Coating composition and preparation thereof

Abstract

The present invention relates to a coating composition comprising a binder comprising a polymer and / or copolymer of at least one acetoacetyl-functional ethylenically unsaturated monomer, at least one of a polyalkylene imine and / or a polyetheramine polyol, and optionally at least one polyetheramine, the coating composition exhibits good formaldehyde elimination, stain resistance, and scrub resistance.

Description

Technical Field

[0001] The present disclosure relates to a coating composition comprising a binder of a polymer and / or copolymer containing at least one acetoacetyl-functional ethylenically unsaturated monomer, at least one of a polyalkyleneimine and / or a polyetheramine polyol, and optionally at least one polyetheramine; and the preparation of the coating composition. Background Art

[0002] In recent years, with the increasing concern about health issues, indoor air quality has attracted more and more attention, and therefore, it is desirable to develop coating compositions with good formaldehyde elimination. In addition to good formaldehyde elimination, it is also desirable for some coatings, especially interior coatings for children's rooms, to have good stain resistance and scrub resistance. Many technical solutions have been proposed to develop interior coatings that can have such properties.

[0003] CN 113185635A discloses a polymer emulsion, which comprises (a) 5% to 35% by weight of dodecyl to octadecyl alkyl (meth)acrylates; (b) 1% to 14% by weight of itaconate monomers; (c) 0.1% to 10% by weight of unsaturated hydrophilic monomers; (d) 41% to 93.9% by weight of other ethylenically unsaturated monomers different from (a), (b) and (c), based on the total amount of the polymer. However, special monomers are used to obtain such a coating composition.

[0004] Therefore, there is still a need to develop coatings with good formaldehyde elimination, stain resistance and scrub resistance. Summary of the invention

[0005] Surprisingly, it has been found that coating compositions comprising a binder comprising a polymer and / or copolymer of at least one acetoacetyl-functional ethylenically unsaturated monomer, at least one of a polyalkyleneimine and / or polyetheramine polyol, and optionally at least one polyetheramine, have good formaldehyde removal, stain resistance, and scrub resistance.

[0006] One object of the present disclosure is to provide a coating composition comprising a binder comprising a polymer and / or copolymer of at least one acetoacetyl-functional ethylenically unsaturated monomer, at least one of a polyalkyleneimine and / or a polyetheramine polyol, and optionally at least one polyetheramine.

[0007] Another object of the present disclosure is to provide a method for preparing the above coating composition according to the present disclosure. DETAILED DESCRIPTION

[0008] Unless otherwise defined, all terms / terminology / nomenclature used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0009] The expressions "a / an" and "the" when used to qualify a term include both the plural and singular forms of the term.

[0010] As used herein, the term "polymer" or "polymers" includes both one or more homopolymers (i.e., polymers prepared from a single reactive compound) and one or more copolymers (i.e., polymers prepared by the reaction of at least two polymer-forming reactive monomer compounds).

[0011] The name (meth)acrylate and similar names are used herein as a shorthand notation for "acrylate and / or methacrylate".

[0012] One object of the present disclosure is to provide a coating composition comprising a binder comprising a polymer and / or copolymer of at least one acetoacetyl-functional ethylenically unsaturated monomer, at least one of a polyalkyleneimine and / or a polyetheramine polyol, and optionally at least one polyetheramine.

[0013] The acetoacetyl-functional ethylenically unsaturated monomer according to the present invention has an acetoacetoxy or acetoacetamido functional group attached to an ethylenically unsaturated moiety. Preferably, the acetoacetyl-functional ethylenically unsaturated monomer has formula (I) or formula (II)

[0014]

[0015]

[0016] in

[0017] R1 is H or C 1-10 -alkyl;

[0018] R2 is H, C 1-10 -alkyl or phenyl, the phenyl group optionally being C 1-10 -alkyl, F, Cl, Br, I, CN, hydroxyl and C 1-10 - at least one substitution in the alkoxy group;

[0019] R3 is H, C 1-10 -alkyl or phenyl, the phenyl group optionally being C 1-10 -alkyl, F, Cl, Br, I, CN, hydroxyl and C 1-10 - at least one substitution in the alkoxy group;

[0020] R4 is C 1-10 - alkylene or phenylene;

[0021] R5 is H, C1-10 -alkyl or phenyl, the phenyl group optionally being C 1-10 -alkyl, F, Cl, Br, I, CN, hydroxyl and C 1-10 - at least one substitution in the alkoxy group;

[0022] R6 is C 1-10 -alkyl;

[0023] R4' is H or C 1-4 -alkyl;

[0024] X and Y are each independently O or N;

[0025] a and b are each independently 0 or 1, but not both zero; and

[0026] c is a number in the range of 2 to 10.

[0027] As used herein, the term “C 1-10 "-alkyl" generally includes groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (C 1-6 -alkyl), more preferably 1 to 4 carbon atoms (C 1-4 The invention also provides a straight chain and branched aliphatic hydrocarbon portion of a (i)-alkyl) radical, such as methyl, ethyl, n-propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl, n-hexyl and isomeric groups, n-heptyl and isomeric groups such as 4,4-dimethylpentyl, n-octyl and isomeric groups such as 2,2,4-trimethylpentyl, n-nonyl and isomeric groups, n-decyl and isomeric groups, or an aliphatic cyclic hydrocarbon radical containing 3 to 10 carbons, preferably 3 to 8 carbons, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0028] As used herein, the term “C 1-10 "-alkylene" generally includes groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (C 1-6 -alkylene), more preferably 1 to 4 carbon atoms (C 1-4 The invention also includes both straight-chain and branched divalent aliphatic hydrocarbon radicals of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl-2-methylethylene, 1,1-dimethylethylene and 1-ethylpropylene.

[0029] As used herein, the term “C 1-10 The term "-alkoxy" generally includes groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (C 1-6 -alkoxy), more preferably 1 to 4 carbon atoms (C 1-4In the invention, there are alkyloxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, heptoxy, octoxy, isooctoxy, nonyloxy and decyloxy.

[0030] In specific embodiments of the acetoacetyl-functional ethylenically unsaturated monomer having formula (I), a is 0 or 1, and b is 1.

[0031] In a preferred embodiment of the acetoacetyl-functional ethylenically unsaturated monomer having formula (I), R1, R2 and R3 are independently selected from H and C 1-4 -alkyl, preferably methyl or ethyl; R4 is C 1-4 -alkylene, preferably methylene or ethylene; R5 is selected from H and methyl, preferably H; R6 is selected from methyl, ethyl and propyl, preferably methyl; X is O or N, preferably O; Y is O; a is 0 or 1, b is 1.

[0032] In further preferred embodiments of the acetoacetyl-functional ethylenically unsaturated monomer having formula (I), R1, R2 and R3 are independently selected from H and methyl; R4 is methylene or ethylene; R5 is H; R6 is methyl; X is O or N, preferably O; a is 0; and b is 1.

[0033] In a preferred embodiment of the acetoacetyl-functional ethylenically unsaturated monomer having formula (I), R1, R2 and R3 are independently selected from H and methyl; R4 is methylene or ethylene; R5 is H; R6 is methyl; X is O or N, preferably O; Y is O; and both a and b are 1.

[0034] In a preferred embodiment of the acetoacetyl-functional ethylenically unsaturated monomer having formula (II), R1, R2 and R3 are independently selected from H and C 1-4 -alkyl, preferably methyl or ethyl; R5 is selected from H and methyl, preferably H; R6 is selected from methyl, ethyl and propyl, preferably methyl; X is O or N, preferably O; R4' is selected from H, methyl and ethyl; and c is 2, 3, 4, 5, 6, 7 or 8.

[0035] In further preferred embodiments of the acetoacetyl-functional ethylenically unsaturated monomer having formula (II), R1, R2 and R3 are independently selected from H and methyl; R5 is H; R6 is methyl; R4' is H or methyl; X is O or N, preferably O; and c is 2, 3, 4, 5, 6, 7 or 8.

[0036] In a further preferred embodiment, the acetoacetyl-functional ethylenically unsaturated monomer having formula (I) may be selected from the compounds listed in Table 1 (wherein X=O, Y=O, R5=H and R6=CH3):

[0037] Table 1

[0038]

[0039]

[0040] In another further preferred embodiment, the acetoacetyl-functional ethylenically unsaturated monomer having formula (I) may be selected from the compounds listed in Table 2 (wherein X=O, Y=N, R5=H and R6=CH3):

[0041] Table 2

[0042]

[0043]

[0044] In a third further preferred embodiment, the acetoacetyl-functional ethylenically unsaturated monomer having formula (II) may be selected from the compounds listed in Table 3 (wherein R4′═H, R5═H and R6═CH3):

[0045] Table 3

[0046]

[0047]

[0048] Examples of specific acetoacetyl-functional ethylenically unsaturated monomers include, but are not limited to, compounds having the formula

[0049]

[0050]

[0051] The copolymer of the acetoacetyl-functional ethylenically unsaturated monomer according to the present disclosure may contain at least one ethylenically unsaturated monomer other than the acetoacetyl-functional ethylenically unsaturated monomer.

[0052] There is no particular limitation on the ethylenically unsaturated monomers that may be included in the copolymer of the acetoacetyl-functional ethylenically unsaturated monomer according to the present disclosure. Examples of optional ethylenically unsaturated monomers may include, but are not limited to, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl methacrylamide, allyl alcohol, vinyl pyridine, C 2-10 -Alkylene glycol diacrylate, C2-10 -Alkylene glycol dimethacrylate, glyceryl acrylate, glyceryl methacrylate, ureido acrylate, ureido methacrylate, N-(1,1-dimethyl-3-oxobutyl) acrylamide, N-vinyl-2-pyrrolidone (NVP), N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methylacetamide, N-vinyl caprolactam, acrylic acid C 1-10 -Alkyl esters and methacrylate C 1-10 -alkyl esters, C 1-10 -Alkyl acrylamide, C 1-10 -Alkyl methacrylamide, acrylonitrile, methacrylonitrile, C 1-10 -Alkanoic acid vinyl ester, C 2-10 -Olefins, C 2-10 -Halogenated olefins, styrene, C 1-6 - alkylstyrenes, vinyl alkyl ethers in which the alkyl moiety has 1 to 6 carbon atoms. Preferably, the optional ethylenically unsaturated monomers are selected from acrylic acid, methacrylic acid, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, 1-butene, butadiene, vinyl toluene and vinyl ethyl ether.

[0053] In one embodiment of the present disclosure, the polymers and / or copolymers of acetoacetyl-functional ethylenically unsaturated monomers have a weight average molecular weight (Mw) in the range of 5,000 to 3,000,000, preferably 50,000 to 1,000,000, more preferably 80,000 to 800,000, most preferably 100,000 to 600,000 as measured by gel permeation chromatography (GPC) in tetrahydrofuran against polystyrene standards.

[0054] There is no particular limitation on the methods by which the polymers and copolymers of acetoacetyl-functional ethylenically unsaturated monomers according to the present disclosure can be prepared. The polymers and copolymers of acetoacetyl-functional ethylenically unsaturated monomers according to the present invention can be prepared by any suitable method known in the art for polymerizing one or more ethylenically unsaturated monomers. For example, the polymers and copolymers of acetoacetyl-functional ethylenically unsaturated monomers according to the present invention can be prepared by emulsion or solution polymerization methods, particularly free radical emulsion polymerization.

[0055] For preparing polymers and copolymers of acetoacetyl-functional ethylenically unsaturated monomers according to the present disclosure by, for example, free radical emulsion polymerization, suitable free radical polymerization initiators are all those capable of initiating free radical emulsion polymerization. These can be, for example, peroxides, hydroperoxides, such as alkali metal peroxydisulfates; and azo compounds. Also suitable are initiator mixtures or redox initiator systems, such as tert-butyl hydroperoxide / sodium hydroxymethyl sulfonate, hydrogen peroxide / ascorbic acid, sodium persulfate / sodium disulfite, tert-butyl hydroperoxide / sodium disulfite and ascorbic acid / iron (II) sulfate / sodium persulfate. The initiator can be used in any conventional amount, for example in an amount of 0.01 to 5 wt.% based on the amount of all monomers to be polymerized.

[0056] For free radical emulsion polymerization, at least one emulsifier may be used in an amount of up to 30 wt.%, preferably 0.3 to 10 wt.% and more preferably 0.5 to 5 wt.%, based on the amount of all monomers to be polymerized. Suitable emulsifiers include, but are not limited to, nonionic emulsifiers such as ethoxylated mono-, di- and tri-alkylphenols (EO: 3 to 50, alkyl: C4-C9), ethoxylates of long chain alcohols (EO: 3 to 50, alkyl: C8-C9), 36 ) and polyethylene oxide / polypropylene oxide block copolymers; anionic emulsifiers such as alkyl sulfates (alkyl: C8-C 12 ) alkali metal salts and ammonium salts, ethoxylated alkanol sulfates (EO: 2 to 50, alkyl: C 12 -C 18 ) alkali metal salts and ammonium salts, ethoxylated alkylphenol (EO: 3 to 50, alkyl: C4-C9) alkali metal salts and ammonium salts, C 12 -C 18 Alkyl sulfonic acid and C9-C 18 Alkali metal salts and ammonium salts of alkylarylsulfonic acids; cationic emulsifiers and / or amphoteric emulsifiers. Further suitable emulsifiers can be found, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Volume 14 / 1, Makromolekulare Stoffe [Macromolecular Substances], Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

[0057] The free radical emulsion polymerization for preparing the polymer and copolymer of the acetoacetyl functional ethylenically unsaturated monomer according to the present disclosure can be carried out in the absence or presence of a seed for regulating the polymer particle size. Any seed known to be suitable for free radical emulsion polymerization can be used, such as an exogenous polymer seed (such as a polystyrene seed) or a polymer seed produced in situ. The polymerization method in the presence of seed is for example described in Encyclopedia of Polymer Science and Technology [Encyclopedia of Polymer Science and Technology], Volume 5, John Wiley & Sons Inc., New York, 1966, in page 847.

[0058] Other conventional materials useful in free radical emulsion polymerization, such as protective colloids, buffers, non-surfactant stabilizers and / or inert salts, may also be used to prepare polymers and copolymers of acetoacetyl-functional ethylenically unsaturated monomers according to the present disclosure.

[0059] The free radical emulsion polymerization for preparing polymers and copolymers of acetoacetyl-functional ethylenically unsaturated monomers according to the present disclosure is not subject to any practical restrictions on process parameters. For example, the free radical emulsion polymerization can be carried out at a temperature between 20°C and 100°C, preferably between 50°C and 95°C, and especially between 60°C and 90°C and at atmospheric pressure or under a slight vacuum.

[0060] In one embodiment, the polyalkylene imine according to the present disclosure includes but is not limited to polyethylene imine and polypropylene imine, etc.

[0061] The term polyethyleneimine refers not only to polyethyleneimine homopolymers, but also to polyalkyleneimines containing NH-CH2-CH2-NH units and other alkylenediamine units, such as NH-CH2-CH2-CH2-NH units, NH-CH2-CH(CH3)-NH units, NH-(CH2)4-NH units, NH-(CH2)6-NH units or NH-(CH2)8-NH units, but in terms of molar proportion, NH-CH2-CH2-NH units account for the majority, for example, 60 mol% or more, more preferably at least 70 mol% relative to all alkyleneimine units. In a specific embodiment, the term polyethyleneimine refers to those polyalkyleneimines that contain only one or zero alkyleneimine units other than NH-CH2-CH2-NH per polyethyleneimine structural unit.

[0062] Polyethyleneimines are commercially available or can be obtained by those skilled in the art via well-known methods. Suitable methods for preparing polyethyleneimines are well known. For example, linear polyethyleneimines can be prepared, for example, by post-modification of other polymers such as poly(2-oxazoline) (as described in High Molecular Weight Linear Polyethylenimine and Poly(N-methylethylenimine), Tanaka, Ryuichi et al., Macromolecules, 16(6), 849-853, 1983) or N-substituted polyethylenimine (as described in New Synthesis of Linear Polyethylenimine, Weyts, Katrien F. and Goethals, Eric J., Polymer Bulletin, 19(1), 13-19, 1988); branched polyethyleneimines can be prepared, for example, by ring-opening polymerization of aziridine (which has been developed for a long time, for example as described in Advances in the Chemistry of Polyethyleneimine (Polyaziridine) [Progress in the Chemistry of Polyethyleneimine (Polyaziridine)], Zhuk, DS, Gembitskii, PA and Kargin VA, Russian Chemical Reviews [Russian Chemical Reviews], Vol. 34 (7), 515-526, 1965).

[0063] In the context of the present invention, the term polypropyleneimine refers not only to polypropyleneimine homopolymers, but also to polyalkyleneimines containing NH-CH2-CH(CH3)-NH units and other alkylenediamine units, such as NH-CH2-CH2-CH2-NH units, NH-CH2-CH2-NH units, NH-(CH2)4-NH units, NH-(CH2)6-NH units or NH-(CH2)8-NH units, but in terms of molar proportion, NH-CH2-CH(CH3)-NH units are predominant. Preferred polypropyleneimines contain NH-CH2-CH(CH3)-NH units in a molar proportion, for example 60 mol % or more, more preferably at least 70 mol %, relative to all alkyleneimine units. In a special embodiment, the term polypropyleneimine refers to those polyalkyleneimines in which each polypropyleneimine structural unit carries only one or zero alkyleneimine units other than NH-CH2-CH(CH3)-NH.

[0064] In one embodiment, the polyalkylene imine according to the present disclosure generally has a carbonyl group of about 100 to about 4×10 6 in the range of about 200 to about 2×10 5 in the range of about 200 to about 2×10 4 In the range of about 300 to about 2×10 4 in the range of about 500 to 2×10 3 The weight average molecular weight (M) in the range of g / mol w ).

[0065] The term "polyetheramine polyol" means a polymer having amine groups, ether groups and hydroxyl groups.

[0066] In one embodiment, the polyetheramine polyol according to the present disclosure is a branched polyetheramine polyol.

[0067] In a preferred embodiment, 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. More preferably, the branched polyetheramine polyol is completely miscible with water at 20° C.

[0068] In another preferred embodiment, substantially all of the amino groups in the branched polyetheramine polyol are tertiary amino groups. The term "substantially" means that at least 90%, preferably at least 95%, more preferably more than 98% and even more preferably more than 99% of the amino groups in the branched polyetheramine polyol are tertiary amino groups. Often, the branched polyetheramine polyol contains less than 0.5 mol / kg of secondary and primary amino groups (if any) on average. Specifically, the polyetheramine polyol contains less than 0.2 mol / kg, especially less than 0.1 mol / kg of secondary and primary amino groups (if any) on average.

[0069] In another embodiment, the branched polyetheramine polyol contains 4 to 8.2 mol / kg, preferably 5 to 8.0 mol / kg, more preferably 5 to 7.9 mol / kg of tertiary amino groups.

[0070] In another embodiment, the polyetheramine polyol according to the present disclosure has an amine value of 100 to 700 mg KOH / g, preferably 200 to 500 mg KOH / g, determined according to the method described in DIN EN ISO 9702: 1998. In addition to determining the total amine content, this method allows for the determination of tertiary amine content, secondary amine content, and primary amine content.

[0071] In addition to amino groups, the polyetheramine polyols according to the present disclosure contain hydroxyl groups. In one embodiment, the OH value of the polyetheramine polyol is at least 100 mg KOH / g (e.g., 100 to 800 mg KOH / g), preferably at least 200 mg KOH / g (e.g., 200 to 700 mg KOH / g), more preferably at least 250 mg KOH / g (e.g., 250 to 650 mg KOH / g), determined according to Part 2 of DIN 53240.

[0072] The number of hydroxyl groups per molecule of the polyetheramine polyol according to the present disclosure depends on the number average molecular weight Mn and the degree of branching of the branched polyetheramine polyol. In one embodiment, the branched polyetheramine polyol contains at least four, more preferably at least six, more preferably at least ten hydroxyl groups per molecule on average (number average). In principle, there is no upper limit to the number of terminal or side functional groups. Preferably, the branched polyetheramine polyol contains at most 500, in particular at most 200 terminal hydroxyl groups per molecule on average (number average).

[0073] The weight average molar mass Mw of the polyetheramine polyol is 1000 to 200000 g / mol, preferably 2000 to 150000 g / mol, more preferably 3000 to 100000 g / mol, most preferably 4000 to 50000 g / mol, as determined by gel permeation chromatography using hexafluoroisopropanol as mobile phase and polymethyl methacrylate as standard. In another embodiment, the Mn of the branched polyetheramine polyol is 500 to 55000 g / mol, preferably 1000 to 40000 g / mol, as determined by gel permeation chromatography using hexafluoroisopropanol as mobile phase and polymethyl methacrylate as standard. The polydispersity of the polyetheramine polyol, i.e. the ratio Mw / Mn, is often in the range of 1.1 to 25, in particular in the range of 1.5 to 20.

[0074] The dynamic viscosity of branched polyetheramine polyols is usually between 5 and 200 Pa. -s In the range of 8 to 150 Pa -s The range is determined according to ASTM D7042 at 23°C.

[0075] The term "branched" describes that the polyetheramine polyol does not have a linear structure, but has a significant amount of branching points within the polymer backbone, which results in branched polymer chains. Such branching points can be tri- or tetra-substituted carbon atoms and / or tertiary amino groups. In particular, the branching points are tertiary amino groups.

[0076] The Hazen color number of the polyetheramine polyols is preferably in the range from 100 to 600 (APHA), determined in accordance with DIN ISO 6271.

[0077] Polyetheramine polyols are often amorphous and may therefore show a glass transition. In one embodiment of the present disclosure, the glass transition temperature of the polyetheramine polyol does not exceed 50° C., preferably in the range of −55° C. to 30° C. and more preferably in the range of −55° C. to 10° C., as determined by differential scanning calorimetry. Branched polyetheramine polyols and their preparation are known, for example, from DE 3206459, EP 441 198, WO 2009 / 047269, WO 2014 / 012812, which disclose branched polyetheramine polyols based on polycondensation products of at least one trialkanolamine.

[0078] In one embodiment of the present disclosure, the branched polyetheramine polyol is obtainable by the polycondensation of at least one trialkanolamine or by the polycondensation of a mixture of at least one trialkanolamine and an aliphatic or alicyclic polyol. The trialkanolamine is preferably selected from tri-C2-C8-alkanolamines, wherein the alkanol groups in the trialkanolamines may be different or identical, preferably, the alkanol groups are identical. More preferably, the trialkanolamines are selected from tri-C2-C4-alkanolamines, wherein the alkanol groups are identical. Particularly preferred trialkanolamines are triethanolamine, tri-n-propanolamine, tri-isopropanolamine, tri-n-butanolamine and tri-isobutanolamine and mixtures thereof. Suitable aliphatic or alicyclic polyols are, for example, aliphatic diols, aliphatic polyols with more than 2 hydroxyls, alicyclic diols and alicyclic polyols with more than 2 hydroxyls. Preferred are aliphatic diols and aliphatic polyols with more than 2 hydroxyls. Examples of aliphatic diols are C2-C20-diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol and structural isomers thereof. Further examples of aliphatic diols are compounds having the general formula HO-((CH2) n -O) m -H polyether diols, wherein n is independently 1 to 10, preferably 2 to 4, and m is in the range of 2 to 100. Preferably, the polyether diols are selected from polyethylene glycol, polypropylene glycol, polybutylene glycol and copolymers thereof. Examples of polyols with more than 2 hydroxyl groups are glycerol, pentaerythritol, trimethylolpropane, sorbitol and the like. The polyols can also be alkoxylated, in particular ethoxylated or propoxylated, such as ethoxylated glycerol, propoxylated glycerol, ethylated pentaerythritol, propoxylated pentaerythritol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated sorbitol and propoxylated sorbitol. Typically, the degree of alkoxylation (i.e. the number average of the alkylene oxide moieties) does not exceed 100 and is often in the range of 2 to 50.

[0079] Preferably, the polyetheramine polyol is obtainable by polycondensation, wherein 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 trialkanolamines, based on the total amount of monomers. The polyetheramine polyol is preferably obtainable by polycondensation of monomers containing 50 to 100 mol % of a compound selected from trialkanolamines and 0 to 50 mol % of a compound selected from aliphatic or cycloaliphatic polyols, preferably 70 to 100 mol % of a compound selected from trialkanolamines and 0 to 30 mol % of a compound selected from aliphatic or cycloaliphatic polyols, more preferably 80 to 100 mol % of a compound selected from trialkanolamines and 0 to 20 mol % of a compound selected from aliphatic or cycloaliphatic polyols, wherein "mol %" is based on the total amount of monomers.

[0080] In a specific embodiment, the polyetheramine polyol is obtainable by polycondensation, wherein the monomers consist only of monomers selected from trialkanolamines. The trialkanolamines are preferably selected from tri-C2-C4-alkanolamines. Preferred tri-C2-C4-alkanolamines are selected from triethanolamine, triisopropanolamine and tri-n-propanolamine.

[0081] The mixture of at least one trialkanolamine with an aliphatic or cycloaliphatic polyol is preferably selected from mixtures of at least one trialkanolamine selected from the group consisting of tri-C2-C4-alkanolamines and an aliphatic or cycloaliphatic C2-C8-polyol.

[0082] Particularly preferred are polyetheramine polyols obtainable by polycondensation of triethanolamine, or of triisopropanolamine, or of a mixture of triethanolamine and triisopropanolamine. In this embodiment, at least one further polyol, in particular at least one further diol, may optionally be present.

[0083] The polycondensation can be carried out in the presence or absence of a catalyst. Suitable catalysts include, but are not limited to, phosphoric acid (H3PO4), phosphorous acid (H3PO3) or hypophosphorous acid (H3PO2), which can be applied in bulk or in aqueous solution. Preferably, the catalyst is added in an amount of 0.001 to 10 mol%, preferably 0.005 to 7 mol%, more preferably 0.01 to 5 mol%, based on the amount of the trialkanolamine.

[0084] The polycondensation can be carried out by using a solvent. Examples of solvents that can be used to carry out the method of the present invention are aromatic and / or alicyclic hydrocarbons and mixtures thereof, halogenated hydrocarbons, ketones, esters and ethers. Preferred are aromatic hydrocarbons, alicyclic hydrocarbons, alkyl esters of alkanoic acids, ketones, alkoxylated alkyl esters of alkanoic acids and mixtures thereof. Particularly preferred are monoalkylated or polyalkylated benzene and naphthalene, ketones, alkyl esters of alkanoic acids and alkoxylated alkyl esters of alkanoic acids and mixtures thereof. The polycondensation is preferably carried out without using a solvent.

[0085] The polycondensation can be performed in such a manner that the temperature during the polycondensation does not exceed 250° C. and preferably does not exceed 230° C. For example, the polycondensation is performed at a temperature in the range of 150 to 230° C., preferably 180 to 215° C., more preferably 180 to 215° C.

[0086] The polycondensation can be carried out at a pressure in the range of 0.02 to 20 bar. Preferably, the polycondensation is carried out at normal pressure. After the polycondensation, the residual monomers are preferably removed or discharged, for example by distilling them off at normal pressure or under reduced pressure (for example in the range of 0.1 to 0.5 bar).

[0087] The water or other volatile products released during the polycondensation can be removed from the reaction mixture to accelerate the reaction. Preferably, the water or other volatile products released during the polycondensation are removed, such as by distillation and optionally under reduced pressure. The removal of water or other low molecular weight reaction byproducts can also be assisted by passing a gas stream (such as nitrogen) or an inert gas (such as helium, neon or argon) stream that is substantially inert under the reaction conditions through the reaction mixture (stripping).

[0088] The branched polyetheramine polyols described herein are typically stable for extended periods of time at room temperature, such as, for example, at least 10 weeks. Specifically, the polyetheramine polyols are stable and do not exhibit turbidity, precipitation, and / or significant increase in viscosity.

[0089] The polycondensation can be terminated by various options. For example, the temperature can be lowered to a range where the reaction stops and the polycondensation product is storage stable. This is typically the case 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.

[0090] The polycondensation can be carried out in a stirred tank reactor or in a cascade of stirred tank reactors. The process can be carried out batchwise, in semi-batch mode or continuously. The polycondensation products of trialkanolamines and co-polycondensation products of trialkanolamines as described herein are preferably used as polyetheramine polyols without chemical modification or derivatization. However, derivatives of the polycondensation products of trialkanolamines or derivatives of the co-polycondensation products of trialkanolamines can be used instead of the non-derivatized polycondensation products.

[0091] The derivatives of such polycondensation and cocondensation products of trialkanolamines include products obtained by alkoxylation of the hydroxyl end groups of non-derivatized polycondensation and cocondensation products. Similarly, the non-derivatized polycondensation or cocondensation products can be modified by hydrophobic groups or hydrophilic groups. Hydrophobization or hydrophilization can be achieved by reacting a portion of the hydroxyl end groups with selected reactants. The amino groups of polycondensation and cocondensation products can also be quaternized by using alkylating agents to obtain permanent cation-modified polymers. The derivatives of such polycondensation and cocondensation products of trialkanolamines are described in, for example, US2011 / 0168045, WO 2009 / 060060 and WO 2009 / 112379 mentioned. In a preferred embodiment, the derivatized product is an alkoxylated polycondensation and cocondensation product.

[0092] 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.

[0093] In one embodiment, the polyetheramine according to the present disclosure has a weight average molecular weight in the range of 104 to 8,000, preferably 148 to 6,000, and more preferably 200 to 4,000. Any polyetheramine commercially available or obtainable by known methods, such as polyetherdiamine, polyethertriamine, or any combination thereof, may be used.

[0094] In another embodiment, the polyetheramine according to the present disclosure may be selected from polyetherdiamines having a structure of formula (III):

[0095]

[0096] in

[0097] R7 is H or methyl, preferably methyl;

[0098] R8 is H or methyl, preferably methyl; and

[0099] x is a number such that the polyetherdiamine has a weight average molecular weight (Mw) in the range of 104 to 8,000, preferably 148 to 6,000, and more preferably 200 to 4,000.

[0100] In another embodiment, the polyetheramine according to the present disclosure may also be selected from polyethertriamines having a structure of formula (IV),

[0101]

[0102] in

[0103] R9 is H, methyl or ethyl, preferably methyl;

[0104] R 10 is H or C1-10-alkyl, preferably H or C1-4-alkyl, more preferably H, methyl, ethyl, propyl or butyl; and

[0105] x, y, z are independent numbers such that the polyether triamine has a weight average molecular weight (Mw) in the range of 300 to 6,000, preferably 400 to 5,000, for example 440 to 3,000.

[0106] In a specific embodiment, the polyether diamine having the structure of the following formula (V)

[0107]

[0108] wherein x is a number such that the polyetherdiamine has a weight average molecular weight (Mw) in the range of 132 to 8,000, preferably 190 to 6,000 and more preferably 230 to 4,000.

[0109] In one embodiment, the amount of at least one acetoacetyl-functional ethylenically unsaturated monomer according to the present disclosure used to prepare polymers and / or copolymers thereof is 0.1 to 10 wt.%, preferably 0.1 to 5 wt.%, more preferably 0.1 to 3 wt.%, and most preferably 0.3 to 2 wt.%, based on the total weight of the coating composition.

[0110] In another embodiment, at least one of the polyalkyleneimine and / or polyetheramine polyol is present in the coating composition in an amount of 0.1 to 10 wt.%, preferably 0.1 to 3 wt.%, more preferably 0.1 to 2 wt.%, and most preferably 0.1 to 1 wt.%, based on the total weight of the coating composition.

[0111] In another embodiment, the at least one polyetheramine is present in the coating composition in an amount of 0 to 10 wt.%, preferably 0.1 to 5 wt.%, preferably 0.2 to 3 wt.%, more preferably 0.3 to 2 wt.%, and most preferably 0.3 to 1 wt.%, based on the total weight of the coating composition.

[0112] The type of coating composition is not limited, and it can be, for example, an interior coating such as wall paint, radiator coating and floor coating, and also a coating for windows and doors. The coating composition can have a solid content of 20 to 80 wt.%, preferably 50 to 75 wt.%, based on the gross weight of the composition. If pigment and / or filler are not included, the coating composition can even have a lower solid content. For example, a coating composition that does not contain either pigment or filler can have a solid content as low as 5 wt.%, based on the gross weight of the composition.

[0113] As used herein, the term "binder" refers to an organic polymer compound that is responsible for film formation together with the other components of the coating composition. The coating composition may include at least one binder. The binder may be present in an amount of 1 to 90 wt.%, preferably 5 to 80 wt.%, preferably 10 to 70 wt.%, more preferably 15 to 60 wt.%, more preferably 20 to 50 wt.%, and most preferably 25 to 40 wt.%, based on the total weight of the coating composition.

[0114] There are no particular restrictions on the binders that may be present in the coating composition according to the present disclosure. Binders that may be used in the coating composition include, but are not limited to, alkyd resins, epoxy resins, polyurethanes, vinyl acetate / ethylene copolymers, waterglass, more specifically potassium waterglass, and also binders based on acrylates, styrenes and / or vinyl esters such as styrene acrylate or butyl acrylate.

[0115] For example, wall paints preferably comprise vinyl acetate / ethylene copolymers, styrene acrylates, butyl acrylate or mixtures of these polymers as binder; and radiator and floor coatings and coatings for windows and doors preferably comprise polyurethanes, acrylates, alkyd resins, epoxy resins and any mixtures thereof.

[0116] There is no particular restriction on the mode of incorporating the polymer and / or copolymer of acetoacetyl functional ethylenically unsaturated monomers into the base material. In one embodiment, the polymer and / or copolymer (its body or aqueous emulsion) of acetoacetyl functional ethylenically unsaturated monomers can be first incorporated into a small portion of the base material to obtain a dispersion of the polymer and / or copolymer containing acetoacetyl functional ethylenically unsaturated monomers, which is then incorporated into the remaining base material to prepare the coating composition. In another preferred embodiment, acetoacetyl functional ethylenically unsaturated monomers can be added before and / or during the polymerization process of alkyd resins, epoxy resins, polyurethanes, vinyl acetate / ethylene copolymers, water glass, etc. to prepare the copolymers contained in the base material. In a more preferred embodiment, acetoacetyl functional ethylenically unsaturated monomers are added together with other monomers of alkyd resins, epoxy resins, polyurethanes, vinyl acetate / ethylene copolymers, water glass, etc. to prepare the copolymers contained in the base material.

[0117] In addition, the coating composition may contain further components such as pigments, fillers, solvents, water and further additives such as preservatives, thickeners, dispersants and defoamers.

[0118] Suitable pigments include, for example, inorganic white pigments, such as titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide and lithopone; inorganic colored pigments, such as iron oxide, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black and manganese violet; organic color pigments, such as indigo, azo dyes, anthraquinones and indidental dyes, as well as dioxazines, quinacridones, phthalocyanines, isoindolinones and metal complex pigments. Also suitable are synthetic white pigments with air inclusions to increase light scattering, such as The pigment, if present, may be present in an amount of 20 to 80 wt.%, preferably 50 to 75 wt.%, in the case of a wall paint, or may be present in an amount of not more than 25 wt.%, most preferably not more than 15 wt.%, most preferably not more than 10 wt.%, in the case of a transparent or translucent coating, based on the total weight of the coating composition.

[0119] Suitable fillers include, for example, kaolin, talc, mica, magnesite, alkaline earth metal carbonates such as calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates such as calcium sulfate, silicon compounds such as silicon dioxide or aluminum silicate or magnesium aluminum silicate, and aluminum oxide or aluminum oxide hydrate. Fillers, if present, may be present in an amount of 1 to 90 wt.%, preferably 20 to 60 wt.%, in the case of wall paints, or may be present in an amount of not more than 5 wt.%, preferably not more than 2 wt.%, most preferably not more than 1 wt.%, based on the total weight of the coating composition.

[0120] Suitable organic solvents include, for example, trimethylpentane, propylene glycol or dipropylene glycol butyl ether.The organic solvent, if present, may be present in an amount of less than 5 wt. %, based on the total weight of the coating composition.

[0121] Suitable preservatives include, for example, isothiazolinone formulations such as 2-methyl-2H-isothiazol-3-one or 1,2-benzisothiazolin-3H-one.The preservative may be present in an amount of less than 2 wt.%, preferably less than 0.3 wt.%, based on the total weight of the coating composition.

[0122] Suitable thickeners include, for example, cellulose ethers, bentonites, polysaccharides, fumed silica, layered silicates or polyurethane thickeners.The thickener may be present in an amount of less than 1 wt.%, preferably less than 0.6 wt.%, based on the total weight of the coating composition.

[0123] Suitable dispersants include, for example, alkylbenzene sulfonates, polycarboxylates, fatty acid amines or salts of polyacrylic acid.The dispersant may be present in an amount of less than 2 wt.%, preferably 0.001 to 0.5 wt.%, based on the total weight of the coating composition.

[0124] Suitable defoamers include, for example, poly(organo)siloxanes, silicone oils or mineral oils.The defoamer may be present in an amount of less than 1 wt.%, more preferably 0 to 0.5 wt.%, based on the total weight of the coating composition.

[0125] Another object of the present disclosure is to provide a method for preparing the above coating composition according to the present disclosure, which comprises mixing a base of a polymer and / or copolymer containing an acetoacetyl-functional ethylenically unsaturated monomer, at least one of a polyalkyleneimine and / or a polyetheramine polyol, and optionally a polyetheramine and other additives at room temperature.

[0126] The present invention is further described and illustrated in the following examples, without however being limited to the embodiments described therein.

[0127] Examples

[0128] As used herein, weight average molecular weight is measured by gel permeation chromatography (GPC) against polystyrene standards in tetrahydrofuran, unless otherwise indicated.

[0129] In the following description, parts and percentage values ​​are by wt. % unless otherwise specified.

[0130] The following materials were used in the following preparation methods.

[0131] AAEMA, 3-oxo-butyric acid 2-[(2-methyl-1-oxo-2-propenyl)oxy]ethyl ester, 100%, Eastman

[0132] EC302, Baxxdour EC302 100%, BASF,

[0133] P25, Polytriethanolamine, 25%, Polystar 25, BASF

[0134] AAEA, 2-acetoacetoxyethyl acrylate, 100%, TCI Corporation

[0135] Lupasol, Lupasol G20, 20%, BASF

[0136] MEO, 2-methylprop-2-enyl 3-oxobutyrate, 100%, BASF

[0137] LDBS23, Disponil LDBS23, 23%, BASF

[0138] Teric305, TERIC305, 100%, Huntsman

[0139] DB45, Calfax DB-45, 45%, Pilot Chemical

[0140] AA, acrylic acid, 100%, Sinopharm

[0141] AM50%, Acrylamide, 50%, BASF

[0142] MMA, methyl methacrylate, 100%, Sinopharm Group

[0143] ST, styrene, 100%, Sinopharm Group

[0144] nBA, n-butyl acrylate, 100%, Sinopharm Group

[0145] NaPS, sodium persulfate, 100%, Sinopharm Group

[0146] t-BHP, tert-butyl hydroperoxide, 10%, BASF

[0147] NaHSO3, sodium bisulfite, 100%, Sinopharm Group

[0148] NaOH, sodium hydroxide, 100%, Sinopharm Group

[0149] In the present invention, the total stains were tested according to HG T 4756-2014, the ASTM scrub resistance was tested according to ASTM D 2486; and the formaldehyde elimination efficiency (anti-FA efficiency) was tested according to GB / T 16129-1995.

[0150] Example 1

[0151] 0.8g LDBS23 and 140.33g DI water were placed in a reactor together and the temperature was heated to 90°C. During the heating period, DI water 236.17g, Teric305 4.53g, DB45 4.03g, Disponil AA 5.91g, AAEMA13.76g, AM50% 4.53g, MMA 111.8g, styrene 45.61g and nBA 277.45g were mixed as a pre-emulsion. When the temperature of the reactor stabilized at 90°C, 25.4g of the pre-emulsion was placed in the reactor within 1 minute, and then 7% NaPS 7.27g was added within another minute. After 5 minutes, the remaining pre-emulsion and 7% NaPS11.93g were added simultaneously within 175 minutes, and post-polymerization was carried out for 30 minutes. After polymerization, 10% t-BHP 7.98g and 13% NaHSO3 10.65g were added simultaneously over 120 minutes to remove residual monomers. After removing the residual monomers, the reactor was cooled to room temperature, and then 8% NaOH 25.91g, EC302 13.76g and P25 47.62g (25% solid content) were added to neutralize the polymer dispersion. The final solid content was adjusted to 50wt.% with water and a final sample was obtained for testing. The Mw of Example 1 was about 400,000 as measured by GPC.

[0152] Example 2-3

[0153] The procedure was the same as Example 1 except that different amounts of AAEMA or P25 were added.

[0154] Example 4-5

[0155] The procedure was the same as in Example 1, except that AAEA or MEO was added instead of AAEMA.

[0156] Example 6

[0157] The procedure was the same as in Example 1 except that Lupasol was added instead of P25.

[0158] Example 7

[0159] The procedure was the same as in Example 1, except that EC302 was not added.

[0160] Comparative Examples 1-6

[0161] The procedure was the same as Example 1, except that no AAEMA, EC302 and / or P25 were added.

[0162] The amounts of AAEMA (or AAEA or MEO), EC302 and P25 (or Lupasol) used in Examples 1-7 and Comparative Examples 1-6 are listed in Table 4.

[0163] Table 4

[0164] serial number AAEMA AAEA MEO EC302 P25 Lupasol Example 1 13.76 13.76 47.62 Example 2 18.35 13.76 47.62 Example 3 13.76 13.76 18.32 Example 4 13.76 13.76 47.62 Example 5 13.76 13.76 47.62 Example 6 13.76 13.76 59.55 Example 7 13.76 47.62 Comparative Example 1 13.76 13.76 Comparative Example 2 13.76 Comparative Example 3 13.76 47.62 Comparative Example 4 47.62 Comparative Example 5 13.76 Comparative Example 6

[0165] The test results of total stain, ASTM scrub resistance and anti-FA efficiency of Examples 1-7 and Comparative Examples 1-6 are listed in Table 5.

[0166] Table 5

[0167]

[0168]

Claims

1. A coating composition comprising: a) a binder comprising a polymer and / or copolymer of at least one acetoacetyl-functional ethylenically unsaturated monomer, b) at least one polyalkyleneimine and / or polyetheramine polyol; and c) optionally at least one polyetheramine.

2. The coating composition according to claim 1, wherein The at least one acetoacetyl-functional ethylenically unsaturated monomer has formula (I) or formula (II) in R1 is H or C 1-10 -alkyl; R2 is H, C 1-10 -alkyl or phenyl, the phenyl group optionally being C 1-10 -alkyl, F, Cl, Br, I, CN, hydroxyl and C 1-10 - at least one substitution in the alkoxy group; R3 is H, C 1-10 -alkyl or phenyl, the phenyl group optionally being C 1-10 -alkyl, F, Cl, Br, I, CN, hydroxyl and C 1-10 - at least one substitution in the alkoxy group; R4 is C 1-10 - alkylene or phenylene; R5 is H, C 1-10 -alkyl or phenyl, the phenyl group optionally being C 1-10 -alkyl, F, Cl, Br, I, CN, hydroxyl and C 1-10 - at least one substitution in the alkoxy group; R6 is C 1-10 -alkyl; R4' is H or C 1-4 -alkyl; X and Y are independently O or N; a and b are independently 0 or 1, but not both zero; and c is a number in the range of 2 to 10.

3. The coating composition according to claim 2, wherein R1, R2 and R3 in formula (I) are independently selected from H and C 1-4 -alkyl, preferably methyl or ethyl; R4 is C 1-4 -alkylene, preferably methylene or ethylene; R5 is selected from H and methyl, preferably H; R6 is selected from methyl, ethyl and propyl, preferably methyl; X is O or N, preferably O; Y is O; a and b are independently 0 or 1, but not both zero.

4. The coating composition according to claim 2, wherein R1, R2 and R3 in formula (I) are independently selected from H and methyl; R4 is methylene or ethylene; R5 is H; R6 is methyl; X is O or N, preferably O; a is 0; and b is 1.

5. The coating composition according to claim 2, wherein R1, R2 and R3 in formula (I) are independently selected from H and methyl; R4 is methylene or ethylene; R5 is H; R6 is methyl; X is O or N, preferably O; Y is O; and a and b are both 1.

6. The coating composition according to claim 2, wherein R1, R2 and R3 in formula (II) are independently selected from H and C 1-4 -alkyl, preferably methyl or ethyl; R5 is selected from H and methyl, preferably H; R6 is selected from methyl, ethyl and propyl, preferably methyl; X is O or N, preferably O; R4' is selected from H, methyl and ethyl; and c is 2, 3, 4, 5, 6, 7 or 8.

7. The coating composition according to claim 2, wherein R1, R2 and R3 in formula (II) are independently selected from H and methyl; R5 is H; R6 is methyl; R4' is H or methyl; X is O or N, preferably O; and c is 2, 3, 4, 5, 6, 7 or 8.

8. The coating composition according to claim 1, wherein The at least one acetoacetyl-functional ethylenically unsaturated monomer is selected from compounds having the formula:

9. The coating composition according to any one of claims 1 to 8, wherein The polymer and / or copolymer of the at least one acetoacetyl-functional ethylenically unsaturated monomer has a weight average molecular weight in the range of 5,000 to 3,000,000, preferably 50,000 to 1,000,000, more preferably 80,000 to 800,000, most preferably 100,000 to 600,000 g / mol.

10. The coating composition according to any one of claims 1 to 9, wherein The polyalkyleneimine is selected from the group consisting of polyethyleneimine and / or polypropyleneimine, and has a weight average molecular weight ranging from 100 to 4,000,000, preferably from 200 to 200,000, more preferably from 300 to 20,000, most preferably from 500 to 2,000.

11. The coating composition according to any one of claims 1 to 10, wherein The polyetheramine polyol is selected from the group consisting of triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine.

12. The coating composition according to any one of claims 1 to 11, wherein The polyetheramine polyol has a weight average molar mass in the range of 1000 to 200000 g / mol, preferably 2000 to 150000 g / mol, more preferably 3000 to 100000 g / mol, most preferably 4000 to 50000 g / mol.

13. The coating composition according to any one of claims 1 to 12, wherein The polyetheramine has a weight average molecular weight in the range of 104 to 8,000, more preferably 148 to 6,000, and even more preferably 200 to 4,000.

14. The coating composition according to any one of claims 1 to 13, wherein Based on the total weight of the coating composition, a) the amount of the at least one acetoacetyl-functional ethylenically unsaturated monomer used to prepare the polymers and / or copolymers thereof is 0.1 to 10 wt.%, preferably 0.1 to 5 wt.%, more preferably 0.1 to 3 wt.%, most preferably 0.3 to 2 wt.%, b) at least one of a polyalkyleneimine and / or a polyetheramine polyol is present in an amount of 0.1 to 10 wt.%, preferably 0.1 to 3 wt.%, more preferably 0.1 to 2 wt.%, most preferably 0.1 to 1 wt.%, c) The polyetheramine is present in an amount of 0 to 10 wt.%, preferably 0.1 to 5 wt.%, preferably 0.2 to 3 wt.%, more preferably 0.3 to 2 wt.%, most preferably 0.3 to 1 wt.%.

15. The coating composition according to any one of claims 1 to 14, wherein The at least one acetoacetyl-functional ethylenically unsaturated monomer is added during the preparation of the copolymer comprised in the binder together with other monomers of alkyd resins, epoxy resins, polyurethanes, vinyl acetate / ethylene copolymers, waterglass.

16. The coating composition according to any one of claims 1 to 15, wherein The composition comprises both a polyalkyleneimine and a polyetheramine polyol, preferably the composition comprises at least one polyetheramine polyol.

17. A method for preparing the coating composition according to any one of claims 1 to 16, comprising mixing the components contained in the coating composition.

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