: The membrane showed only very slight yellowing.

[0398] Drying test (early rain resistance)

[0399] Equipment: Glass carrier, 200-micron blade, artificial climate chamber, stopwatch

[0400] Test method: Apply a 200-micron (wet) film of paint or coating to a glass substrate at the required test temperature. Allow the coating to dry for 10 minutes after application.

[0401] Ten minutes after film application, the dryness of the coating was tested by pressing and releasing with a thumb under moderate force without any twisting. The coating surface was visually analyzed for adhesion and surface damage. The thumb-press-release test was repeated every 5 minutes until no adhesion or damage was observed. The results are summarized in Table 2.

[0402] Table 2

[0403] Example 3 Comparative Example 1 Comparative Example 4 23℃ 10min 3 Condensation 3 15min 2 Condensation 2 20min 2 Condensation 1 25min 1 Condensation 0 30min 0 Condensation 0 10℃ 10min 2 Condensation 2 15min 1 Condensation 2 20min 0 Condensation 1 25min 0 Condensation 0 30min 0 Condensation 0

[0404] Rating: From 0 to 3, where 3 indicates that the paint is still wet, sticky, and the surface is severely damaged, and 0 indicates that the paint is dry and there is no surface damage.

[0405] Compared to Comparative Example 4, the adhesive composition of Example 3 of the present invention exhibited faster drying performance at a low temperature of 10°C and slightly slower drying performance at a moderate temperature of 23°C. The results are summarized in Table 3:

[0406] Table 3

[0407] Example 4 Example 5 23℃ 10min 3 3 15min 2 2 20min 2 1 25min 0 0 30min 0 0 15℃ 10min 2 2 15min 2 2 20min 0 2 25min 0 0 30min 0 0

[0408] Rating: From 0 to 3, as shown in Table 2.

[0409] The adhesive composition of Example 4 dries faster at 15°C than at 23°C, and has sufficient application time at both 15°C and 23°C. The adhesive composition of Example 5 exhibits almost identical drying properties at 15°C and 23°C, and has sufficient application time at both 15°C and 23°C.

Claims

1. An aqueous adhesive composition comprising: (a) Aqueous polymer latex of film-forming carboxylated polymers; (b) 0.05 to 7.5% by weight of branched polyetheramine polyol dissolved in the aqueous phase of the polymer latex based on the dry weight of the carboxylated polymer, wherein at least 90% of the amino groups in the branched polyetheramine polyol are tertiary amine groups, and the branched polyetheramine polyol contains an average of 4 to 8.2 mol / kg of tertiary amine groups. The aqueous polymer latex of the carboxylated polymer is obtained by free radical emulsion polymerization of monomer component M, wherein monomer component M is composed of the following: a) 70% to 99.95% by weight of one or more olefinically unsaturated monomers M1 based on the total weight of monomeric component M, wherein said monomer M1 is selected from C1-C of monoolefinically unsaturated monocarboxylic acids having 3 to 6 carbon atoms. 20 Alkyl esters, mono-olefinic unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and di-C1-C2 alkyl esters. 20 Alkyl esters, C5-C monocarboxylic acids with 3 to 6 carbon atoms in a monoene bond 20 Cycloalkyl esters, C1-C 20 Vinyl esters of alkanonic acids, vinyl aromatic monomers, C2-C6 monoolefins and butadiene; b) 0.05% to 10% by weight of one or more mono-olefin unsaturated monomers M2, based on the total weight of monomer component M, wherein said monomer M2 is selected from mono-olefin unsaturated monocarboxylic acids having 3 to 6 carbon atoms and mono-olefin unsaturated dicarboxylic acids having 4 to 6 carbon atoms. c) One or more nonionic monomers M3, which are different from monomer M1, based on 0% to 20% by weight of the total weight of monomer component M.

2. The aqueous adhesive composition according to claim 1, wherein, According to DIN 53240 Part 2, the branched polyetheramine polyol has an OH value of 100 to 800 mg KOH / g.

3. The aqueous adhesive composition according to any one of the preceding claims, wherein the branched polyetheramine polyol has a number-average molecular weight M n The value ranges from 500 to 55000 g / mol.

4. The aqueous adhesive composition according to claim 1 or 2, wherein the branched polyetheramine polyol comprises an average of 5 to 8.0 mol / kg of tertiary amine groups.

5. The aqueous adhesive composition according to claim 1 or 2, wherein the branched polyetheramine polyol can be obtained by polycondensation of at least one trialkanolamine or by polycondensation of a mixture of at least one trialkanolamine and an aliphatic or alicyclic polyol.

6. The aqueous adhesive composition according to claim 1 or 2, wherein the monomer M1 is a mixture of the following monomers: - At least one monomer M1a, selected from C1-C of acrylic acid 20 C5-C of alkyl esters and methacrylic acid 20 Alkyl esters; and - At least one monomer M1b, which is selected from vinyl aromatic monomers and C1-C4 alkyl esters of methacrylic acid and mixtures thereof.

7. The aqueous adhesive composition according to claim 1 or 2, wherein the monomer M2 is selected from acrylic acid, methacrylic acid, and mixtures thereof.

8. The aqueous adhesive composition according to claim 1 or 2, wherein the aqueous polymer latex of the carboxylated polymer is obtained by free radical emulsion polymerization of monomer component M, wherein at least 90% of the monomer component M to be polymerized is metered into the polymerization reaction under polymerization conditions during the metering time period P, and wherein the composition of a portion of the monomer component M metered into the polymerization reaction under polymerization conditions is changed at least once during the metering time period P.

9. The aqueous adhesive composition according to claim 1 or 2, wherein the branched polyetheramine polyol is present in the composition in an amount of 0.1% to 5% by weight, based on the dry weight of the carboxylated polymer.

10. A water-based coating composition comprising the water-based adhesive composition of any one of the preceding claims.

11. The waterborne coating composition according to claim 10, further comprising at least one pigment and / or at least one filler.

12. Use of the aqueous adhesive composition according to any one of claims 1 to 9 as an adhesive or co-adhesive in an aqueous coating composition.

13. A method for forming a coating on a surface, comprising: (a) Applying the waterborne adhesive composition of any one of claims 1 to 9 and / or the waterborne coating composition of claim 10 or 11 to a surface, and (b) Dry the composition to produce a coating.

14. Use of branched polyetheramine polyols as additives for aqueous polymer latexes of film-forming carboxylated polymers, wherein at least 90% of the amino groups in the branched polyetheramine polyol are tertiary amine groups, and the branched polyetheramine polyol contains an average of 4 to 8.2 mol / kg of tertiary amine groups, wherein the amount of the branched polyetheramine polyol is from 0.05% to 7.5% by weight, based on the dry weight of the carboxylated polymer, wherein the aqueous polymer latex of the carboxylated polymer is obtained by free radical emulsion polymerization of monomer component M, wherein monomer component M consists of the following: a) 70% to 99.95% by weight of one or more olefinically unsaturated monomers M1 based on the total weight of monomeric component M, wherein said monomer M1 is selected from C1-C of monoolefinically unsaturated monocarboxylic acids having 3 to 6 carbon atoms. 20 Alkyl esters, mono-olefinic unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and di-C1-C2 alkyl esters. 20 Alkyl esters, C5-C monocarboxylic acids with 3 to 6 carbon atoms in a monoene bond 20 Cycloalkyl esters, C1-C 20 Vinyl esters of alkanonic acids, vinyl aromatic monomers, C2-C6 monoolefins and butadiene; b) 0.05% to 10% by weight of one or more mono-olefin unsaturated monomers M2, based on the total weight of monomer component M, wherein said monomer M2 is selected from mono-olefin unsaturated monocarboxylic acids having 3 to 6 carbon atoms and mono-olefin unsaturated dicarboxylic acids having 4 to 6 carbon atoms. c) One or more nonionic monomers M3, which are different from monomer M1, based on 0% to 20% by weight of the total weight of monomer component M.

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