Water-based polyurethane-vinyl polymer hybrid dispersion

Abstract

The present invention relates to aqueous polyurethane-vinyl polymer hybrid dispersions prepared by polymerization, free radical initiated, of ethylenically unsaturated monomers and polyurethane prepolymers containing acid and hydroxyl groups, to a process for their preparation, and to their use, especially as coating binders in multilayer coatings.

Description

[Technical field]

[0001] The present invention relates to aqueous polyurethane-vinyl polymer hybrid dispersions prepared by free-radical initiated polymerization of ethylenically unsaturated monomers and polyurethane prepolymers containing (pendant) acid and hydroxyl groups, to a process for their preparation and to their use, in particular as coating binders in multilayer coatings. [Background technology]

[0002] Dispersions of polyurethane-vinyl polymer hybrids made by radical initiated copolymerization of ethylenically unsaturated monomers and polyurethane macromonomers are known in the art.

[0003] EP 0522420 A2 discloses polyurethane dispersions prepared by free radical initiated polymerization of polyurethane macromonomers containing carboxyl, phosphonyl, or sulfonyl groups and terminal vinyl groups, and optionally urethane, thiourethane, or urea groups, wherein the terminal vinyl groups are not derived from hydroxyalkyl (meth)acrylates.

[0004] EP1173491B1 discloses polymers obtainable by a multi-stage polymerization process which comprises in a first step the aqueous phase polymerization of at least one ethylenically monofunctional compound, alone or together with at least one ethylenically di- or polyfunctional compound, in the presence of a polyester polyol, a polyurethane and / or a polyacrylate, followed by reaction of the resulting product with a crosslinker.

[0005] EP1185568B1 discloses polymers obtained in a multi-stage polymerization process. In a first stage, polymerization is carried out in an aqueous phase of at least one ethylenically monofunctional compound, optionally including at least one ethylenically di- or polyfunctional compound, in the presence of polyester polyols, polyurethanes, and / or polyacrylates, and in the following stages, the resulting product is reacted with at least one ethylenically monofunctional compound, optionally including at least one ethylenically di- or polyfunctional compound, and later the resulting product is reacted with a crosslinking agent. EP1185568B1 further relates to the use of said polymers.

[0006] EP1391471B1 describes a method for preparing aqueous polyurethane-polyacrylate hybrid dispersions, comprising the steps of: (I) preparing a hydrophilic or hydrophilizable polyurethane by reacting one or more isocyanate components (A) with one or more components (B) in the presence of ethylenically unsaturated monomers (C1) which are inert towards NCO groups, provided that components (A) and (B) are used in a ratio of NCO groups and OH / NH / NH2 groups of 1:1, where component (B) is (B1) one or more diols or polyols having a molecular weight of 500 to 6000 and an OH functionality of 1.8 to 5, (B2) one or more low molecular weight diols or polyols in the molecular weight range of 62 to 400 containing two or more OH functional groups as chain extenders, (B3) one or more hydrophilic compounds containing non-ionic and / or ionic and / or potentially ionic groups and having at least one NCO-reactive group, (B4) optionally one or more polyamines and / or alkanolamines with a molecular weight in the range from 60 to 300 g / mol and with at least two NH functions, (B5) optionally a monofunctional compound with a molecular weight in the range of 17 to 350 g / mol and (II) then dispersing the polyurethane from (I) in water; (III) (i) an ethylenically unsaturated monomer (C1) which is inert towards NCO groups, and (ii) an ethylenically unsaturated monomer (C1) which is inactive towards NCO groups and an ethylenically unsaturated monomer (C2) which contains a Zerevitinov active hydrogen atom and emulsion polymerizing a monomer (C) comprising one of the following: The present invention discloses a method including:

[0007] EP1497349B1 describes an aqueous polyurethane dispersion comprising polyurethane-acrylate particles dispersed in an aqueous medium, the particles being (A) (i) a polyol, (ii) a polymerizable ethylenically unsaturated monomer containing at least one hydroxyl group; (iii) a compound containing a C1 to C30 alkyl group having at least two active hydrogen-containing groups selected from a carboxylic acid group and a hydroxyl group, at least one of the active hydrogen-containing groups being a hydroxyl group; and (iv) Polyisocyanate An active hydrogen-containing polyurethane acrylate prepolymer comprising a reaction product obtained by the reaction of (B) one or more hydrophobic polymerizable ethylenically unsaturated monomers, and (C) a crosslinking monomer having two or more polymerizable ethylenically unsaturated sites and a reaction product obtained by polymerizing the components of a pre-emulsion formed from The present invention discloses an aqueous polyurethane dispersion, wherein the active hydrogen-containing polyurethane acrylate prepolymer (A) comprises at least 30% by weight of a polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at one end of the molecule and at least one active hydrogen-containing group at the other end of the molecule, and at least 10% by weight of a polyurethane acrylate prepolymer comprising one or more prepolymers having at least one terminal polymerizable site of ethylenic unsaturation at each end of the molecule.

[0008] EP 2 655 458 B1 describes polyurethane-polyacrylate hybrid dispersions obtainable by two-stage free radical polymerization of ethylenically unsaturated compounds in the presence of at least one polyurethane (P1), in which in a first stage a monomer mixture (e) of at least one ethylenically unsaturated compound is subjected to at least partial free radical polymerization in the presence of at least one polyurethane (P1), at least one redox initiator system (I) and at least one iron compound (F), and then in a second stage a monomer mixture (f) of at least one ethylenically unsaturated compound is subjected to free radical polymerization, at least one polyurethane (P1) is composed exclusively of aliphatic and / or cycloaliphatic isocyanates as isocyanate group-containing synthesis components and has an at least partially neutralized acid group content of less than 500 mmol / kg of polyurethane, the first-stage polymerized monomer mixture (e) has a glass transition temperature of at least 50° C., the second-stage polymerized monomer mixture (f) has a glass transition temperature of up to 20° C., the weight ratio of the first and second stage polyurethanes (P1) to the sum of the ethylenically unsaturated compounds (e) and (f) is 50:50 to 30:70, The temperature during the free radical polymerization is below 85°C and the glass transition temperature is measured by differential scanning calorimetry (DSC) at a heating rate of 10°C / min according to ASTM standard D3418-03; Polyurethane-polyacrylate hybrid dispersions are disclosed.

[0009] EP 3022242 B1 describes an aqueous dispersion comprising at least one copolymer, the copolymer being (i) initially charging an aqueous dispersion of at least one polyurethane, followed by (ii) polymerizing the mixture of olefinically unsaturated monomers in the presence of the polyurethane from (i); (a) a water-soluble initiator is used; (b) the metered addition of the olefinically unsaturated monomer is effected in such a way that a concentration of 6.0% by weight, based on the total amount of olefinically unsaturated monomer in the reaction solution, is not exceeded over the entire duration of the reaction; and (c) the mixture of olefinically unsaturated monomers comprises at least one polyolefinically unsaturated monomer; Steps and The present invention discloses an aqueous dispersion, preferably

[0010] US2019169353A1 has the following components: Hydrophobically modified hydroxy-functional polyester A, acids B which have further groups which react with isocyanates under the formation of urethanes, ureas or thiourethanes, Optionally, hydroxy-functional oligomeric or polymeric compounds C, which may be polyesters, polycarbonates, polyethers, polyamides, polydienes and polyenes, have at least two hydroxyl groups per molecule, optionally monomeric hydroxy compounds D having at least two hydroxyl groups per molecule, optionally a compound E having at least one primary or secondary amino group and at least one hydroxyl group per molecule, optionally a compound F having two or more primary or secondary amino groups per molecule and no hydroxyl groups, a compound G having only one hydroxyl group and one or more tertiary amino groups, an olefinically unsaturated monomer H2 having a polymerizable ethylenic unsaturation and a further functional group which reacts with an isocyanate group under bond formation, olefinically unsaturated monomers H1 which have at least one polymerizable ethylenic unsaturation and which have no further functional groups which react with isocyanate groups, and The present invention discloses an aqueous polyurethane-vinyl polymer hybrid dispersion comprising a polyfunctional isocyanate I having at least two isocyanate groups per molecule, The hydrophobically modified polyester A is obtained from a polyester A' having residual hydroxyl and acid groups by reaction of its acid groups with a monofunctional compound A4 having an epoxide or aziridine functionality and a linear or branched alkyl residue of at least 4 carbon atoms, in which reaction at least 90% of the residual acid groups of the polyester A' are converted into ester or amide groups. Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention aims to provide an aqueous dispersion for a coating composition which does not exhibit the disadvantages of the prior art.

[0012] It is an object of the present invention to provide surfactant-free aqueous polyurethane-vinyl polymer hybrid dispersions with increased solids content compared to the current state of the art systems.

[0013] It is a further object of the present invention to provide an aqueous polyurethane-vinyl polymer hybrid dispersion having improved water and moisture resistance and improved interlayer adhesion in multi-layer coating films. [Means for solving the problem]

[0014] The present invention discloses an aqueous polyurethane-vinyl polymer hybrid dispersion D comprising a reaction product E of one or more ethylenically unsaturated monomers MU2, MU2 being polymerized in the presence of a polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups, said prepolymer PUSpp comprising pendant polyvinyl chains, said prepolymer PUSpp being the reaction product of one or more ethylenically unsaturated monomers MU1 being polymerized in the presence of an acid salt-containing hydroxyl functional polyurethane PUSoh having pendant ethylenically unsaturated groups and pendant groups of acid salts.

[0015] Preferred embodiments of the present invention disclose one or more of the following features: The hydroxyl functional polyurethane PUoh is characterized in that the unsaturated equivalent weight (UEW) is 3,500-35,000 g / equiv and the ethylenically unsaturated groups are pendant groups; Hydroxyl-functional polyurethane PUoh is characterized by an acid value of 30-60 mg KOH / g; The dispersed particles of reaction product E are characterized by a Z-average particle size according to ISO 22412 of 50-150 nm; The aqueous polyurethane-vinyl polymer hybrid dispersion D comprises 40-55% by weight, preferably 43-50% by weight, of solids and 45-60% by weight, preferably 50-57% by weight of water.

[0016] Coating compositions comprising the aqueous polyurethane-vinyl hybrid dispersion D are useful for producing anti-corrosion coatings or anti-corrosion multi-coat build-ups for metal substrates.

[0017] A method for the preparation of an aqueous polyurethane-vinyl polymer hybrid dispersion D, comprising the steps of rapidly adding a mixture comprising one or more primary or secondary amines Aoh(s) having at least one hydroxyl group, and optionally and preferably one or more ethylenically unsaturated monomer(s) MU1 to an isocyanate-functional polyurethane prepolymer comprising pendant ethylenically unsaturated groups and pendant acid groups, to form a hydroxyl-functional polyurethane prepolymer PUoh in the ethylenically unsaturated monomer(s) MU1; A method is further disclosed, comprising the steps of adding a neutralizing agent An to form an acid-group-containing hydroxyl-functional polyurethane PUSoh containing pendant ethylenically unsaturated group(s), adding water to form an emulsion, followed by gradually adding at least one of the redox system components, polymerizing the emulsion to form PUSpp, and later further reacting the PUSpp by a second fast addition of an ethylenically unsaturated monomer MU2 after completing further redox polymerization to form an aqueous polyurethane-vinyl polymer hybrid dispersion D1.

[0018] A preferred embodiment of the method of the present invention comprises further rapid addition of a mixture of ethylenically unsaturated monomer mixtures MU1 and / or MU2 to the aqueous polyurethane-vinyl polymer hybrid dispersion D1 and carrying out redox polymerization to form an aqueous polyurethane-vinyl polymer hybrid dispersion D2.

[0019] The present invention further discloses a coating composition comprising the aqueous polyurethane-vinyl polymer hybrid dispersion D and one or more additive(s) selected from the group consisting of defoamers, leveling agents, UV absorbers, coalescing agents, flow control agents, rheology additives, fillers, pigments, active pigments, and wetting agents.

[0020] The coating composition may further comprise a crosslinking agent.

[0021] The present invention further discloses the use of said coating composition for coating a metal, wood, plastic or paper substrate, preferably for coating a metal substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] In the present invention, it has been found that an aqueous dispersion D of a polyurethane-vinyl polymer hybrid E is prepared by polymerization, initiated by free radicals, of a mixture of ethylenically unsaturated monomers MU2 in the presence of a polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups, resulting in an improved basecoat coating composition.

[0023] More specifically, an aqueous polyurethane-vinyl polymer hybrid dispersion D comprising the reaction product E of one or more ethylenically unsaturated monomers MU2(s), MU2 being polymerized in the presence of a polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups (thereby forming the reaction product E); The acid-group-containing polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups is acid salt-containing hydroxyl-functional polyurethanes PUSoh having pendant ethylenically unsaturated groups and pendant groups of acid salts, and one or more ethylenically unsaturated monomers MU1 is the reaction product of MU1 is polymerized in the presence of an acid group-containing hydroxyl functional polyurethane PUSoh (thereby forming a polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups); The acid-group-containing hydroxyl-functional polyurethane PUSoh is Hydroxyl-functional polyurethanes PUoh, and one or more compounds An(s) capable of reacting with an acid group to form a base (thereby forming PUSoh) is the reaction product of The hydroxyl-functional polyurethane PUoh comprises one or more polyisocyanates I, one or more isocyanate-reactive compounds having at least two isocyanate-reactive groups selected from the group consisting of monomeric compounds Moh, polymeric compounds Poh, and mixtures thereof, one or more isocyanate-reactive monomers MAoh(s) having at least two isocyanate-reactive groups and at least one acid group or group capable of forming an acid when in contact with water, one or more isocyanate-reactive monomers MUoh(s) having at least two isocyanate-reactive groups and an ethylenically unsaturated group, and one or more primary or secondary amines Aoh(s) having at least one hydroxyl group is the reaction product of An aqueous polyurethane-vinyl polymer hybrid dispersion D is provided.

[0024] The hydroxyl-functional polyurethane PUoh is preferably characterized by a hydroxyl number of 10 to 100 mg KOH / g, more preferably 15 to 85 mg KOH / g, even more preferably 20 to 75 mg KOH / g (the amount of ethylenically unsaturated monomer(s) MU1 is not taken into account for determining the hydroxyl number of said hydroxyl-functional polyurethane PUoh).

[0025] Without being bound by theory, it is believed that the monomer MU1(s) co-reacts with the ethylenically unsaturated groups leading from PUSoh to form the homogeneous polymer phase of the polyurethane-vinyl polymer hybrid prepolymer PUSpp, whereas the monomer MU2(s) is copolymerized in the presence of PUSpp to build a separate polymer phase (i.e., a separate polymer phase from the homogeneous polymer phase of the polyurethane-vinyl polymer hybrid prepolymer PUSpp).

[0026] In the context of this detailed description, "Polyurethane-vinyl polymer hybrid E" is also referred to as "reaction product E".

[0027] In the context of this detailed description, "PUSpp" refers to "acid salt group-containing polyurethane-vinyl polymer hybrid prepolymer," or in other words, "polyurethane-vinyl polymer hybrid prepolymer that includes acid salt groups." More specifically, "PUSpp" refers to "polyurethane-vinyl polymer hybrid prepolymer with pendant acid salt groups."

[0028] In the context of this detailed description, "PUSoh" refers to "acid salt group-containing hydroxyl functional polyurethane, or in other words, "a hydroxyl functional polyurethane that includes an acid salt group," and more specifically, "PUSoh" refers to "an acid salt group-containing hydroxyl functional polyurethane having pendant ethylenically unsaturated groups and pendant groups (or pendant salt groups) of acid salts."

[0029] In the context of this detailed description, "MAoh" refers to an "isocyanate-reactive monomer having at least two isocyanate-reactive groups and at least one acid group or group capable of forming an acid when contacted with water."

[0030] In the context of this detailed description, "MUoh" refers to an "isocyanate-reactive monomer having at least two isocyanate-reactive groups and an ethylenically unsaturated group."

[0031] In the context of this detailed description, "renewable feedstock" refers to a natural resource that replenishes either through natural renewal or other repetitive processes (over a finite amount of time on a human time scale) to replace portions that are depleted through use and consumption. Substances or mixtures of substances obtained from such renewable feedstocks should have a bio-based carbon content, in total, greater than 20% by weight of the total carbon content of the substance or mixture, where the bio-carbon content is measured using the ASTM D6866-20 standard.

[0032] The ethylenically unsaturated monomer MU2 is preferably selected from the group consisting of monoethylenically unsaturated monomers, polyethylenically unsaturated monomers, and mixtures thereof.

[0033] The ethylenically unsaturated monomer MU2 is preferably an ester of (meth)acrylic acid and an aliphatic linear, branched, or cyclic monoalcohol having 1 to 12 carbon atoms in the alkyl group, more preferably selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, and mixtures thereof.

[0034] The ethylenically unsaturated monomer MU2 optionally comprises a monomer selected from the group consisting of ketone-functional (meth)acrylates such as acetoacetoxyethyl methacrylate, hydroxy-functional (meth)acrylates such as hydroxyethyl methacrylate, epoxy-functional (meth)acrylates such as glycidyl methacrylate, (meth)acrylamides such as diacetone acrylamide, vinyl monomers such as styrene, vinyl toluene, acrylonitrile, methacrylonitrile, and mixtures thereof.

[0035] The ethylenically unsaturated monomer MU2 may further comprise up to 10% by weight of the total amount of ethylenically unsaturated monomers, more particularly the ethylenically unsaturated monomer MU2 may optionally comprise ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, butane-1,4-diol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triplyl glycol di(meth)acrylate, tetramethyl ... The polyethylenically unsaturated monomer comprises up to 10% by weight of the total amount of ethylenically unsaturated monomers selected from the group consisting of pyrene glycol di(meth)acrylate, hexanediol di(meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, glyceryl tri(meth)acrylate, trimethylolpropane di(meth)acrylate monoallyl ether, trimethylolpropane (meth)acrylate diallyl ether, pentaerythritol tri(meth)acrylate monoallyl ether, pentaerythritol di(meth)acrylate diallyl ether, pentaerythritol (meth)acrylate triallyl ether, triallylsucrose, and pentaallylsucrose, and mixtures thereof.

[0036] The ethylenically unsaturated monomer MU2 is more preferably selected from the group consisting of alkyl acrylates, alkyl (meth)acrylates, and mixtures thereof.

[0037] Polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups is acid-group-containing hydroxyl-functional polyurethanes PUSoh having pendant ethylenically unsaturated groups and pendant salt groups, and one or more ethylenically unsaturated monomers MU1 which are polymerized in the presence of an acid-group-containing hydroxyl-functional polyurethane PUSoh is the reaction product of The one or more ethylenically unsaturated monomers MU1 are selected from the group consisting of esters of (meth)acrylic acid with aliphatic linear, branched, or cyclic monoalcohols having 1 to 12 carbon atoms in the alkyl group, ketone-functional (meth)acrylates, hydroxy-functional (meth)acrylates, epoxy-functional (meth)acrylates, (meth)acrylamides, vinyl monomers, and mixtures thereof.

[0038] The ethylenically unsaturated monomer MU1 is preferably selected from the same group of monomers as any of the polyethylenically unsaturated monomers described above for MU2 (see above), but other than for MU1 (i.e., the ethylenically unsaturated monomer MU1 is preferably a monoethylenically unsaturated monomer).

[0039] Furthermore, the weight percentage of each monomer in MU1 is preferably different from the weight percentage of the corresponding monomer in MU2, such that the sum of the weight percentages of all monomers in MU1 is 100% and the sum of the weight percentages of all monomers in MU2 is 100%.

[0040] Optionally, the ethylenically unsaturated monomer MU1 is selected such that the polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups comprises pendant polymerized ethylenically unsaturated monomers and terminal polymerized ethylenically unsaturated monomers.

[0041] The ethylenically unsaturated monomer MU1 is preferably selected such that the polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups is substantially free of polyurethane chains having terminal polymerized ethylenically unsaturated monomers.The ethylenically unsaturated monomer MU1 is more preferably selected such that the polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups contains 0% terminal polymerized ethylenically unsaturated monomers.

[0042] Alternatively and preferably, where possible, the ethylenically unsaturated monomers MU1 and / or MU2 are derived from renewable feedstocks (i.e., for example, monomers such as n-heptyl acrylate, isobornyl methacrylate, and / or isobutyl acrylate are derived partially or completely from (bio)renewable resources). The exact amount of biocarbon in these monomers can be measured by the method described in ASTM D6866-20, where the carbon originating from current biomass-based energy is differentiated from that originating from fossil energy, and the biocarbon content is reported as a percentage of the total organic carbon content (TOC). Other standard methods for measuring the percentage of renewable carbon are ISO16620-2 and CEN16640.

[0043] Another alternative method to reduce the carbon footprint of the polymer hybrid dispersion is to use recycled monomers for its preparation. Polymers such as poly(methyl methacrylate) or poly(styrene) can be pyrolyzed at temperatures above their ceiling temperature. Purification of pyrolysis products can then obtain recycled monomers such as methyl methacrylate or styrene, which can be further used in emulsion polymerization to prepare the polymer dispersion.

[0044] In yet another alternative, the ethylenically unsaturated monomers MU1 and / or MU2 are monomers obtained and / or recycled from petrochemical and / or renewable feedstocks.

[0045] In the context of this detailed description, "biological carbon content" refers to biological carbon content.

[0046] The acid-group-containing hydroxyl-functional polyurethane PUSoh is Hydroxyl-functional polyurethanes PUoh containing pendant acid groups or pendant acid group precursors and pendant ethylenically unsaturated groups, and one or more neutralizing compounds An(s) It is the reaction product of

[0047] In the context of this detailed description, "acid group precursor" refers to a group that is capable of forming an acid when contacted with water.

[0048] The one or more neutralizing compounds An(s) are preferably selected from the group consisting of primary, secondary and tertiary amines and strong Arrhenius bases such as hydroxides of alkali metals and alkaline earth alkali metals.

[0049] The neutralizing compound(s) An are more preferably selected from the group consisting of ammonia and compounds having not more than one hydroxyl group and at least one tertiary amino group per molecule.

[0050] The neutralizing compound(s) An are most preferably selected from the group consisting of ammonia, N,N-dimethylaminoethanol, 1-dimethylamino-2-propanol, 1-dimethylamino-3-propanol, and also N-(2-hydroxyethyl)piperazine and mixtures thereof.

[0051] The hydroxyl-functional polyurethane PUoh is composed of one or more polyisocyanates I, one or more isocyanate-reactive compounds Moh and / or Poh having at least two isocyanate-reactive groups, one or more isocyanate-reactive monomers MAoh having at least two isocyanate-reactive groups and at least one acid group or acid group precursor, one or more isocyanate-reactive monomers MUoh having at least two isocyanate-reactive groups and an ethylenically unsaturated group, and one or more primary or secondary amines Aoh(s) having at least one hydroxyl group It is the reaction product of

[0052] The one or more polyisocyanates I are selected from the group consisting of aromatic or aliphatic or mixed aliphatic aromatic isocyanates, preferably trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), propylene diisocyanate, ethyl ethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, cyclopentylene 1,3-diisocyanate, cyclohexylene 1,4-diisocyanate, cyclohexylene 1,2-diisocyanate, phenylene 1,3-diisocyanate, phenylene 1,4-diisocyanate, toluylene 2,4-diisocyanate, toluylene 2,6-diisocyanate, biphenylene 4,4'-diisocyanate, isocyanate, bis-(4-isocyanatophenyl)methane (MDI), naphthylene-1,5-diisocyanate, naphthylene 1,4-diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3-tri-methylcyclohexane (IPDI), bis-(4-isocyanatocyclohexyl)methane (H12-MDI), 4,4'-diisocyanatodiphenyl ether, 2,3-bis-(8-isocyanatooctyl)-4-octyl-5-hexylcyclohexene, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, uretdiones of the above diisocyanates, isocyanurates of the above diisocyanates, and allophanates of the above diisocyanates, and mixtures thereof.

[0053] Alternatively and preferably, where possible, the polyisocyanate I is obtained from renewable feedstocks. In particular, isophorone diisocyanate obtained from bio-based acetone is preferred. Other preferred polyisocyanates partially derived from renewable feedstocks are, for example, 1,5-pentaethylene diisocyanate, diisocyanate of methyl or ethyl ester of l-lysine, isosorbide-based diisocyanates, furan-based diisocyanates, bis(4-isocyanato-2-methoxyphenoxy)alkanes, bis(4-isocyanato-2,6-dimethoxyphenoxy)alkanes, 2,4-diisocyanato-1-pentadecylbenzene, fatty acid-based di- and polyisocyanates, dimer fatty acids and vegetable oils, 1-isocyanato-10-[(isoisocyanatomethyl)thio]decane, and the product known under the trade name TOLONATE®X FLO100.

[0054] The isocyanate-reactive compound having at least two isocyanate-reactive groups is selected from the group consisting of a monomeric compound Moh having at least two isocyanate-reactive groups, a polymeric compound Poh having at least two isocyanate-reactive groups, and mixtures thereof.

[0055] A polymeric compound Poh having at least two isocyanate-reactive groups is to be understood as a compound which comprises at least two repeat units.

[0056] The polymeric compound Poh having at least two isocyanate-reactive groups is preferably selected from the group consisting of polyesters, polylactones, polyethers, polycarbonates, polyamides, polyenes, polydienes, and mixtures thereof, more preferably selected from the group consisting of hydroxyl-functional polyesters, hydroxyl-functional polylactones, hydroxyl-functional polyethers, hydroxyl-functional polycarbonates, hydroxyl-functional polyamides, hydroxyl-functional polyenes, hydroxyl-functional polydienes, and mixtures thereof, and most preferably selected from the group consisting of hydroxyl-functional polyesters, hydroxyl-functional polycarbonates, hydroxyl-functional polyethers, and mixtures thereof.

[0057] The polymeric compound Poh is preferably characterized by a number average molecular weight of 300 to 10,000 g / mol, more preferably 400 to 8,000 g / mol, most preferably 500 to 5,000 g / mol, and even more preferably 500 to 3,000 g / mol.

[0058] The polymeric compound Poh having at least two isocyanate-reactive groups is more preferably selected from the group consisting of hydroxyl-functional polyesters, hydroxyl-functional polycarbonates, hydroxyl-functional polyethers, and mixtures thereof, said polymeric compound Poh being characterized in that it has a number average molecular weight of 500 to 3,000 g / mol.

[0059] The polymeric compound Poh having at least two isocyanate-reactive groups is preferably a polymeric compound having at least two hydroxyl groups (more specifically, in the polymeric compound Poh, the at least two isocyanate-reactive groups are preferably at least two hydroxyl groups).

[0060] The polymeric compound Poh is preferably characterized by a hydroxyl number between 40 and 300 mg KOH / g, even more preferably between 50 and 250 mg KOH / g, most preferably between 70 and 150 mg KOH / g.

[0061] The polymeric compound Poh having at least two hydroxyl groups is more preferably selected from the group consisting of polyester Poh1 having at least two hydroxyl groups, polyether Poh2 having at least two hydroxyl groups, polycarbonate Poh3 having at least two hydroxyl groups, and mixtures thereof.

[0062] More specifically, the polymeric compound Poh1 is a hydroxyl functional polyester, which is the reaction product of a stoichiometric excess of one or more diol(s) and one or more diacid(s), which polyester is characterized in that it has a hydroxyl number of 40-300 mg KOH / g and an acid number of less than 3 mg KOH / g, the acid number being the remainder, generated by terminal unreacted acid functional groups.

[0063] The polyester Poh1 having at least two hydroxyl groups preferably has two hydroxyl groups and is prepared from a stoichiometric excess of one or more diols and one or more diacids, the diol is preferably selected from the group consisting of 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,2- and 1,4-butanediol, 2,2'-oxydi(ethan-1-ol), 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 1,4-bis-hydroxymethylcyclo-hexane, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,18-octadecanediol, 1,21-heneicosanediol, 1,25-pentacosanediol, isosorbide, isomannide, isoidide, and mixtures thereof; The diacid is preferably selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, octanedioic acid, further dimer fatty acids having up to 40 carbon atoms, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and mixtures thereof.

[0064] Optionally, one or more hydroxy-carboxylic acid(s), such as hydroxybenzoic acid, lactic acid, γ-hydroxybutyric acid, Δ-hydroxyvaleric acid, Υ-hydroxycaproic acid, etc., in combination with one or more diols may be used in the preparation of the hydroxyl-functional polyester Poh1.

[0065] Alternatively and preferably, where possible, the diol (i.e., 1,3-propanediol), diacid (i.e., succinic acid), or hydroxy-carboxylic acid(s) (i.e., lactic acid) used in the preparation of the hydroxyl-functional polyester Poh1 are derived from renewable feedstocks.

[0066] The polyester Poh1 is more preferably a condensation product of adipic acid with one or more diols selected from the group consisting of 1,4-butanediol, 1,6-hexanediol, and 2,2-dimethyl-1,3-propanediol, said polyester being characterized in that it has a hydroxyl number of 40 to 300 mg KOH / g, even more preferably 40 to 150 mg KOH / g, an acid number of less than 3 mg KOH / g, preferably less than 2 mg KOH / g, more preferably less than 1 mg KOH / g, said acid number being the remainder, generated by unreacted terminal acid functional groups.

[0067] The hydroxyl functional polyester Poh1 having two hydroxyl groups should be understood as a polyester having approximately two hydroxyl groups and a negligible amount of carboxylic acid groups, since it rarely achieves 100% conversion.

[0068] The polyester Poh1 having two hydroxyl groups does not contain any carboxylic acid side groups resulting from the co-condensation of a hydroxyl functional monomer (MAoh) having at least two hydroxyl groups and at least one carboxylic acid group (or, in other words, the polyester Poh1 having two hydroxyl groups contains 0% carboxylic acid side groups resulting from the co-condensation of a hydroxyl functional monomer MAoh having at least two hydroxyl groups and at least one carboxylic acid group).

[0069] Thus, the polyester Poh1 in the present invention is prepared from a stoichiometric excess of diol relative to the diacid, said diol excluding compounds having at least two hydroxyl groups and at least one carboxylic acid group (MAoh), such as 2,2-(bis-hydroxymethyl)acetic acid, 2,2-(bishydroxymethyl)-propionic acid, or 2,2-(bishydroxymethyl)butyric acid.

[0070] The polyether compound Poh2 is preferably a poly(oxyalkylene) glycol containing 2 to 6 alkyl radicals, more preferably the polyether Poh2 is selected from the group consisting of poly(oxyethylene) glycol, poly(oxypropylene) glycol, poly(oxytetramethylene) glycol, and mixtures thereof.

[0071] Alternatively and preferably, where possible, the polyether compound Poh2 is a poly(oxyalkylene) glycol obtained from renewable feedstocks, more preferably they are poly(oxyalkylene) glycols obtained from biobased 1,3-propanediol.

[0072] The polycarbonate compound Poh3 is preferably prepared by reaction of a polyol such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, 1,4-bishydroxymethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, neopentyl glycol, trimethylolpropane, or pentaerythritol with a dicarbonate such as dimethyl, diethyl, or diphenyl carbonate, or with phosgene.

[0073] Alternatively and preferably, where possible, the polycarbonate compounds Poh3 are obtained from renewable feedstocks, more preferably they are polycarbonate compounds obtained from bio-based polyols (i.e. bio-based 1,3-propanediol or 1,5-pentanediol).

[0074] The monomeric compound Moh having at least two isocyanate-reactive groups is preferably a monomeric compound having at least two hydroxyl groups, or having at least two primary amino groups, or having at least one hydroxyl group and at least one primary amino group.

[0075] The monomeric compound Moh having at least two hydroxyl groups is preferably 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,2- and 1,4-butanediol, 2,2'-oxydi(ethane-1-ol), 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 1,4-bis-hydroxymethylcyclohexane, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,18-octadecanediol, 1,21-heneicosanediol, 1,25-pentacosanediol, isosorbide , isomannide, isoidide, and mixtures thereof, more preferably selected from the group consisting of 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,2- and 1,4-butanediol, 2,2'-oxydi(ethan-1-ol), 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 1,4-bis-hydroxymethylcyclohexane, and mixtures thereof, and most preferably selected from the group consisting of 1,2-ethanediol, 1,4-butanediol, 2,2'-oxydi(ethan-1-ol), 2,2-dimethyl-1,3-propanediol, and mixtures thereof.

[0076] The monomeric compound Moh having at least two primary amino groups is preferably selected from the group consisting of 1,4-diaminobutane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane, and mixtures thereof.

[0077] The monomeric compound Moh having at least one hydroxyl group and at least one primary amino group is preferably selected from the group consisting of ethanolamine, propanolamine, 2-(2-amino-ethylamino-)ethanol, and mixtures thereof.

[0078] The monomeric compound Moh may comprise a mixture of one or more monomeric compounds having at least two hydroxyl groups and one or more monomeric compounds having at least two primary amino groups.

[0079] The one or more isocyanate-reactive monomers MAoh having at least two isocyanate-reactive groups and at least one acid group or acid group precursor such as an anhydride are preferably monomers having at least two hydroxyl groups and at least one acid group, more preferably the one or more MAoh monomers are selected from the group consisting of 2,2-(bis-hydroxymethyl)acetic acid, 2,2-(bishydroxymethyl)-propionic acid, 2,2-(bishydroxymethyl)butyric acid, and mixtures thereof.

[0080] The one or more isocyanate-reactive monomers MUoh having at least two isocyanate-reactive groups and an ethylenically unsaturated group are preferably selected from the group consisting of compounds having at least two hydroxyl groups and an ethylenically unsaturated group, more preferably glycerin mono(meth)acrylate (also called glycerin mono(meth)acrylate), trimethylolpropane mono(meth)acrylate, and mixtures thereof.

[0081] The one or more primary or secondary amines Aoh having at least one hydroxyl group are preferably selected from the group consisting of 2-aminoethanol, 2-methylaminoethanol, 3-aminopropanol, 2-amino-1,3-propanediol, diethanolamine, 1,1'-iminodi-2-propanol, and mixtures thereof.

[0082] The isocyanate-reactive monomer MUoh having at least two isocyanate-reactive groups and an ethylenically unsaturated group is preferably provided in an amount such that the hydroxyl-functional polyurethane PUoh has an unsaturation equivalent weight (UEW) of 3,500 to 35,000 g / equiv, preferably 4,500 to 20,000 g / equiv, more preferably 6,000 to 15,000 g / equiv, said unsaturation being provided by pendant ethylenically unsaturated groups (or pendant ethylenically unsaturated groups).

[0083] The hydroxyl-functional polyurethane PUoh preferably has an acid number of 30 to 60 mg KOH / g, said acid number being characterised in that said MAoh is produced by an isocyanate-reactive monomer MAoh having at least two isocyanate-reactive groups and at least one acid group or group capable of forming an acid when in contact with water, said MAoh being incorporated in the polyurethane to at least 95% via urethane or urea bonds, preferably via urethane bonds.

[0084] Optionally, the hydroxyl functional polyurethane PUoh and the acid salt group-containing hydroxyl functional polyurethane PUSoh contain pendant and terminal ethylenically unsaturated groups that can be obtained from a monomer containing one hydroxyl group and an ethylenically unsaturated group, such as, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or hydroxybutyl (meth)acrylate, added as part of the MU1 monomer.

[0085] The hydroxyl functional polyurethane PUoh and the acid salt group-containing hydroxyl functional polyurethane PUSoh are preferably substantially free of terminal ethylenically unsaturated groups. The hydroxyl functional polyurethane PUoh and the acid salt group-containing hydroxyl functional polyurethane PUSoh more preferably contain 0% terminal ethylenically unsaturated groups.

[0086] Polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups is 60 to 85% by weight, preferably 65 to 80% by weight, of an acid-group-containing hydroxyl-functional polyurethane PUSoh having pendant ethylenically unsaturated groups and pendant salt groups, and One or more polymerized ethylenically unsaturated monomers MU1 (single or multiple) from 15 to 40% by weight, preferably from 20 to 35% by weight The total of PUSoh and MU1 is 100%.

[0087] The polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups is preferably characterized by a weight ratio of acid group-containing hydroxyl functional polyurethane PUSoh to vinyl polymer derived from MU1 of greater than one.

[0088] The acid-group-containing hydroxyl-functional polyurethane PUSoh having pendant ethylenically unsaturated groups and pendant salt groups is 30 to 50% by weight, preferably 35 to 45% by weight, of one or more polyisocyanates I, 30 to 40% by weight, preferably 33 to 37% by weight, of one or more polymeric compounds Poh(s) having at least two isocyanate-reactive groups, (optionally) 1 to 4% by weight, preferably 2 to 3% by weight, of one or more monomeric compounds Moh(s) having at least two isocyanate-reactive groups, 7 to 11% by weight, preferably 8 to 10% by weight, of one or more isocyanate-reactive monomers MAoh(s) having at least two isocyanate-reactive groups and at least one acid group, 0.5 to 4% by weight, preferably 1 to 3% by weight, of one or more isocyanate-reactive monomers MUoh(s) having at least two isocyanate-reactive groups and an ethylenically unsaturated group, and 7 to 11% by weight, preferably 8 to 10% by weight, of one or more primary or secondary amines Aoh(s) carrying at least one hydroxyl group wherein the reaction product is The sum of I, Poh, Moh, MAoh, MUoh, and Aoh is 100%, and the acid group of MAoh is further converted to acid-base by the addition of one or more neutralizing compounds An(s).

[0089] The aqueous polyurethane-vinyl polymer hybrid dispersion D is Polymerized ethylenically unsaturated monomer MU2 30 to 80% by weight, preferably 40 to 70% by weight, Polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups 20-70% by weight, preferably 30-60% by weight The total of PUSpp and polymerized MU2 is 100%.

[0090] Preferably, the reaction product E of one or more ethylenically unsaturated monomers MU2(s) polymerized in the presence of said polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups is characterized by a weight ratio of acid salt group-containing hydroxyl functional polyurethane PUSoh to the total vinyl polymer derived from MU1 and MU2 of 1 or less than 1. More preferably, the reaction product E of one or more ethylenically unsaturated monomers MU2(s) polymerized in the presence of said polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups is characterized by a weight ratio of acid salt group-containing hydroxyl functional polyurethane PUSoh to the total vinyl polymer derived from MU1 and MU2 of less than 1.

[0091] The aqueous polyurethane-vinyl polymer hybrid dispersion D of the present invention is preferably 40-55 wt. % of reaction product E, preferably 43-50 wt. % (or wt. % of solids), and Water: 45 to 60% by weight, preferably 50 to 57% by weight Includes.

[0092] The polyurethane-vinyl polymer hybrid (or reaction product) E of the aqueous polyurethane-vinyl polymer hybrid dispersion D preferably has a core-shell structure, which is a core (substantially) comprising polymerized ethylenically unsaturated monomers, and A shell that essentially consists of polyurethane As will be appreciated by those skilled in the art, the core-shell structure can be demonstrated by transmission electron microscopy and attenuated total reflection-Fourier transform infrared spectroscopy.

[0093] The dispersed particles of reaction product E are preferably characterized by a Z-average particle size according to ISO 22412 of 50-150 nm, preferably 60-120 nm (measured by dynamic light scattering).

[0094] The aqueous polyurethane-vinyl polymer hybrid dispersion D is a) mixing a polymeric compound Poh having at least two isocyanate-reactive groups, preferably at least two hydroxyl groups, in the presence of one or more isocyanate-reactive monomers MAoh(s) having at least two isocyanate-reactive groups, preferably at least two hydroxyl groups and an acid group or an acid group precursor, and optionally in the presence of one or more isocyanate-reactive monomers Moh(s) having at least two isocyanate-reactive groups, preferably at least two hydroxyl groups or at least two primary amino groups or at least a hydroxyl group and a primary amino group, heating the mixture under stirring to a temperature of at least 60° C., preferably at least 70° C., more preferably at least 80° C. and at most 150° C., preferably at most 130° C., more preferably at most 130° C., b) continuously adding sub-stoichiometric amounts of polyfunctional isocyanate I to the mixture of step a), preferably over a period of 10-60 minutes, preferably 20-40 minutes, while maintaining the temperature in the range of 60°C-150°C, preferably 80°C-130°C, thereby forming an isocyanate-reactive polyurethane prepolymer, preferably a hydroxyl-functional polyurethane prepolymer, characterized in that the hydroxyl number is 30-140 mgKOH / g, preferably 40-130 mgKOH / g; c) adding one or more isocyanate-reactive monomer(s) MUoh having at least two isocyanate-reactive groups, preferably at least two hydroxyl groups and an ethylenically unsaturated group, and optionally one or more isocyanate-reactive monomer(s) Moh having at least two isocyanate-reactive groups, preferably at least two hydroxyl groups or at least two primary amino groups or at least a hydroxyl group and a primary amino group, and preferably one or more ethylenically unsaturated monomer(s) MU1 to the isocyanate-reactive polyurethane prepolymer, preferably a hydroxyl-functional prepolymer, of step b) and homogenizing the mixture, optionally in the presence of an antioxidant or a radical scavenger, d) adding a further amount of polyfunctional isocyanate I to the homogenized mixture of step c) in stoichiometric excess while stirring at a temperature in the range of 60°C to 100°C, preferably in the range of 70 to 90°C, thereby forming an isocyanate-functional polyurethane prepolymer, preferably said isocyanate-functional polyurethane prepolymer being characterized by an isocyanate equivalent weight of 600 to 2,200 g / equiv, more preferably 800 to 2,000 g / equiv, most preferably 1,000 to 1,800 g / equiv, the amount of ethylenically unsaturated monomer(s) MU1 optionally added in step c) being not taken into account for the measurement of the equivalent weight of said isocyanate-functional polyurethane prepolymer. e) rapidly adding a mixture comprising one or more primary or secondary amine(s) Aoh having at least one hydroxyl group and preferably one or more ethylenically unsaturated monomer(s) MU1 to the isocyanate-functional polyurethane prepolymer of step d), thereby forming a hydroxyl-functional polyurethane PUoh from the ethylenically unsaturated monomer(s) MU1, said hydroxyl-functional polyurethane PUoh being preferably characterized by a hydroxyl number between 10 and 100 mg KOH / g, more preferably between 15 and 85 mg KOH / g, even more preferably between 20 and 75 mg KOH / g, the amount of ethylenically unsaturated monomer(s) MU1 optionally added in step c) and / or in this step e) not being taken into account for the determination of the hydroxyl number of said hydroxyl-functional polyurethane PUoh. f) adding a neutralizing agent An to the mixture of step e) and homogenizing the mixture at a temperature ranging from 40° C. to 80° C., preferably from 50° C. to 80° C., for at least 5 minutes, preferably from 5 to 15 minutes, thereby forming an acid salt group-containing hydroxyl functional polyurethane PUSoh from the ethylenically unsaturated monomer(s) MU1; g) adding water to the homogenized mixture of step f), thereby forming an emulsion; h) homogenizing the emulsion of step g) at a temperature in the range of 40° C. to 80° C., preferably in the range of 50° C. to 70° C., for at least 10 minutes, preferably 20 to 30 minutes; i) redox polymerizing the homogenized emulsion of step h) by gradually adding at least one of the redox system components for at least 10 minutes, preferably 10 to 30 minutes, while maintaining a temperature in the range of 60° C. to 80° C., thereby forming a polymerization mixture; j) maintaining the temperature of the polymerization mixture at a temperature of 65-85° C. for at least 15 minutes, preferably 20-30 minutes, for further polymerization, thereby forming a polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups; k) rapidly adding the mixture of ethylenically unsaturated monomers MU2 to the polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups of step j) and homogenizing the mixture at a temperature ranging from 40° C. to 80° C. for at least 10 minutes, preferably 20 to 30 minutes; l) redox polymerizing the homogenized emulsion of step k) by gradually adding at least one of the redox system components for at least 10 minutes, preferably 10 to 30 minutes, while maintaining a temperature in the range of 60° C. to 80° C., thereby forming a polymerization mixture; m) maintaining a temperature in the range of 60°C to 80°C for at least 15 minutes, preferably 20 to 30 minutes, to complete the polymerization, thereby forming an aqueous polyurethane-vinyl polymer hybrid dispersion D1 comprising a polyurethane-vinyl polymer hybrid E; It is prepared in a multi-step process including:

[0095] Preferably, in step c), one or more isocyanate-reactive monomers MUoh(s) having at least two isocyanate-reactive groups, preferably at least two hydroxyl groups and an ethylenically unsaturated group, and one or more isocyanate-reactive monomers Moh having at least two isocyanate-reactive groups, preferably at least two hydroxyl groups or at least two primary amino groups, or at least hydroxyl groups and primary amino groups, and preferably one or more ethylenically unsaturated monomers MU1(s) are added to the hydroxyl-functional polyurethane prepolymer of step b) and the mixture is optionally homogenized in the presence of an antioxidant or a radical scavenger.

[0096] In the process for the preparation of the aqueous dispersion of the acid-group-containing hydroxyl-functional polyurethane PUSoh, the ethylenically unsaturated monomer MU1 may be added in any of steps a) to e).

[0097] The ethylenically unsaturated monomer MU1 is preferably added in at least one of steps a) to e).

[0098] The ethylenically unsaturated monomer MU1 is more preferably added (only) in step c) and / or in step e).

[0099] Fast addition (i.e., fast addition) of one or more compound(s) should be understood as the addition of one or more compound(s) for a time that is at least 50% less, preferably at least 60% less, more preferably at least 70% less, even more preferably at least 80% less, and most preferably at least 90% less, or even at least 95% less than the homogenization time of the resulting final mixture.

[0100] More specifically, a fast addition of the ethylenically unsaturated monomer in steps e) and k) is to be understood as an addition time that is at least 50% less, preferably at least 60% less, more preferably at least 70% less, even more preferably at least 80% less, most preferably at least 90% less, or even at least 95% less than the homogenization time of the resulting final mixture containing said ethylenically unsaturated monomer. The ethylenically unsaturated monomer MU1 in step e) and the ethylenically unsaturated monomer MU2 in step k) are preferably added in a one shot addition.

[0101] As used herein, "one shot addition of one or more compound(s)" refers to the addition of one or more compound(s) for a time that is substantially 100% less than the homogenization time of the resulting final mixture.

[0102] Redox polymerization, as referred to throughout this specification, is a polymerization method well known to those skilled in the art.

[0103] The redox polymerization of steps i) and l) is in fact Add the redox solution first and then slowly add the peroxide, or Add the peroxide first and then slowly add the redox solution, or · Gradual supply of redox solution and peroxide Includes.

[0104] The antioxidants or radical scavengers optionally added in step c) are sterically hindered phenols such as phenols bearing bulky substituents, preferably tert-butyl groups at the 2- and 6-positions, and an alkyl substituent at the 4-position.

[0105] The aqueous dispersion D1 containing polyurethane-vinyl polymer hybrid E may be subjected to a subsequent fast addition (step n) of a mixture of ethylenically unsaturated monomers MU2, where the mixture of E and MU2 is homogenized (thereby forming a homogenized mixture or emulsion) for at least 10 minutes, preferably 20 to 30 minutes, at a temperature of 40° C. to 80° C. Then, the homogenized mixture is redox polymerized (step o) as described in step l) (see above), and the polymerization is terminated (step p) as described in step m) (see above), to obtain an aqueous polyurethane-vinyl polymer hybrid dispersion D2 (containing polyurethane-vinyl polymer hybrid E).

[0106] The aqueous polyurethane-vinyl polymer hybrid dispersions D according to the invention are suitable for a variety of applications, for example for the preparation of coating systems as binders for water-dilutable adhesives or as resins for printing inks.

[0107] They can be combined, and are generally mixed, with other aqueous dispersions and solutions of plastics, such as acrylic and / or methacrylic polymers, polyurethanes, polyurea resins, polyester resins and epoxy resins, polyvinyl acetates, polyvinyl chlorides, polyvinyl ethers, polychloroprene, polyacrylonitriles and thermoplastics based on ethylene / butadiene / styrene copolymers. They can also be combined with substances based on inorganic thixotropic agents, such as polyacrylates or polyurethanes, which have a thickening action and contain carboxyl groups, hydroxyethylcellulose, polyvinyl alcohols and bentonite, sodium magnesium silicate and lithium fluoride sodium magnesium silicate.

[0108] The aqueous polyurethane-vinyl polymer hybrid dispersions D according to the invention can be applied to the most diverse substrates, such as ceramics, wood, glass, concrete, and preferably plastics such as polycarbonate, polystyrene, polyvinyl chloride, polyester, poly(meth)acrylate, acrylonitrile / butadiene / styrene polymers, most preferably metals such as iron, copper, aluminum, steel, brass, bronze, tin, zinc, titanium, magnesium, etc. They adhere to the various substrates without adhesion-promoting primers or intermediate layers, although such layers may of course be present in the final coated article set-up (and the dispersions D according to the invention can be applied to those layers as well).

[0109] The aqueous polyurethane-vinyl polymer hybrid dispersions D are suitable, for example, for the production of anti-corrosion coatings and / or intermediate coatings for the most diverse fields of use, in particular for the production of metal and solid base paints in the multicoat build-up of paints for the field of automotive and plastics painting, and for the production of primer paints for the field of plastics painting.

[0110] The aqueous coating system comprising the aqueous polyurethane-vinyl hybrid polymer dispersion D can contain all the inorganic or organic pigments and dyes known and common in paint technology, as well as wetting agents, foam suppressors, flow control agents, stabilizers, catalysts, fillers, plasticizers, solvents, and the usual additives such as thickeners, flow control agents, wetting agents, light stabilizers, etc. Crosslinking agents (or crosslinkers) common in the paint industry, such as water-soluble or emulsifiable aminoplast crosslinkers, for example urea, cyclic urea, melamine or benzoguanamine resins, polyisocyanates or prepolymers with terminal isocyanate groups, water-soluble or water-dispersible polyaziridines and block polyisocyanates, can be added during the formation (of the aqueous coating system). Alternatively, the crosslinking agents can be added during the synthesis of the aqueous polyurethane-vinyl hybrid polymer dispersion D.

[0111] The aqueous coating system comprising the aqueous polyurethane-vinyl hybrid polymer dispersion D may alternatively comprise a crosslinking agent selected from the group of di- or polyamines, carbohydrazides, and di- or poly-carboxylic acid hydrazides, and mixtures thereof. For example, the crosslinking agent may be adipic acid dihydrazide. The crosslinking agent may be added to the aqueous polyurethane-vinyl hybrid polymer dispersion D during its synthesis or may be added at a later stage, for example during the formation of the aqueous coating system.

[0112] It will be apparent to one skilled in the art that the selection of an appropriate crosslinker will depend on the desired coating application and the curing temperature to be used. EXAMPLES

[0113] The following illustrative examples are meant merely to illustrate the invention, but are not intended to limit or otherwise define its scope.

[0114] (Example 1a) Synthesis of polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups In a nitrogen purged reactor, 369 g of polyadipate of 1,6-hexanediol with a number average molecular weight of 1000 g / mol and a hydroxyl number of 112 mg KOH / g, and 79 g of dimethylolpropionic acid were heated to 130° C. and the mixture was maintained at this temperature until a homogeneous solution was formed. 117.9 g of isophorone diisocyanate was then measured for 30 minutes with continued stirring at 130° C. until no more free isocyanate groups were detected.

[0115] After cooling to 100°C, 1.05g 2,6-di-tert-butyl-4-methylphenol, 15.5g 1,4-butylene glycol, 17g glycerol monomethacrylate, and 254g 2-ethylhexyl acrylate were added in succession and the mixture was homogenized. After further cooling to 80°C, 237.7g isophorone diisocyanate was added for 15 minutes and the components were reacted at 75°C until the theoretical NCO content corresponding to complete conversion of the isocyanate reactive groups was obtained and confirmed by titration. Then, 77.8g diethanolamine and 106g methyl methacrylate were added rapidly in one shot and the reaction mixture was held at the resulting temperature with stirring until all the isocyanate groups had reacted. After the addition of 42g N,N-dimethylethanolamine (DMEA), the mixture was homogenized at 75°C for 15 minutes. 1350 g of deionized water were then added to the prepolymer solution with strong stirring at 65°C for 30 minutes. Afterwards, 102 g of a 1.9% aqueous solution of BRUGGOLITE® FF6M was added at 65°C and homogenized for 10 minutes, after which 201.4 g of a 0.5% aqueous solution of tert-butyl hydroperoxide was added continuously for 30 minutes, while maintaining the temperature at 65-75°C by parallel cooling. The reaction mixture was then kept at a temperature of 65-75°C for another 30 minutes for completion of the polymerization and cooled to room temperature (23°C). The dispersion thus obtained had the following characteristics: solids content: 43.3%; pH (10% aqueous solution): 7.6; dynamic viscosity (100s -1 , 23℃): 324mPa.s; Z average particle size (ISO22412): 39nm.

[0116] (Example 1b) Synthesis of aqueous polyurethane-vinyl polymer dispersion D1 250 g of deionized water was added to a nitrogen-purged reactor containing the polyurethane-vinyl polymer hybrid prepolymer PUSpp with pendant acid salt groups of Example 1a. The resulting dispersion was heated to 60° C., whereupon 225 g of methyl methacrylate and 450 g of 2-ethylhexyl acrylate were added rapidly in one shot. The resulting mixture was homogenized at 60° C. for 30 minutes. Then, 208 g of a 3.8% aqueous solution of BRUGGOLITE® FF6M was added at 60° C. for 10 minutes, homogenized, and then 253 g of a 0.8 aqueous solution of tert-butyl hydroperoxide was added continuously for 30 minutes. The reaction temperature was increased to 75° C., while maintaining the temperature below 80° C. by parallel cooling. Once the addition of the tert-butyl hydroperoxide solution was completed, the reaction medium was cooled to 65° C. and maintained at this temperature for 30 minutes.

[0117] (Example 1c) Synthesis of aqueous polyurethane-vinyl polymer dispersion D2 To the aqueous polyurethane-vinyl polymer dispersion D1 of Example 1b, left at 65° C., 225 g of methyl methacrylate and 450 g of 2-ethylhexyl acrylate were added rapidly in one shot and the reaction mixture was homogenized for 30 minutes at 65° C. Then, 253 g of a 0.8% aqueous solution of tert-butyl hydroperoxide were added continuously for 30 minutes and the temperature of the reaction mixture was raised to 75° C., while maintaining a temperature below 80° C. by parallel cooling. Once the addition of the tert-butyl hydroperoxide solution was finished, the reaction medium was cooled to 65° C. and maintained at this temperature for 30 minutes. The dispersion thus obtained had the following characteristics: solids content: 49.7%; pH (10% aqueous solution): 7.7; dynamic viscosity (100 s -1 , 23℃): 737mPa.s; Z average particle size (ISO22412): 102nm.

[0118] (Examples 2 to 14 and Comparative Examples 1 to 3) In Table 1A, the different ingredients for the preparation of polyurethane-vinyl polymer hybrid prepolymers PUSpp with pendant acid groups of Examples 2a to 8a are shown along with the properties of said PUSpp.

[0119] In Table 1B, the different ingredients for the preparation of polyurethane-vinyl polymer hybrid prepolymers PUSpp with pendant acid salt groups of Comparative Examples 1a to 3a are shown along with the properties of said PUSpp.

[0120] In Tables 2A and 2B, the different components for the preparation of the aqueous polyurethane-vinyl polymer dispersions D1 of Examples 2b to 14b are shown, which are prepared from the polyurethane-vinyl polymer hybrid prepolymers PUSpp having pendant acid groups of Examples 1a to 8a, In Table 2A: Examples 2b to 5b were prepared from the PUSpp of Example 1a, Examples 6b and 7b were prepared from the PUSpp of Example 2a, Example 8b was prepared from the PUSpp of Example 3a, Examples 9b and 10b were prepared from the PUSpp of Example 4a, In Table 2B: Example 11b was prepared from the PUSpp of Example 5a, Example 12b was prepared from the PUSpp of Example 6a, Example 13b was prepared from the PUSpp of Example 7a, Example 14b is prepared from the PUSpp of Example 8a.

[0121] In Table 2C, the different components for the preparation of the aqueous polyurethane-vinyl polymer dispersion D1 of Comparative Example 1b to Comparative Example 3b, which is prepared from the acid-group-containing polyurethane-vinyl polymer hybrid prepolymer PUSpp of Comparative Example 1a to Comparative Example 3a, are shown; Comparative Example 1b was prepared from the PUSpp of Comparative Example 1a, Comparative Example 2b was prepared from the PUSpp of Comparative Example 2a, and Comparative Example 3b is prepared from the PUSpp of Comparative Example 3a.

[0122] In Tables 3A and 3B, different components for preparing the aqueous polyurethane-vinyl polymer dispersion D2 of Example 2c to Example 14c prepared from the aqueous polyurethane-vinyl polymer dispersion D1 of Example 2b to Example 14b are shown together with the properties of said aqueous polyurethane-vinyl polymer dispersion D2. The components listed in Table 3A were added to the dispersion D1 prepared in Example 2b to Example 10b of Table 2A without isolation. The components listed in Table 3B were added to the dispersion D1 prepared in Example 11b to Example 14b of Table 2B without isolation.

[0123] In Table 3C, different components for preparing aqueous polyurethane-vinyl polymer dispersion D2 of Comparative Example 1c to Comparative Example 3 prepared from aqueous polyurethane-vinyl polymer dispersion D1 of Comparative Example 1b to Comparative Example 3b are shown together with the characteristics of said aqueous polyurethane-vinyl polymer dispersion D2. The components listed in Table 3C were added to the dispersion D1 prepared in Comparative Example 1b to Comparative Example 3b of Table 2C without isolation.

[0124] [Table 1A-1] [Table 1A-2] [Table 1A-3] [Table 1B-1] [Table 1B-2]

[0125] [Table 2A-1] [Table 2A-2] [Table 2B] [Table 2C]

[0126] [Table 3A] [Table 3B] [Table 3C]

[0127] In Tables 1A and 1B, Examples 2a-8a and Comparative Examples 1a-3a describe compositions for the preparation of polyurethane-vinyl polymer hybrid prepolymers PUSpp having pendant acid salt groups; Polyester diol 1 (Poh) is a polyester prepared from adipic acid and a stoichiometric excess of 1,6-hexanediol and characterized by a number average molecular weight of 1,000 g / mol; Polyester diol 2 (Poh) is a polyester prepared from adipic acid and a stoichiometric excess of 2,2'-dimethyl-1,3-propanediol and characterized by a number average molecular weight of 1,000 g / mol; PolyTHF1000 (Poh) is a poly(tetramethylene oxide) characterized by a number average molecular weight of 1,000 g / mol; Polycarbonate Diol 1000 (Poh) is the reaction product of dimethyl carbonate and a stoichiometric excess of 1,6-hexanediol and is characterized by a number average molecular weight of 1,000 g / mol.

[0128] In Comparative Example 1a, the hydroxyl-functional polyurethane PUoh does not contain any ethylenically unsaturated bonds.

[0129] In Comparative Example 2a, the amount of pendant ethylenically unsaturated double bonds in the hydroxyl-functional polyurethane PUoh is too high (3,322 g / equiv.).

[0130] In Comparative Example 3a, the hydroxyl-functional polyurethane PUoh contains only terminal ethylenically unsaturated double bonds.

[0131] Comparative Example 4 In a nitrogen purged reactor, 369 g of polyadipate of 1,6-hexanediol having a number average molecular weight of 1,000 g / mol and a hydroxyl number of 112 mg KOH / g and 79 g of dimethylolpropionic acid were heated to 130° C. and the mixture was maintained at this temperature until a homogeneous solution was formed. 117.9 g of isophorone diisocyanate was then measured for 30 minutes with continued stirring at 130° C. until no more free isocyanate groups were detected.

[0132] After cooling to 100°C, 1.05 g of 2,6-di-tert-butyl-4-methylphenol, 15.5 g of 1,4-butylene glycol, 17 g of glycerol monomethacrylate, and 254 g of 2-ethylhexyl acrylate were added in succession and the mixture was homogenized. After further cooling to 80°C, 237.7 g of isophorone diisocyanate were added for 15 minutes and the components were reacted at 75°C until the theoretical NCO content corresponding to the complete conversion of the isocyanate reactive groups was obtained and confirmed by titration. Then, 77.8 g of diethanolamine and 106 g of methyl methacrylate were added in succession and the reaction mixture was kept at the resulting temperature with stirring until all the isocyanate groups had reacted. After the addition of 42 g of N,N-dimethylethanolamine, the mixture was homogenized at 75°C for 15 minutes. 1350 g of deionized water was then added to the prepolymer solution with vigorous stirring at 65°C for 30 minutes. Thereafter, 102 g of a 1.9% aqueous solution of BRUGGOLITE™ FF6M was added at 65° C. and homogenized for 10 minutes, followed by continuous addition of 201.4 g of a 0.5% aqueous solution of tert-butyl hydroperoxide during 30 minutes, while maintaining the temperature at 65° C.-75° C. by parallel cooling. The reaction mixture was then held at a temperature of 65-75° C. for another 30 minutes for completion of polymerization (thereby obtaining PUSpp). Then, 250 g of deionized water was added. The resulting dispersion was heated to 60° C., whereupon 208 g of a 3.8% aqueous solution of BRUGGOLITE® FF6M was added and homogenized at 60° C. for 10 minutes. Then, a premixed monomer blend containing 450 g of methyl methacrylate and 900 g of 2-ethylhexyl acrylate, and 505.74 g of a 0.8 aqueous solution of tert-butyl hydroperoxide were added continuously in parallel with stirring for 3 hours, while maintaining the temperature at 60 and 65° C. by external cooling. At the third hour of parallel feeding of the monomer and hydroperoxide solutions, a sudden viscosity increase and very significant coagulum formation were observed. Finally, the reaction had to be stopped after 2.5 hours of parallel feeding of the monomer and hydroperoxide solutions due to complete coagulum of the reaction product.

[0133] Comparative Example 5 Comparative Example 4 was repeated, adding 250 g of deionized water and 10.21 g of DOWFAX™ 2A1 (external surfactant) to the PUSpp of Comparative Example 4. The resulting dispersion was heated to 60° C., whereupon 208 g of a 3.8% aqueous solution of BRUGGOLITE™ FF6M was added and homogenized at 60° C. for 10 minutes. Thereafter, a premixed monomer blend containing 450 g of methyl methacrylate and 900 g of 2-ethylhexyl acrylate, and 505.74 g of a 0.8 aqueous solution of tert-butyl hydroperoxide were added continuously in parallel under stirring for 3 hours, while maintaining the temperature at 60 and 65° C. by external cooling. Once both additions were completed, the reaction medium was cooled to 65° C. and maintained at this temperature for 30 minutes. The dispersion thus obtained had the following characteristics: solids content: 49.8%; pH (10% aqueous solution): 7.5; dynamic viscosity (100 s -1 , 23℃): 851mPa.s; Z average particle size (ISO22412): 72nm. The synthesis of the aqueous dispersion of Comparative Example 5 was carried out without any problems, no increase in viscosity and / or agglomeration was observed throughout the reaction, and application results were poor due to the presence of external surfactant.

[0134] The application tests were carried out using steel panels painted with a conventional multi-layer coating such as is used in car bodies by the automotive industry. The following paints were prepared therefor:

[0135] (Example 15) CED resin 2572 g of bisphenol A based epoxy resin with a number average molecular weight of 380 g / mol, 440 g of polycaprolactone diol with a number average molecular weight of 550 g / mol, 661 g of bisphenol A, and 1734 g of methoxypropanol were charged successively to a resin kettle and heated with stirring to 43° C. The mixture was stirred for an additional 30 minutes and then cooled to 41° C. At this temperature, 221 g of diethanolamine was added, followed by 194 g of dimethylaminopropylamine, at which time the temperature was increased to a maximum of 125° C. under cooling. After continuing the reaction for an additional 2 hours under stirring at 125° C., the dynamic viscosity of a sample withdrawn and diluted with methoxypropanol to a mass fraction of 40% was measured at 23° C. and 25° C.-1 The viscosity was measured at a shear rate of 765 mPa.s. The reaction was then cooled to 120°C.

[0136] (Example 16) CED Hardener In separate steps, 105 g of diethanolamine and 102 g of propylene carbonate were reacted at 120° C. for 3 hours to form the adduct. 687.5 g of MDI were charged into a resin kettle under dehumidification. At 25° C., 445.5 g of diethylene glycol monobutyl ether were slowly added under gentle cooling, while maintaining the temperature at a maximum of 40° C. The mass fraction of isocyanate groups, calculated as -N=C=O molar mass of 42.02 g / mol, was 9.9%. At a temperature of 40° C., 207 g of the adduct prepared in the first step were added together with 0.4 g of dibutyltin dilaurate. Due to an exothermic reaction, the temperature rose to 80° C. and was maintained as an upper limit by cooling. The reaction was continued under stirring at that temperature for 3 hours, after which 5 g of ethanol and 61.8 g of methoxypropanol were added at 80° C. and stirring was continued for another hour. 60 g of water were then added and the mixture was homogenized whilst the temperature was allowed to drop to ambient temperature (23° C.).

[0137] (Example 17) CED resin emulsion 5822 g of the resin solution of Example 15 was charged into a reactor and heated to 120° C. under stirring. 1426 g of methoxypropanol was distilled at that temperature under reduced pressure. The remaining liquid was then cooled to 95° C. and 107 g of deionized water was added, thus lowering the temperature to 80° C. 2408 g of the hardener of Example 16 was then added and the mixture was homogenized at 80° C. for 1 hour.

[0138] In a separate step, an acidic catalyst solution was prepared by dissolving 107 g of bismuth(III) oxide in 298.3 g of an aqueous solution of methanesulfonic acid with a mass fraction of solute of 70% and diluting after complete dissolution by adding 7913 g of deionized water. A homogenized mixture of resin and hardener was then added to this catalyst solution within 30 minutes under sufficient stirring, whereby the mixture was assumed to have a temperature of 40° C. The mixture was stirred for another 2 hours at this temperature and then diluted to a mass fraction of solids of 37% by adding 2058 g of deionized water.

[0139] (Example 18) Grinding Resin 258 g of 2-ethylhexylamine was added to a resin kettle equipped with a stirrer, a thermometer, and a distillation apparatus and heated to 80°C. At this temperature, 380 g of epoxy resin made from polypropylene glycol and epichlorohydrin with a specific content of epoxy groups of 5.26 mol / kg were added uniformly for 1 hour with the temperature increasing to 120°C. The reaction was continued for another hour at 120°C. Then, 1175 g of 2-butoxyethanol was added, and the temperature was reduced to 70°C, at which 1900 g of bisphenol A-based epoxy resin and epichlorohydrin with a specific content of epoxy groups of 2.11 mol / kg were added. The mixture was heated to 120°C and left to react for 90 minutes. The intermediate thus obtained has a mass fraction of polyoxyalkylene units (-CH(CH3)-CH2-O-) of 11% and a mass fraction of alkyl groups with more than 3 carbon atoms of 9%.

[0140] This intermediate was brought to a temperature of 100° C., 1204 g of 3-(N,N-dimethyl)-aminopropylamine was added and the mixture was reacted at 100° C. for 1 hour. 314 g of 2-butoxyethanol were then added together with 66 g of paraformaldehyde with a formaldehyde mass fraction of 91%. The temperature was increased to 140° C. and 36 g of water formed in the reaction were distilled by azeotropic distillation using methyl isobutyl ketone as carrier. When the water was separated, the ketone was removed by vacuum distillation and the residue was diluted to a solid mass fraction of 55% by adding 774 g of 2-butoxyethanol.

[0141] (Example 19) Pigment paste The following materials were added to a mixing tank in the order shown: 207.9 g deionized water, 16.9 g aqueous acetic acid (30 g acetic acid in 100 g aqueous dilution), 18.7 g 2-butoxyethanol, 268 g grinding resin solution of Example 18, 10.2 g 50% strength solution of 2,4,7,9-tetramethyl-5-decyne-4,6-diol in 2-butoxyethanol (SURFYNOL™ 104BC, Air Products Nederland BV), 7.3 g carbon black pigment (PRINTEX™ 201, Evonik Industries), and 479.2 g titanium dioxide white pigment (KRONOS™ RN59, Kronos Titan). The mixture was dispersed in a dissolver for 15 minutes and then ground in a ball mill for 1 hour.

[0142] (Example 20) Preparation of CED coating composition A CED coating composition was prepared from the emulsion of Example 17, the pigment paste of Example 19, and water by the following procedure. · 3392 g of CED resin emulsion (Example 17), 5982 g deionized water, and 626 g of pigment paste (Example 19). The ingredients were mixed in the order shown under stirring and homogenized at 23° C. for 30 minutes.

[0143] (Example 21) Preparation of primer / surfacer coating composition The primer surfacer coating composition 21b used was prepared from a grey pigment paste 21ba, which was completed by adding a mixture 21bb consisting of deionized water, the aqueous dispersion of Example 21ad, and the condensation product of Example 21ac, adjusted to a solids mass fraction of 42% by the addition of a highly methoxymethylated melamine crosslinker.

[0144] (Example 21aa) Acid Functional Polyurethane In the first reaction, acid functional polyurethane 21aa was prepared by charging a mixture of 810 g dimethylolpropionic acid in a mixture of 946 g diethylene glycol dimethyl ether and 526 g methyl isobutyl ketone in a resin kettle and heating the mixture to 100° C. until complete dissolution. At this temperature, a mixture of 870 g toluylene diisocyanate (TDI) and 528 g semi-capped TDI, which is the reaction product of 1 mole of TDI with 1 mole of ethylene glycol mono-ethyl ether, was added for 4 hours while keeping the temperature constant at 100° C. The reaction mixture was stirred at this temperature for 1 hour to complete the consumption of the total isocyanate groups. The mass fraction of solids was 60%. This acid functional polyurethane 21aa had an acid number of 140 mg KOH / g and a Staudinger index of 9.3 cm, measured at 20° C. in a solution in N,N-dimethylformamide (DMF). 3 Semi-capped TDI was prepared separately by addition of 300 g of ethylene glycol mono-ethyl ether to 580 g of TDI within 2 hours and subsequent reaction for an additional 2 hours at 30° C. after the time when the final mass fraction of isocyanate groups in the adduct was found to be 16.5%.

[0145] (Example 21ab) Hydroxyl-functional polyesters In separate steps, the hydroxyl-functional polyester 21ab was prepared by mixing 190 g tripropylene glycol, 625 g neopentyl glycol, 140 g isomerized linoleic acid, 415 g isophthalic acid, and 290 g trimellitic anhydride in a resin kettle and esterifying at 230° C. until the acid number of the reaction mixture decreased to 4 mg KOH / g. The efflux time of a 50% strength solution of the formed resin in 2-n-butoxyethanol, measured according to DIN 53211 at 20° C., was 165 s. The value of the Staudinger index of the hydroxyl-functional polyester 21ab, measured in N,N-dimethylformamide at 20° C., was 10.5 cm 3 / g.

[0146] (Example 21ac) Condensation product 21ac of the acid functional polyurethane of Example 21aa and the hydroxyl functional polyester of Example 21ab 300 g of the acid functional polyurethane of Example 21aa and 700 g of the hydroxyl functional polyester of Example 21ab were charged to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet, and distillation apparatus and mixed and heated under stirring to 155° C. Solvent was removed under a nitrogen blanket by vacuum distillation to maintain a steady flow of the separated solvent in the condenser. The progress of the reaction was monitored by drawing samples and analyzing them for acid number and viscosity. The acid number was 36 mg KOH / g and the Staudinger index was 16.2 cm. 3 Upon reaching 21ac / g, the reaction was stopped and the condensation product was then cooled to ambient temperature (23° C.) and discharged. This condensation product, designated 21ac, could be fully diluted in water after neutralization with dimethylethanolamine without precipitation or phase separation.

[0147] (Example 21ad) Modified Polyester In a resin kettle equipped with a stirrer and reflux condenser, 192 g of tri-propylene glycol and 104 g of neopentyl glycol were charged and the charges were heated to 110° C. under stirring. 192 g of trimellitic anhydride was then added and the mixture was heated to 170° C. within 2 hours. The reaction mixture was held at that temperature until the acid number was 87 mg KOH / g. After cooling to 150° C., 40 g of a commercial mixture of glycidyl esters of alpha-branched capric acid (CARDURA™ E10, Momentive Specialty Chemicals) and 14 g of linseed oil fatty acid were added. The mixture was then heated to 180° C. within 1 hour and held at that temperature until the acid number reached 55 mg KOH / g. The reaction mixture was then cooled and diluted by the addition of methoxypropanol to 70% of the mass fraction of solids. To 100 g of this solution, 7 g of dimethylethanolamine and 68 g of deionized water were added and the mixture was stirred for 600 min. -1 The mixture was homogenized with a mechanical stirrer at RT for 15 min. An aqueous dispersion with a solid mass fraction of 40% was obtained.

[0148] (Example 21b) Preparation of Pigmented Primer Surfacer Coating Composition A pigmented primer surfacer coating composition was prepared by the following procedure: 21.10 g of the condensation product of Example 21ac, adjusted to a mass fraction of solids of 42% by addition of deionized water, was charged with 3.35 g of deionized water, 12.65 g of rutile titanium dioxide pigment (surface treated with Al and Zr compounds, KRONOS™ 2190, Kronos Titan), 12.65 g of precipitated barium sulfate pigment (Blabc fixe F, Sachtleben), and 0.05 g of carbon5black (PRINTEX™ U, Evonik Carbon Black), in the order listed, and then stirred for 1200 min. -1 The mixture was homogenized with a mechanical stirrer at 50° C. for 15 minutes. This premix was transferred to a bead mill and milled at a temperature not exceeding 50° C. After 45 minutes of milling time, the required particle size of 10 μm was achieved, milling was stopped and the paste thus formed, designated 21ba, was separated from the beads.

[0149] Mixture 21bb was prepared by charging 9.00 g of the condensation product of Example 21ac, adjusted to a mass fraction of solids of 42% by addition of deionized water, and adding, in that order, 27.20 g of the aqueous dispersion of Example 21ad, 1.75 g of a highly methoxymethylated melamine crosslinker having a molar ratio of methoxy groups to methylene groups to melamine derived moieties of 5.0 mol:5.8 mol:1 mol (CYMEL™ 303, Allnex USA, Inc.), and 12 g of deionized water.

[0150] This mixture 21bb was added to the paste 21ba at ambient temperature (23° C.) and stirred for 1200 min to obtain the pigmented primer surfacer coating composition 21b. -1 The coating composition 21b was homogenized with a mechanical stirrer at 25° C. for 15 minutes. The dynamic viscosity of the coating composition 21b was 300 mPa.s (25° C.). -1 (measured at a shear rate of 100 rpm) and its pH value was 8.0.

[0151] (Example 22) Preparation of the Base Coating Composition Basecoat coating compositions were prepared from the polyurethane-vinyl polymer hybrid dispersions of Example 1c and Comparative Examples 1c, 3c, and 5 according to the procedures in Table 4. [Table 4]

[0152] The basecoat compositions were prepared by the following procedure: Polyurethane-vinyl polymer hybrid dispersions (Example 1c, Comparative Example 1c, Comparative Example 3c, and Comparative Example 5) were charged with a methylated high imino melamine crosslinker (CYMEL™ 327, Allnex), dimethylethanolamine (10% solution in deionized water), and deionized water (Part A) in the order listed, and then incubated for 900 min. -1 After 15 min of stirring, a 10% strength solution of acrylic copolymer thickener in deionized water (RHEOVIS™ AS1130, BASF) and further deionized water (Part B) were added and the mixture was stirred for 900 min. -1 The aluminum flake slurry (Part C) was homogenized for another 10 minutes at 35° C. for 600 minutes by adding aluminum flakes (silica encapsulated aluminum flakes HYDROLAN™ 2154, Eckart), anionic wetting agent (ADDITOL XL™ 250, Allnex) and butyl glycol. -1 The homogenized part C was then mixed with the premixed parts A and B for 900 min. 1 In the final step, isobutanol (Part D) was added and homogenized for 900 min. -1 Homogenize for an additional 5 minutes at RT.

[0153] The base coat prepared as described is left to stand for 12 hours at ambient temperature (23° C.). After this standing time, the pH value is adjusted to 8.3 with a 10% strength by weight solution of dimethylethanolamine in deionized water (measured according to DIN ISO 976 at 23° C. on a paint diluted by adding deionized water with a mass fraction of solids of 10%) and the viscosity of the paint is adjusted to 300 mPa.s by adding deionized water (25 s according to DIN EN ISO 3219 at 23° C.). -1 (measured at a shear rate of 100 s).

[0154] (Example 23) Preparation of Clearcoat Coating Composition (Example 23a) Hydroxyl-functional acrylic polymers The acrylic copolymer was prepared by the following procedure: A reactor equipped with a stirrer, an inert gas inlet, a heating and cooling system, and an addition funnel was charged with the glycidyl ester of neodecanoic acid and heated to 175°C. Within 6 hours, a mixture of monomers and initiators was added continuously, consisting of 74.8 g acrylic acid, 229.3 g hydroxyethyl methacrylate, 178.3 g tert-butyl methacrylate, 62.7 g methyl methacrylate, 222.4 g styrene, and 19.8 g di-tert-amyl peroxide, to form the polymer. The reaction mixture was stirred for another 2 hours, until a conversion of more than 95% was observed. The copolymer was diluted to a mass fraction of solids of 75% by the addition of butyl acetate, and the solution was filtered after cooling to room temperature to remove suspended solids, and the mass fraction of solids was then adjusted to 70% by the addition of more butyl acetate.

[0155] (Example 23b) Preparation of Clearcoat Coating Composition Two premixes were prepared by the following procedure: Part A: 825 g of hydroxy-functional acrylic polymer, Example 23a 51g Butyl acetate 51g xylene Methoxypropyl acetate 51g 5 g hindered amine light stabilizer (mixture of bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1-(methyl)-8-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, sold as TINUVIN® 292 by BASF) Benzotriazole type light stabilizer (mixture of β-[3-(2-H-benzotriazol-2-yl)-4-hydroxy-5-tert-butylphenyl]propionic acid poly[ethylene glycol] 300-ester and bis{β-[3-(2-H-benzotriazol-2-yl)-4-hydroxy-5-tert-butylphenyl]propionic acid} poly[ethylene glycol] 300-ester, sold as TINUVIN(TM) 1130, BASF) 15g Modified silicone leveling agent (ADDITOL(TM) VXL4930, allnex Austria) 2g Part B: 322 g of HDI trimer dissolved in butyl acetate, mass fraction of the solution 90% (DESMODUR® N3390BA, isocyanurate type, CAS Nr: 28182-81-2, sold by Covestro) 97g Butyl acetate 40g xylene Solvent naphtha 150 / 180 (a mixture of aromatic hydrocarbons with a boiling point range of 150-180°C) 24g

[0156] The ingredients of Part A were added in the order listed above and homogenized with a mechanical stirrer for 15 minutes at 23°C (900 min -1 ).

[0157] In separate steps, the solution of trimer HDI and the solvent were added to the premixed Part A for 900 min. -1 After 10 minutes of homogenization, the viscosity of the clear coat is adjusted to 130 mPa.s (according to DIN EN ISO 3219 and 25s at 23° C.) by adding a mixture of butyl acetate and solvent naphtha 150 / 180 in a mass ratio of 60 / 40. -1(Measured by shear rate of 100 rpm.) This ready-to-use clearcoat coating composition must be applied within 90 minutes.

[0158] (Example 24) Preparation of multilayer coatings Multi-layer coatings were prepared from the CED coating composition of Example 20, the primer surfacer coating composition of Example 21b, the basecoat compositions (L1-L4) of Example 22, and the clearcoat coating composition of Example 23 by the following procedure. Preparation of test panels: Four zinc phosphated steel panels (P1 to P4) (GARDOBOND™ 26S 6800OC from Chemetall) were painted with a CED paint according to Example 20 under the following conditions: CED chamber temperature: 30℃ Deposition time: 2 minutes Voltage: 300V All the painted panels were evaporated at ambient temperature for 30 minutes and then baked at 180°C for 20 minutes. The dry film thickness of the CED layer was 22 μm for the whole panel. In the next step, the primer surfacer coating composition of Example 21b was applied to all four panels (dry film thickness: 30 μm) and, after an evaporation step (10 minutes at 23°C), baked at 165°C for 20 minutes. In a third step, the four panels were overcoated with the base coat composition of Example 22 (L1-L4). The base coat layer (10 μm dry film thickness) was evaporated at 23°C for 10 minutes and then baked at 80°C for 10 minutes. Finally, all the panels were overcoated with the clear coat composition of Example 23 (50 μm dry film thickness) and baked at 140°C for 20 minutes.

[0159] Table 5 outlines the details of the panel preparation. [Table 5]

[0160] Panels 1 to 4 (P1, P2, P3, P4) were subjected to a moisture resistance test according to DIN EN ISO 6270-2 (condensed atmosphere with constant humidity, test duration 240 h). After 240 h, the panels were regenerated for 1 h at 23° C. and 65% relative humidity before the appearance of the panels was evaluated according to DIN EN ISO 4628-2 (Settings for the amount and size of defects and the intensity of constant appearance changes - Part 2: Evaluation of the degree of blistering).

[0161] The results obtained are shown in Table 6. [Table 6]

[0162] As can be seen from Table 6, the comparison clearly shows that the use of the novel aqueous polyurethane-vinyl polymer hybrid dispersion according to the present invention unexpectedly and unexpectedly results in significantly improved water resistance in the basecoat layer of a multi-layer coating, which, according to the present inventors, could not be predicted or obtained from the prior art.

Claims

1. An aqueous polyurethane-vinyl polymer hybrid dispersion D containing a reaction product E of 30 to 80% by weight of one or more ethylenically unsaturated monomers MU2 (singular or plural), wherein the MU2 is polymerized in the presence of a polyurethane-vinyl polymer hybrid prepolymer PUSpp having 20 to 70% by weight of pendant acid salt groups, the total of MU2 and PUSpp is 100%, the polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid salt groups is ・60 to 85% by weight of an acid salt group-containing hydroxyl-functional polyurethane PUSoh having pendant ethylenically unsaturated groups and pendant groups of an acid salt, and ・15 to 40% by weight of one or more ethylenically unsaturated monomers MU1 (singular or plural) is a reaction product of, the total of PUSoh and MU1 is 100%, the MU1 is polymerized in the presence of an acid salt group-containing hydroxyl-functional polyurethane PUSoh, the acid salt group-containing hydroxyl-functional polyurethane PUSoh is ・a hydroxyl-functional polyurethane PUoh, and ・one or more compounds An (singular or plural) capable of reacting with an acid group to form a base is a reaction product of, the hydroxyl-functional polyurethane PUoh is 30 to 50% by weight of one or more polyisocyanates I (singular or plural), and ・optionally, 1 to 4% by weight of one or more monomeric isocyanate-reactive compounds Moh (singular or plural) having at least two isocyanate-reactive groups, ・30 to 40% by weight of one or more polymeric isocyanate-reactive compounds Poh having at least two isocyanate-reactive groups, ・7 to 11% by weight of one or more isocyanate-reactive monomers MAoh (singular or plural) having at least two isocyanate-reactive groups and at least one acid group or a group capable of forming an acid when contacted with water, ・0.5 to 4% by weight of one or more isocyanate-reactive monomers MUoh (singular or plural) having at least two isocyanate-reactive groups and an ethylenically unsaturated group, and ・7 to 11% by weight of one or more primary or secondary amines Aoh (singular or plural) having at least one hydroxyl group is a reaction product of, the total of I, Poh, Moh, MAoh, MUoh, and Aoh is 100%, Aqueous polyurethane-vinyl polymer hybrid dispersion D.

2. The hydroxyl-functional polyurethane P Uoh has an unsaturation equivalent weight (UEW) of 3,500 to 35,000 g / equiv, and the ethylenically unsaturated group is a pendant group. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

3. The isocyanate-reactive monomer M Uoh has at least two isocyanate-reactive groups and an ethylenically unsaturated group. The M Uoh, which is a part of the hydroxyl-functional polyurethane P Uoh, is selected from the group consisting of glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, and mixtures thereof. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

4. The hydroxyl-functional polyurethane P Uoh is characterized by an acid value of 30 to 60 mg KOH / g. The acid value is generated by the isocyanate-reactive monomer M Aoh having at least two isocyanate-reactive groups and at least one acid group or a group capable of forming an acid when contacted with water. The M Aoh is incorporated into the polyurethane by at least 95% via urethane or urea linkages. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

5. The polymer compound P oh having at least two isocyanate-reactive groups is a part of the hydroxyl-functional polyurethane P Uoh, is selected from the group consisting of polyester, polylactone, polyether, polycarbonate, polyamide, polyene, polydiene, and mixtures thereof, and the polymer compound P oh has a number average molecular weight of 300 to 10,000 g / mol. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

6. The polymer compound Poh having at least two isocyanate-reactive groups is part of the hydroxyl-functional polyurethane P Uoh, and is selected from the group consisting of hydroxyl-functional polyesters, hydroxyl-functional polycarbonates, hydroxyl-functional polyethers, and mixtures thereof, and the polymer compound Poh has a number average molecular weight of 500 to 3,000 g / mol. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

7. The polymer compound Poh having at least two isocyanate-reactive groups is hydroxyl-functional polyester Poh1, and the polyester is a reaction product of a stoichiometric excess of one or more diols and one or more diacids, and the polyester has a hydroxyl value of 40 to 300 mgKOH / g and an acid value of less than 3 mgKOH / g, and the acid value is the remainder and is generated by unreacted acid functional groups at the ends. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

8. One or more ethylenically unsaturated monomers MU1 and / or MU2 are selected from the group consisting of alkyl (meth)acrylates, (meth)acrylamides, hydroxy (meth)acrylates, epoxy-functional (meth)acrylates, ketone-functional (meth)acrylates, vinyl monomers, and mixtures thereof, and the alkyl (meth)acrylate is an ester of an aliphatic straight-chain, branched, or cyclic monoalcohol having 1 to 12 carbon atoms in the alkyl group and (meth)acrylic acid. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

9. The weight percentage of each monomer contained in MU1 is different from the weight percentage of the corresponding monomer in MU2, and the total weight percentage of all monomers contained in MU1 and MU2 is 100%. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

10. - The polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid bases is characterized by a weight ratio of acid-base-containing hydroxyl-functional polyurethane PUSoh to vinyl polymer derived from MU1 of greater than 1, and ・ The reaction product E of one or more ethylenically unsaturated monomers MU2 (singular or plural) polymerized in the presence of the polyurethane-vinyl polymer hybrid prepolymer PUSpp having a pendant acid base is characterized by a weight ratio of the acid base-containing hydroxyl-functional polyurethane PUSoh to the total vinyl polymer derived from MU1 and MU2 of 1 or less than 1. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

11. The polyurethane-vinyl polymer hybrid prepolymer PUSpp having a pendant acid base is ・ 65 to 80% by weight of an acid base-containing hydroxyl-functional polyurethane PUSoh having a pendant ethylenically unsaturated group and a pendant base, and ・ 20 to 35% by weight of one or more polymerized ethylenically unsaturated monomers MU1 (singular or plural) which is a reaction product, and the total of PUSoh and MU1 is 100%. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

12. The acid base-containing hydroxyl-functional polyurethane PUSoh having a pendant ethylenically unsaturated group and a pendant base is ・ 35 to 45% by weight of one or more polyisocyanates I (singular or plural), ・ 33 to 37% by weight of one or more polymer compounds Poh (singular or plural) having at least two isocyanate-reactive groups, ・ 2 to 3% by weight of one or more monomer compounds Moh (singular or plural) having at least two isocyanate-reactive groups, ・ 8 to 10% by weight of one or more isocyanate-reactive monomers MAoh (singular or plural) having at least two isocyanate-reactive groups and at least one acid group, ・ 1 to 3% by weight of one or more isocyanate-reactive monomers MUoh (singular or plural) having at least two isocyanate-reactive groups and an ethylenically unsaturated group, and ・ 8 to 10% by weight of one or more primary or secondary amines Aoh (singular or plural) having at least one hydroxyl group which is a reaction product, the total of I, Poh, Moh, MAoh, MUoh, and Aoh is 100%, and the acid group of MAoh is further converted by the addition of one or more neutralizing compounds An (singular or plural) in the acid base. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

13. The reaction product E is - 40 to 70% by weight of the polymerizable ethylenically unsaturated monomer MU2, - 30 to 60% by weight of the polyurethane-vinyl polymer hybrid prepolymer PUSpp having pendant acid groups comprising, with the total of PUSpp and polymerized MU2 being 100%, the aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1.

14. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1, characterized in that the dispersed particles of the reaction product E have a Z-average particle size of 50 to 150 nm according to ISO 22412.

15. The aqueous polyurethane-vinyl polymer hybrid dispersion D according to claim 1, comprising 40 to 55% by weight of solids and 45 to 60% by weight of water.

16. A process for the preparation of the aqueous polyurethane-vinyl polymer hybrid dispersion D according to any one of claims 1 to 15, a) mixing a polymeric compound Poh having at least two isocyanate-reactive groups with one or more isocyanate-reactive monomers MAoh having at least two isocyanate-reactive groups and a group capable of forming an acid when contacted with an acid group or water, and optionally in the presence of one or more isocyanate-reactive monomers Moh having at least two isocyanate-reactive groups, and heating the mixture to a temperature of at least 60 °C with stirring; b) continuously adding a semi-stoichiometric amount of a polyfunctional isocyanate I to the mixture of step a), preferably while maintaining the temperature in the range of 60 °C to 150 °C for 10 to 60 minutes, thereby forming an isocyanate-reactive polyurethane prepolymer; c) adding one or more isocyanate-reactive monomers MUoh having at least two isocyanate-reactive groups and ethylenically unsaturated groups, and optionally one or more isocyanate-reactive monomers Moh having at least two isocyanate-reactive groups, preferably one or more ethylenically unsaturated monomers MU1, to the isocyanate-reactive polyurethane prepolymer of step b) and homogenizing the mixture, optionally in the presence of an antioxidant or a radical scavenger. d) While stirring at a temperature in the range of 60 °C to 100 °C, adding a further amount of the polyfunctional isocyanate I to the stoichiometrically excess homogenized mixture of step c), thereby forming an isocyanate-functional polyurethane prepolymer; e) Quickly adding a mixture comprising one or more primary or secondary amines Aoh (singular or plural) having at least one hydroxyl group and preferably one or more ethylenically unsaturated monomers MU1 (singular or plural) to the isocyanate-functional polyurethane prepolymer of step d), thereby forming a hydroxyl-functional polyurethane P Uoh in the ethylenically unsaturated monomer(s) MU1; f) Adding a neutralizing agent An to the mixture of step e) and homogenizing the mixture at a temperature in the range of 40 °C to 80 °C for at least 5 minutes, thereby forming an acid-base-containing hydroxyl-functional polyurethane P USoh in the ethylenically unsaturated monomer(s) MU1; g) Adding water to the homogenized mixture of step f), thereby forming an emulsion; h) Homogenizing the emulsion of step g) at a temperature in the range of 40 °C to 80 °C for at least 10 minutes; i) While maintaining a temperature in the range of 60 °C to 80 °C, gradually adding at least one of the redox components over at least 10 minutes to redox polymerize the homogenized emulsion of step h), thereby forming the polymerization mixture; j) For further polymerization, maintaining the temperature of the polymerization mixture at 65 to 85 °C for at least 15 minutes, thereby forming the polyurethane-vinyl polymer hybrid prepolymer P USpp having pendant acid-base groups; k) Quickly adding a mixture of ethylenically unsaturated monomer MU2 to the polyurethane-vinyl polymer hybrid prepolymer P USpp having pendant acid-base groups of step j) and homogenizing the mixture at a temperature in the range of 40 °C to 80 °C for at least 10 minutes; l) While maintaining a temperature in the range of 60 °C to 80 °C, gradually adding at least one of the redox components over at least 10 minutes to redox polymerize the homogenized emulsion of step k), thereby forming the polymerization mixture; m) maintaining a temperature in the range of 60°C to 80°C for at least 15 minutes to terminate the polymerization, thereby forming the aqueous polyurethane-vinyl polymer hybrid dispersion D1; A method comprising the steps of:

17. a) quickly adding a mixture of ethylenically unsaturated monomer MU2 to the aqueous polyurethane-vinyl polymer hybrid dispersion D1 of step m), and homogenizing the mixture at a temperature in the range of 40°C to 80°C for at least 10 minutes; b) while maintaining the temperature in the range of 60°C to 80°C, gradually adding at least one of the redox components for at least 10 minutes to subject the homogenized emulsion of step n) to redox polymerization, thereby forming the polymerization mixture; c) maintaining a temperature in the range of 60°C to 80°C for at least 15 minutes to terminate the polymerization, thereby forming the aqueous polyurethane-vinyl polymer hybrid dispersion D2; The method according to claim 16, further comprising the steps of:

18. The method according to claim 16, wherein said one or more primary or secondary amines Aoh having at least one hydroxyl group are selected from the group consisting of 2-aminoethanol, 2-methylaminoethanol, 3-aminopropanol, 2-amino-1,3-propanediol, diethanolamine, 1,1'-iminodi-2-propanol, and mixtures thereof.

19. An aqueous polyurethane-vinyl polymer hybrid dispersion D according to any one of claims 1 to 15, and one or more additives selected from the group consisting of defoamers, leveling agents, ultraviolet absorbers, fusion aids, flow regulators, rheology additives, crosslinking agents, fillers, pigments, active pigments, and wetting agents. A coating composition comprising:

20. The coating composition according to claim 19, wherein the crosslinking agent is added to the aqueous polyurethane-vinyl hybrid polymer dispersion D during its synthesis.

21. Use of the coating composition according to claim 19 for coating a metal, wood, plastic, or paper substrate.

22. A corrosion prevention coating comprising the coating composition according to claim 19.

23. The corrosion prevention coating according to claim 22 for use in multi-coat build-up on or for a metal substrate.