Crosslinkers for water-borne alkyd resins

Abstract

The invention pertains generally to hydrocarbyl mercapto crosslinkers including at least one hydrolysable organosilane group, which crosslinkers can be added to an alkyd coating to improve at least one physical property of the water-borne alkyd coating compared to a coating without the addition and compositions, methods, and processes related thereto.

Description

Crosslinkers for Water-Borne Alkyd ResinsCross-Reference to Related Applications

[0001] None.Technical Field

[0002] The invention described herein pertains generally to a compound containing one or more thiol groups used as a crosslinker which can be added to an alkyd coating that can boost hardness in water-borne alkyds, and in some instances, crosslinker with hydrolysable organosilanes containing one or more thiol groups.Background of the Invention

[0003] Primary paint driers, typically metal carboxylates like cobalt neodecanoate, are used to catalyse the oxidative drying (curing) of alkyd resins. Generally, these driers are complexes based on transition metals. Cobalt driers are the most used drying catalysts as they result in highly cross-linked and hard films. Highly cross-linked and hard films are desirable because they have higher scratch, chemical and corrosion resistance. However, several environmental studies have suggested potential reclassification of cobalt-based alkyd driers. Borchi® Oxy Coat (“BOC”), is a primary drier for alkyds. At least three patent families are linked to Borchi® Oxy Coat that cover the use of the catalyst in different delivery forms, and variations of the structure, in formulation, for coatings and composites. It has been found that BOC shows faster curing and less yellowing of alkyd films at much lower concentrations than cobalt. However, BOC when compared to some cobalt driers, has been found lacking in the formation of hard films

[0004] Therefore, there is a need for non-cobalt-based driers as alternatives, particularly in the field of water-borne alkyd coatings. The lack of hardness impacts the use of BOC as a cobalt replacement in more demanding applications, such as direct to metal coatings or decorative coatings, to allow scratch resistance, improved corrosion resistance and the ability to stack painted pieces quickly.

[0005] It has been determined that organic solvent soluble polythiols such as pentaerythritol tetrakis(3-mercaptopropionate) (“ME-4”), that had been used previous work for solvent-borne alkyds was relatively ineffective when tested in water-borne alkyds. It had been assumed that even though ME-4 was not soluble in water, it would still be compatible with the non-polar alkyd once the aqueous phase was evaporated. However, ME-4 crosslinker demonstrated an incompatibility with alkyd resin when organic solvents were not used.

[0006] Research has indicated that a much more effective approach to speeding up dry time as well as improving hardness in water-borne alkyd resins can be achieved by employing crosslinkers with hydrolysable organosilane containing one or more thiol groups.Summary of the Invention

[0007] The present invention is directed to a new class of crosslinkers for water-borne alkyd resins, the crosslinkers having a thiol functionality which reacts with the unsaturation of the fatty acid and a silanol functionality which could self-condense to add more crosslinking to the coating in combination with Borchi® Oxy Coat 1101 (“BOC 1101”) or Borchi® Dragon or Vanadium catalysts (e.g., V-TS).

[0008] In a first embodiment of the invention, a process is described to improve at least one physical property of a water-borne alkyd resin comprising the steps of without regard to order of:(a) adding at least one hydrocarbyl mercapto crosslinker compound, the at least one mercapto crosslinker compound containing at least one thiol group, preferably two or more thiol groups; and at least one hydrolysable organosilane group in which the hydrolysable group contains at least one alkoxy group having from 1 to 4 carbon atoms or with at least one acyloxy group having from 1 to 8 carbon atoms;(b) adding at least one drier complex, the drier complex comprising:(i) at least one transition metal ion selected from the group consisting of vanadium, iron, copper and manganese; and(ii) at least optionally one polydentate accelerant ligand which bonds to the at least one transition metal ion by way of one or more donor sites wherein the ligand is a bi-, tri-, tetra-, penta- or hexa-dentate ligand coordinating through nitrogen or oxygen donor atoms respectively; and(c) adding the water-borne alkyd resin; the combination of (a), (b) and (c) improving at least one physical property of the water-borne alkyd resin, the physical property selected from the group consisting of accelerated dry time, improved hardness and improved corrosion resistance with the proviso that when the at least one transition metal ion is vanadium, no polydentate accelerant ligand is added.

[0009] In a second embodiment of the first embodiment, the organosilane group is selected from the group consisting of 3- (triethoxysilyl)propyl, 4-(triethoxysilyl)butyl, 2-methyl-3-(triethoxysilyl)propyl, 3- (trimethoxysilyl)propyl, 3-triacetoxysilylpropyl, 3-(diethoxymethylsilyl)propyl, 3- (diethoxyethylsilyl)propyl, 3-(dimethoxymethylsilyl)propyl or 3-(diacetoxymethylsilyl)propyl, triacetoxysilylalkyl, and diacetoxymethylsilylalkyl groups; orthe at least one hydrocarbyl mercapto crosslinker compound is selected from the group consisting of (3-mercaptopropy)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, triacetoxy(3-mercaptopropyl)silane.

[0010] In a third embodiment of the first or second embodiment, the hydrocarbyl mercapto crosslinker compound is of formula (VI):

[0011] In a fourth embodiment of the first embodiment, the hydrocarbyl mercapto crosslinker compound is selected from the group consisting of formulae (A) and (B) below:in which formula (A):Ri, R2 and R3, which may be identical or different, represent: a hydrogen atom, or a group chosen from C1-20 alkoxy, C3-9 cycloalkyloxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkyloxy such as cyclopentyloxy or cyclohexyloxy, C1-6 alkylcarbonyloxy or C1-6 alkyl- C(O)-O-, G-C 1-20 alkyl, and G-C1-20 alkoxy with G representing a hydroxyl, C1-6 alkoxy, or thiol SH group; orALK represents a C1-20 alkylene chain, which is optionally interrupted or terminated, in the a-position with respect to the silicon atomin which formula (B): p, q, r, s, t and u are 0 or 1 ; x is an integer between 1 and 20, limits included, in particular between 1 and 10, limits included; m is an integer between 1 and 4, limits included, and n is an integer between 1 and 3, limits included;R'i, R'2, R S, R'4 and R's, which may be identical or different, represent:(i) the same groups as Ri, R2 and R3 as defined above,(ii) a trisubstituted siloxane group RaRbRcSi-O- with Ra, Rb and Rc, which may be identical or different, representing the same groups as R1, R2 and R3 as defined above, or(iii) a group R'aR'bR'cSi-O-Si (R'd)(R'e)-ALK"-, with ALK" being as defined for ALK above, and R'a, R'b, R'c, R'd and R'e, which may be identical or different, representing: a hydrogen atom, a hydroxyl group, a (C1-4) alkoxy group, a (C1-4) alkyl group, or a group R"aR"bR"cSi-O-, with R"a, R"b and R"c, which may be identical or different, representing a hydrogen atom or a (Ci-4)alkyl group;ALK and ALK', which may be identical or different, represent a group as defined for ALK above;X and X', which may be identical or different, represent:(i) a o bond,(ii) a heteroatom such as oxygen, or an NR group with R representing a hydrogen atom or a (C1-4) alkyl group; and wherein preferably, in formula (B):X does not represent a bond when s is zero,when m is 1 , then p, q and r are 1 , when m is 2, then p is 0, and q and r are 1 , when m is 3, then p and q are 0 and r is 1 , when m is 4, then p, q and r are 0, when n is 1 , then t and u are 1 , when n is 2, then t is 1 and u is 0, and when n is 3, then t and q are 0.

[0012] In a fifth embodiment of any of the first to fourth embodiments, the at least one transition metal ion is selected from the group consisting of: a vanadium-containing drier wherein the vanadium is selected from the group consisting of V(ll), V(lll), V(IV) or V(V) compounds, an iron-containing drier wherein the iron is selected from the group consisting of Fe(ll) or Fe(lll) compounds, a manganese-containing drier wherein the manganese is selected from the group consisting of Mn(ll), Mn(lll) or Mn(IV) compounds, and a copper-containing drier wherein the copper is selected from the group consisting of Cu(l) and Cu(ll).

[0013] In a sixth embodiment of any of the first to fifth embodiments of the invention the at least one drier complex is BOC, namely iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)- 7-[(2-pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1) illustrated below as Formula (I).

[0014] In a seventh embodiment of any of the first to fifth embodiments of the invention the at least one drier complex is selected from the group consisting of is oxidovanadium p-toluenesulfonate, illustrated below as formula (III)and oxidovanadium p-dodecylbenzenesulfonate, illustrated below as formula (IV)

[0015] In an eighth embodiment of the first embodiment of the invention, the product of the result of the process of any of the previous embodiments one through seven.

[0016] In a ninth embodiment of any of the first to seventh embodiments, the at least one hydrocarbyl mercapto silane crosslinker compound containing at least one thiol group has a thiol functional group that reacts with the unsaturation of the water-borne alkyd resin and at least one silanol functional group that self-condenses to add more crosslinking to the water-borne alkyd resin.

[0017] In a tenth embodiment of the invention, a water-borne alkyd resin is described which comprises:(a) at least one hydrocarbyl mercapto crosslinker compound, the at least one mercapto crosslinker compound containing at least one thiol group, preferably two or more thiol groups; and at least one hydrolysable organosilane group in which the hydrolysable group contains at least an alkoxy group with 1 to 4 or 1 to 8 carbon atoms such as methoxy, ethoxy, isopropoxy or butoxy groups or at least an acyloxy such as acetoxy groups. The organosilane group compound could be groups such as 3-(triethoxysilyl)propyl, 4-(triethoxysilyl)butyl, 2-methyl-3- (triethoxysilyl)propyl, 3-(trimethoxysilyl)propyl, 3-triacetoxysilylpropyl, 3- (diethoxymethylsilyl)propyl, 3-(diethoxyethylsilyl)propyl, 3-(dimethoxymethylsilyl)propyl or 3- (diacetoxymethylsilyl)propyl, triacetoxysilylalkyl, or diacetoxymethylsilylalkyl groups.(b) at least one drier complex, the drier complex comprising:(i) at least one transition metal ion selected from the group consisting of vanadium, iron, copper and manganese; and(ii) at least optionally one polydentate accelerant ligand which bonds to the at least one transition metal ion by way of one or more donor sites wherein the ligand is a bi-, tri-, tetra-, penta- or hexa-dentate ligand coordinating through nitrogen or oxygen donor atoms respectively; and(c) a water-borne alkyd resin; with the proviso that when the at least one transition metal ion is vanadium, no polydentate accelerant ligand is added.

[0018] In an eleventh embodiment of the tenth embodiment of the invention, the hydrocarbyl mercapto crosslinker compound is selected from the group consisting of (3-mercaptopropy) trimethoxysilane, (3-mercaptopropyl)triethoxysilane, triacetoxy(3- mercaptopropyl)silane, and mercaptofunctional silicone materials of formula (VI),

[0019] In a twelfth embodiment of the eleventh embodiment of the invention the hydrocarbyl mercapto crosslinker compound is of formula (VI):

[0020] In a thirteenth embodiment of the tenth embodiment of the invention the mercapto crosslinker compound is selected from the group consisting of formulae (A) and (B) below:in which formula (A):Ri, R2 and R3, which may be identical or different, represent: a hydrogen atom, or a group chosen from C1-20 alkoxy, C3-9 cycloalkyloxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkyloxy such as cyclopentyloxy or cyclohexyloxy, C1-6 alkylcarbonyloxy or C1-6 alkyl- C(O)-O-, G-C 1-20 alkyl, and G-C1-20 alkoxy with G representing a hydroxyl, C1-6 alkoxy, or thiol SH group; orALK represents a C1-20 alkylene chain, which is optionally interrupted or terminated, in the a-position with respect to the silicon atomin which formula (B): p, q, r, s, t and u are 0 or 1 ; x is an integer between 1 and 20, limits included, in particular between 1 and 10, limits included; m is an integer between 1 and 4, limits included, and n is an integer between 1 and 3, limits included;R'i, R'2, R S, R'4 and R's, which may be identical or different, represent:(i) the same groups as Ri, R2 and R3 as defined above,(ii) a trisubstituted siloxane group RaRbRcSi-O- with Ra, Rb and Rc, which may be identical or different, representing the same groups as R1, R2 and R3 as defined above,(iii) a group R'aR'bR'cSi-O-Si (R'd)(R'e)-ALK"-, with ALK" being as defined for ALK above, and R'a, R'b, R'c, R'd and R'e, which may be identical or different, representing: a hydrogen atom, a hydroxyl group, a (C1-4) alkoxy group, a (Ci-4)alkyl group, or a group R"aR"bR"cSi-O-, with R"a, R"b and R"c, which may be identical or different, representing a hydrogen atom or a (Ci-4)alkyl group;ALK and ALK', which may be identical or different, represent a group as defined for ALK above;X and X', which may be identical or different, represent:(i) a o bond,(ii) a heteroatom such as oxygen, or an NR group with R representing a hydrogen atom or a (C1-4) alkyl group; and wherein preferably, in formula (B):X does not represent a bond when s is zero, when m is 1 , then p, q and r are 1 , when m is 2, then p is 0, and q and r are 1 , when m is 3, then p and q are 0 and r is 1 , when m is 4, then p, q and r are 0, when n is 1 , then t and u are 1 , when n is 2, then t is 1 and u is 0, and when n is 3, then t and q are 0.

[0021] In a fourteenth of the tenth to thirteenth embodiments of the invention the at least one transition metal ion is selected from the group consisting of: a vanadium-containing drier wherein the vanadium is selected from the group consisting of V(ll), V(lll), V(IV) or V(V) compounds, an iron-containing drier wherein the iron is selected from the group consisting of Fe(ll) or Fe(lll) compounds, and a manganese-containing drier wherein the manganese is selected from the group consisting of Mn(ll), Mn(lll) or Mn(IV) compounds, and a copper-containing drier wherein the copper is selected from the group consisting of Cu(l) and Cu(ll).

[0022] In a fifteenth embodiment of the tenth to fourteenth embodiments of the invention the at least one drier complex is:BOC, namely iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2- pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1) illustrated below as Formula (I):oxidovanadium p-toluenesulfonate, illustrated below as formula (III):or oxidovanadium p-dodecylbenzenesulfonate, illustrated below as formula (IV):10023] These and other objects of this invention will be evident when viewed considering the detailed description, and appended claims.Detailed Description of the Invention

[0024] The best mode for carrying out the invention will now be described for the purposes of illustrating the best mode known to the applicant at the time of the filing of this invention. The examples are illustrative only and not meant to limit the invention, as measured by the scope and spirit of the claims.

[0025] Unless the context clearly indicates otherwise: the word “and” indicates the conjunctive; the word “or” indicates the disjunctive; when the article is phrased in the disjunctive, followed by the words “or both” or “combinations thereof” both the conjunctive and disjunctive are intended.

[0026] As used in this application, the term “approximately” is within 10% of the stated value, except where noted.

[0027] The invention has broad utility in relation to a wide variety of solvent and water-based coating compositions, which term is to be interpreted broadly herein. Examples of coating compositions include clear or colored varnishes, primary coats, filling pastes, glazes, emulsions and floor coverings, e.g. linoleum floor coverings. Embodiments of the invention relate to solvent and water-based paints and inks, particularly paints such as high-specification paints intended for domestic use and paints intended for general industrial applications.

[0028] Use of the term “oxidatively curable coating compositions” herein is thus intended to embrace a wide variety of colored (e.g. by way of pigment or ink) and non-colored materials, including oils and binders, which form a continuous coating through the course of oxidative reactions, typically to form cross-linkages and other bond formations. Generically, such coating compositions may be characterized by the presence of typically (poly) unsaturated resins that react to form a solid film on a substrate, the resins being initially present in the oxidatively curable solvent-based coating compositions either as liquids, dissolved in an organic solvent or as solids dispersed in a continuous liquid phase. Reaction to form the desired coating upon curing arises from polymerization reactions initiated by oxidation. Examples of oxidatively curable coating compositions include alkyd-, acrylate-, urethane-, polybutadiene- and epoxy ester-based resins. Typically, the curable (e.g. alkyd resin) portion of the curable composition will comprise between about 1 and about 90% by weight of the total weight of the oxidatively curable solvent-based coating composition, e.g. between about 20 wt.% and about 70% wt.% of the total weight of the oxidatively curable solvent-based coating composition.

[0029] Alkyd resins are a particularly important member of the class of oxidatively curable coating compositions and are a well-studied class of resin to which the present invention may be applied. Hereinafter, embodiments of the invention are described with reference to the use of alkyd resins, also referred to as alkyd-based resins or alkyd(-based) binders. Whilst these represent particularly significant embodiments of the invention, the invention is not to be so limited. To be clear: the invention is applicable to a wide range of oxidatively curable coating compositions, typically those comprising at least 1 or 2% by weight of an unsaturated compound (e.g., comprising unsaturated (non-aromatic) double or triple carbon-carbon bonds).

[0030] As used herein, the term “alkyd binder” or “alkyd resin” are used interchangeably. Suitable autoxidizable alkyd resin for use in the invention, are in general the reaction product of the esterification of polyhydric alcohols with polybasic acids (or their anhydrides) and unsaturated fatty acids (or glycerol esters thereof), for example derived from linseed oil, tung oil, tall oil as well as from other drying or semi-drying oils. Alkyd resins are well-known in the art and need not to be further described herein. The properties are primarily determined by the nature and the ratios of the alcohols and acids used and by the degree of condensation. Suitable alkyd resins include long oil and medium oil alkyd resins e.g., derived from 45 wt.% to 70 wt.% of fatty acids. To improve the performance of the resins, the composition of the long oil and medium oil alkyd may be modified. For example, polyurethane modified alkyds, silicone modified alkyds, styrene modified alkyds, acrylic modified alkyds (e.g. (meth)acrylic modified alkyds), vinylated alkyds, polyamide modified alkyds, and epoxy modified alkyds or mixtures thereof are also suitable alkyd resins to be used in the present composition.

[0031] Preferably, the at least one autoxidizable alkyd binder is selected from a medium or long oil unmodified alkyd, a silicone modified alkyd, a polyurethane modified alkyd or a combination thereof. Most preferably, the alkyd binder is a long oil (unmodified) alkyd, a silicone modified alkyd, a polyurethane modified alkyd or a combination thereof.

[0032] The amount of alkyd binder in the present compositions can typically range from about 20 wt.% to 98 wt.%, such as about 30 wt.% to about 90 wt.%, preferably about 35 wt.% to 70 wt.% based on the total weight of the composition.

[0033] As used herein, the terms “drier” (which are also referred to synonymously as “siccatives” when in solution) refer to organometallic compounds that are soluble in organic solvents and binders. They are added to unsaturated oils and binders in order to appreciably reduce their drying times, i.e., the transition of their films to the solid phase. Driers are available either as solids or in solution. Suitable solvents are organic solvents and binders and sometimes including water. The driers are present in amounts expressed as weight percent of the metal based on the weight of binder solids (or resin) unless stated otherwise.

[0034] As used herein, the term “drier composition” refers to the mixture of driers as presently claimed. The drier composition according to the invention can comprises several drier compounds. The inventors have found that the present selection of driers in a coating composition improves the drying speed of the coating composition.

[0035] Where percentages by weight are referred to herein (wt. % or % w / w), this means, unless a context clearly dictates to the contrary, percentages by weight with respect to the solid coating film resultant from curing, i.e. components of the oxidatively curable solvent-based coating compositions that serve to provide the coating upon curing. With an oxidatively curable alkyd coating composition, therefore, the combined weights of the components of the composition that become, i.e., are incorporated into, the alkyd resin coating, i.e., once cured, are those with respect to which weight percentages herein are based. For example, the composition, either resultant from conducting themethod according to the first aspect of the invention, or according to the second aspect of the invention, typically comprises about 0.0001 to about 1% w / w, e.g., about 0.0005 to about 0.5% w / w water, or about 0.01 to about 1% w / w, e.g., about 0.05 to about 0.5% w / w water, based on the components of the composition that, when cured, from the coating.

[0036] By oxidatively curable solvent-based compositions is meant herein, consistent with the nomenclature used in the art, compositions that are based on organic (i.e., non-aqueous) solvents. Examples of suitable solvents include aliphatic (including alicyclic and branched) hydrocarbons, such as hexane, heptane, octane, cyclohexane, cycloheptane and isoparaffins; aromatic hydrocarbons such as toluene and xylene; ketones, e.g. methyl ethyl ketone and methyl isobutyl ketone; alcohols, such as isopropyl alcohol, n-butyl alcohol and n-propyl alcohol; glycol monoethers, such as the monoethers of ethylene glycol and diethylene glycol; monoether glycol acetates, such as 2- ethoxyethyl acetate; as well as mixtures thereof. Isomeric variants are included. Thus, the term hexane embraces mixtures of hexanes. According to embodiments of the invention, the solvent is a hydrocarbyl (i.e., hydrocarbon) solvent, e.g., an aliphatic hydrocarbyl solvent, e.g., solvents comprising mixtures of hydrocarbons. Examples include white spirit and solvents available under the trademarks Shellsol, from Shell Chemicals and Solvesso and Exxsol, from Exxon.

[0037] One of the transition metal ions used in the invention is vanadium. The valency of the metal may range from +2 to +5. Embodiments of the invention mixtures of transition metal ions. Where a vanadium-containing drier is provided this is usually as a V(ll), (III), (IV) or (V) compound, where an iron-containing drier is provided, this is usually as an Fe(ll) or Fe(lll) compound. Where a manganese drier is provided, this is usually as a Mn (II), (III) or (IV) compound.

[0038] To enhance the activity of the transition metal ions a so-called accelerating compound, such as a carboxylic acid or a pentadentate amine, is also included. As the language suggests the carboxylic acid or polydentate amine accelerant ligand is a compound capable of coordinating to the transition metal ion by way of more than one donor site within the ligand and serves to accelerate the drying (curing process) of the oxidatively curable coating composition after application.

[0039] According to some embodiments of the invention the polydentate amine accelerant ligand is a bi-, tri-, tetra-, penta- or hexadentate ligand coordinating through nitrogen and / or oxygen donor atoms. In particular embodiments of the invention the ligand is a bi-, tri-, tetra-, penta- or hexadentate nitrogen donor ligand, in particular a tri-, tetra-, penta-, or hexadentate nitrogen donor ligand. However, the invention is not so limited. Examples of a wide variety of polydentate accelerant ligands are discussed below.

[0040] The metal drier, as described herein, e.g., as a pre-formed complex of transition metal ion(s) and polydentate accelerant ligand(s)), is typically dissolved in water at a concentration of about 0.001 to about 10 wt.%, e.g., about 0.01 to about 5 wt.%, or about 0.001 to about 1 wt.%, based on the weight of water. Increasing the concentration of the metal drier in the aqueous solution allows a relatively smaller volume of the metal drier-containing aqueous solution to be added to the coating composition. This may be desired by the skilled person. The actual amount of the metal drier dependson the number of metal atoms present in the metal drier molecule and its total molecular weight, as well as the desired degree of its incorporation. For example, if the molecular weight of a desired complex is 560 and contains one iron ion (mw 56) and a level of 0.1 % of iron is mentioned, the amount of compound dissolved in water is 1% (w / w) or 10 gram / kg water. If the complex is not preformed but formed in-situ, a metal salt will also be typically dissolved in water at a concentration of about 0.001 to about 1 wt.% based on the metal ion to water ratio. An appropriate amount of polydentate accelerant ligand can then be added to form the desired complex.

[0041] After preparation, a solution of the metal drier may then be contacted with, e.g., added to, a coating composition.

[0042] The resultant composition, comprising the metal drier, and typically from 0.0001 to 1% of water, based on the weight of the oxidatively curable coating, will typically be a solution, i.e., a single homogeneous phase. However, it may also be an emulsion or dispersion, e.g., comprising discontinuous regions of aqueous solution comprising the transition metal drier.

[0043] As used in this application, the term “Binder solutions (alkyds)” means one of the following: SYNAQUA 4804 (water-borne short oil alkyd, Arkema); SYNAQUA 2070 (water-borne medium oil alkyd, Arkema); Beckosol AQ101 (water-borne long oil alkyd, Polyont Composites USA Inc.);WorleeKyd S 351 (solve nt- borne medium oil alkyd, Worlee); andTOD 3AK0211Y (water-reducible alkyd, TOD, China) and other binder solutions having similar characteristics to the named above. In a more generic sense, “alkyd resin(s)” means a synthetic resin made by condensation reaction (release of water) between a polyhydric alcohol (glycerol, etc.) and dibasic acid (or phthalic anhydride). It is the non-volatile portion of the vehicle of a paint. After drying, it binds the pigment particles together with the paint film as a whole.

[0044] As used herein, BOC is iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl- kN)-7-[(2-pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1) illustrated below as Formula (I).

[0045] As used in this application, “Borchers Deca Cobalt 7 aqua” is Deca Co 7a, in water dispersible oil, Borchers; synonymously cobalt neodecanoate (cobalt(2+);7,7-dimethyloctanoate) (see formula II).

[0046] As used herein, the term (“V-TS”) is oxidovanadium p-toluenesulfonate, illustrated below as formula (III).

[0047] As used herein, the term (“V-DS”) is oxidovanadium p-dodecylbenzenesulfonate, illustrated below as formula (IV).

[0048] As used in this application, the term “secondary driers”, synonymously “auxiliary driers” means Calcium-Hydrochem (based on Calcium neodecanoate in organic solvents, Borchers; and Octa Soligen Zirconium 10 aqua (Zr-2-ethylhexanoate in organic solvents, Borchers) and other secondary driers having similar characteristics to the named above. Additionally, one or more auxiliary driers may be added to the fully formulated oxidatively curable coating composition. Such auxiliary driers may be optional additional components within, but are often not present in, the formulation of the invention. Such auxiliary driers include fatty acid soaps of zirconium, bismuth, barium, cerium, calcium, lithium, strontium, and zinc. Typically, fatty acid soaps are optionally substituted octanoates, hexanoates and naphthenates. Without being bound by theory, auxiliary driers (sometimes referred to as through driers) are generally understood to diminish the effect of adsorption of the main drier on solid particles often present in an oxidatively curable coating composition. Other non-metal based auxiliary driers may also be present if desired. Concentrations of auxiliary driers within oxidatively curable coating compositions (or formulations of the invention) are typically between about 0.01 wt.% and 2.5 wt.% as is known in the art.

[0049] The coating composition may furthermore contain one or more additives conventionally found in curable coating compositions, such as, but not limited to: UV stabilisers, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame-retardants, lubricants, antifoaming agents, antifouling agents, bactericides, fungicides, algaecides, insecticides, extenders, plasticisers, antifreezing agents, waxes and thickeners.

[0050] In certain embodiments, the coating compositions of the present invention comprise at least one colorant. The colorant component of the coating composition may comprise one or more inorganic or organic, transparent or non-transparent pigments. Non-limiting examples of such pigments are titanium dioxide, iron oxides, mixed metal oxides, bismuth vanadate, chromium oxide green, ultramarine blue, carbon black, lampblack, monoazo and diazo pigments, anthraquinones, isoindolinones, isoindolines, quinophthalones, phthalocyanine blues and greens, dioxazines, quinacridones and diketo-pyrrolopyrroles; and extender pigments including ground and crystalline silica, barium sulfate, magnesium silicate, calcium silicate, mica, micaceous iron oxide, calcium carbonate, zinc oxide, aluminum hydroxide, aluminum silicate and aluminum silicate, gypsum, feldspar, talcum, kaolin, and the like. The amount of pigment that is used to form the coating composition is understood to vary, depending on the composition application, and can be zero when a clear composition is desired.

[0051] The composition according to the invention can be used as a clear varnish or may contain pigments. Examples of pigments suitable for use are metal oxides, such as titanium dioxide or iron oxide, or other inorganic or organic pigments.

[0052] The coating composition may furthermore contain one or more additives such as UV stabilisers, cosolvents, dispersants, surfactants, inhibitors, fillers, anti-static agents, flame-retardant agents, lubricants, anti-foaming agents, extenders, plasticisers, anti-freezing agents, waxes, thickeners, thixotropic agents, etc. Furthermore, the coating composition according to the invention may optionally comprise various anti-oxidants and anti-skinning agents known in the art of the formulation of coating compositions, for example: phenol derivatives, e.g. pyrogallol, 2,6-di- tert. butylhydroxytoluene, hydroquinone, octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate - Irganox® 1076 (available from Ciba SC), bis(2-mercapto-ethyl)-(3-(3,5-di-tert.butyl-4- hydroxyphenyl)propionate) sulphide - Irganox® 1035 (available from Ciba SC), monomethyl ether of hydroquinone, propenyl phenol, 4-acetoxystyrene, iso-eugenol, lauryl gallate; sulphides, e.g. phenothiazine, dodecylsulphide, di(dodecyl)thiodipropionate; phosphines, e.g. trimethylphosphine, tri- n. octylphosphine, triphenylphosphine; phosphites, e.g. trimethylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, ethyl-bis(2,4-di-tert.butyl-6-methylphenyl)phosphite - lrgafos®38 (available from Ciba SC), tris(2,4-di-tert.butylphenyl)phosphite - lrgafos® 168 (available from Ciba SC), bis(2,4-di-tert.butylphenyl)pentadiphosphite - Ultranox®626 (available from General Electric); phosphonites, e.g. tetrakis(2,4-di-tert. butylphenyl)(1 ,1-biphenyl)-4,4'-diylbisphosphonite - Irgafos® P- EPQ (available from Ciba SC); dioxo-compounds, e.g. 2,4-pentanedione, dibenzoylmethane, 2,4- hexanedione, 1 ,3-cyclohexanedione, oxopropionic acid, 2-methyl-3-oxosuccinic acid diethyl ester, oxalacetic acid; oximes, e.g. butanone oxime, butyraldehyde oxime, cyclohexanone oxime; hydroxyacetone, diethylhydroxylamine, 3,5-dimethylpyrazole, ascorbic acid, Hindered Amine Light Stabilisers (HALS), e.g. Tinuvin® 123 and Tinuvine® 292 (available from Ciba SC), 2,3-butenediol, dibenzoyloxybutene, dibenzylthiocarbamic acid zinc salt, Vitamin E, Vitamin E acetate, hypophosphorous acid, 2-butylbenzofuran, 3,4-dihydro-2-ethoxy-2H-pyran, dodecylmercaptane, dicyclopentadiene.

[0053] The curable coating composition according to the various aspects of the invention may be used as a decorative coating, e.g., applied to wood substrates, such as door or window frames, or for other substrates such as those made of synthetic materials (such as plastics including elastomeric materials), concrete, leather, textile, glass, ceramic or metal. The curable coating composition according to the various aspects of the invention may be used as an industrial coating, e.g., applied to metal substrates, such as for automotive parts, bridges, equipment or for coil coatings. The thus applied composition may then be allowed to cure. The invention also provides a composition, when cured.

[0054] Thus, the invention also provides a method comprising applying to a substrate a composition to a substrate. The thus applied composition may then be allowed to cure.

[0055] Any known method can be used to apply the coating compositions of the invention to a substrate. Non-limiting examples of such application methods are spreading (e.g., with paint pad or doctor blade, or by brushing or rolling), spraying (e.g., air-fed spray, airless spray, hot spray, and electrostatic spray), flow coating (e.g., dipping, curtain coating, roller coating, and reverse roller coating), and electrodeposition. (See generally, R. Lambourne, Editor, Paint and Surface Coating: Theory and Practice, Eilis Horwood, 1987, page 39 et seq.).

[0056] The coating compositions of the present invention can be applied and fully cured at ambient temperature conditions in the range of from about -10°C. to 50°C. Curing of said polymer composition according to the invention typically can proceed very rapidly, and in general can take place at a temperature within the range of from -10°C. to +50°C., in particular from 0°C. to 40°C., more in particular from 3°C to 25°C. However, compositions of the present invention may be cured by additional heating.

[0057] The coating compositions of the present invention may be used as a single coating, a top coating, a base coating in a two-layered system, or one or more layers of a multi-layered system including a clear top coating composition, colorant layer and base coating composition, or as a primer layer. A typical opaque system may comprise: 1 or 2 layers of primer and 1 or 2 layers of topcoat (a total of 3 layers). Alternative opaque systems may comprise: 1 primer layer, 1 layer of midcoat and 1 layer topcoat. Examples of transparent systems may comprise 1 layer of impregnant and 3 layers of topcoats or 3 layers of topcoat for maintenance work.

[0058] As used herein, and unless otherwise stated, the term “alkyl” means straight and branched chain saturated acyclic hydrocarbon monovalent groups; said alkyl group may further optionally include one or more suitable substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting examples of straight-chain or branched alkyl groups are C1-20 alkyls, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and stearyl groups. It is recognized that the alkyl may be interrupted with oxygen, sulfur or nitrogen.

[0059] As used herein, and unless otherwise stated, the term “alkenyl” means straight and branched chain unsaturated acyclic hydrocarbon monovalent groups; said alkenyl group may further optionally include one or more suitable substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting examples of the straight-chain or branched alkenyl groups are those having 2 to 30 carbon atoms wherein the position of the double bond may vary, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl groups. It is once again, recognized that the alkenyl may be interrupted with oxygen, sulfur or nitrogen.

[0060] As used herein, and unless otherwise stated, the terms “cycloaliphatic” refer to a mono- or polycyclic saturated hydrocarbon monovalent group having from 3 to 10 carbon atoms, or a C7-10polycyclic saturated hydrocarbon monovalent group having from 7 to 10 carbon atoms. Specific nonlimiting examples of the cycloaliphatic or cyclic alkyl groups which may have substituents are cycloalkyl groups having 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl groups, and the alkylcycloalkyl groups having 6 to 11 carbon atoms wherein the position of the alkyl group may vary, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylcycloheptyl, and diethylcycloheptyl groups. It is once again, recognized that the cycloaliphatic may be interrupted with oxygen, sulfur or nitrogen.

[0061] As used herein, and unless otherwise stated, As used herein, and unless otherwise stated, the terms "aromatic" and "aryl" designate any mono- or polycyclic aromatic monovalent hydrocarbon group having from 6 up to 30 carbon atoms, including fused benzo-C.sub.4-8 cycloalkyl groups (the latter being as defined above), all of the said groups being optionally substituted with one or more substituents independently selected from the group consisting of halogen, amino, haloalkyl, hydroxyl, sulfhydryl and nitro.

[0062] As used herein, and unless otherwise stated, the term "heterocyclic" means a mono- or polycyclic, saturated or mono-unsaturated or poly-unsaturated monovalent hydrocarbon group having from 2 up to 15 carbon atoms and including one or more heteroatoms in one or more rings, each of said rings having from 3 to 10 atoms (and optionally further including one or more heteroatoms attached to one or more carbon atoms of said ring, for instance in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and / or to one or more heteroatoms of said ring, each of said heteroatoms being independently selected from the group consisting of nitrogen, oxygen, sulfur, selenium and phosphorus, also including groups wherein a heterocyclic ring is fused to one or more aromatic hydrocarbon rings for instance in the form of benzo-fused, dibenzo-fused or naphtho-fused heterocyclic groups, including all possible isomeric forms thereof, wherein each carbon atom of said heterocyclic ring may be independently substituted with a substituent selected from the group consisting of halogen, nitro, C1-7 alkyl (such as above defined, in particular methyl), C3-7 alkenyl, trifluoromethyl, C3-10 cycloalkyl, aryl, arylalkyl, alkylaryl, hydroxyl, sulfhydryl, alkoxy (such as above defined, in particular methoxy), aryloxy, arylalkyloxy, thio C1-7 alkyl, thio C3-10 cycloalkyl, thioaryl, arylalkylthio, cyano, carboxylic acid or esters thereof; depending upon the number of unsaturations in each of said rings, heterocyclic groups may be sub-divided into heteroaromatic (or "heteroaryl") groups and non-aromatic heterocyclic groups; when a heteroatom of the said non-aromatic heterocyclic group is nitrogen, the latter may be substituted with a substituent selected from the group consisting of C1-7 alkyl, C3-10 cycloalkyl, aryl, arylalkyl and alkylaryl (each of said groups being as defined herein).

[0063] As used herein, and unless otherwise stated, the term "alkoxy" refer to substituents wherein an alkyl group is attached to an oxygen atom through a single bond.

[0064] As used herein, and unless otherwise stated, the terms "halo" or "halogen" means any atom selected from the group consisting of fluoro, chloro, bromo and iodo.

[0065] As used herein, and unless otherwise stated, the term "arylalkyl" refers to an aliphatic saturated hydrocarbon monovalent group onto which an aryl group (such as defined above) is attached, and wherein the said aliphatic or aryl groups may be optionally substituted with one or more substituents independently selected from the group consisting of halogen, amino, hydroxyl, sulfhydryl, alkyl, haloalkyl and nitro. Specific examples of the arylalkyl groups are those having 7 to 40 carbon atoms wherein the alkyl group may be straight-chain or branched, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl groups.

[0066] As used herein, and unless otherwise stated, the term "alkylaryl" refers to an aryl group (such as defined above) onto which an aliphatic saturated hydrocarbon monovalent group is attached, and wherein the said aliphatic or aryl groups may be optionally substituted with one or more substituents independently selected from the group consisting of halogen, amino, hydroxyl, sulfhydryl, alkyl, trifluoromethyl and nitro. Specific non-limiting examples of the unsubstituted or alkyl-substituted aryl groups are the aryl groups having 6 to 18 carbon atoms such as phenyl, diphenyl and naphthyl groups, and alkylaryl groups having 7 to 40 carbon atoms wherein the alkyl group may be straightchain or branched and may be bonded to any position on the aryl group, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, diethylphenyl, dibutylphenyl and dioctylphenyl groups. The alkylaryl groups may additionally have substituents including functional groups such as alkoxy, hydroxy, cyano, nitro, halides, carboxylic acids, etc.

[0067] As used herein, and unless otherwise stated, the term "acyl" refers to a substituent derived from an acid such as an organic monocarboxylic acid, a carbonic acid, a carbamic acid (resulting into a carbamoyl substituent) or the thioacid or imidic acid (resulting into a carbamidoyl substituent) corresponding to said acids, wherein said acids comprise an aliphatic, aromatic or heterocyclic group in the molecule. A more specific kind of "acyl" group within the scope of the above definition refers to a carbonyl(oxo) group adjacent to an alkyl, a cycloalkyl, an aryl, an arylalkyl or a heterocyclic group, all of them being such as herein defined.

[0068] As used herein, and unless otherwise stated, the term "heterocyclic" means a mono- or polycyclic, saturated or mono-unsaturated or poly-unsaturated monovalent hydrocarbon group having from 2 up to 15 carbon atoms and including one or more heteroatoms in one or more rings, each of said rings having from 3 to 10 atoms (and optionally further including one or more heteroatoms attached to one or more carbon atoms of said ring, for instance in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and / or to one or more heteroatoms of said ring, each of said heteroatoms being independently selected from the group consisting of nitrogen, oxygen, sulfur, selenium and phosphorus,, heterocyclic groups, including all possible isomeric forms thereof, wherein each carbon atom of said heterocyclic ring may be independently substituted with a substituent selected from the group consisting of halogen, nitro, C1-7 alkyl (such as above defined, in particular methyl), C3-7 alkenyl, trifluoromethyl, C3-10 cycloalkyl, hydroxyl, sulfhydryl, C1-7 alkoxy (such as above defined, in particular methoxy), thio C1-7 alkyl, thio C3-10 cycloalkyl, cyano, carboxylic acid or esters, depending upon the number of unsaturations in each of said rings, heterocyclic groups may be sub-divided into heteroaromatic (or "heteroaryl") groups and non-aromatic heterocyclic groups; when a heteroatom of the said non-aromatic heterocyclic group is nitrogen, the latter may be substituted with a substituent selected from the group consisting of C1-7 alkyl, C3-10 cycloalkyl, aryl, arylalkyl and alkylaryl (each of said groups being as defined herein).

[0069] As used herein, and unless otherwise stated, the term “alkoxy” refer to substituents wherein an alkyl group is attached to an oxygen atom through a single bond.

[0070] As used herein, and unless otherwise stated, the terms “halo” or “halogen” means any atom selected from the group consisting of fluoro, chloro, bromo and iodo.

[0071] As used herein, and unless otherwise stated, the term “acyl” refers to a substituent derived from an acid such as an organic monocarboxylic acid, a carbonic acid, a carbamic acid (resulting into a carbamoyl substituent) or the thioacid or imidic acid (resulting into a carbamidoyl substituent) corresponding to said acids, wherein said acids comprise an aliphatic, aromatic or heterocyclic group in the molecule. A more specific kind of "acyl" group within the scope of the above definition refers to a carbonyl (oxo) group adjacent to an alkyl, a cycloalkyl, an aryl, an arylalkyl or a heterocyclic group, all of them being such as herein defined.

[0072] As used herein, and unless otherwise stated, the term “mercapto” or “thiol” or “sulfhydryl” refers to an SH group.

[0073] Two water-born alkyds were used in this work (short and long oil). For this test, Borchi Oxy Coat 1101 (BOC 1101) was added as 0.5% on resin solid while the crosslinker ME-4 was added, in combination with BOC 1101 0.5% on resin solids, as 5% on resin solid as in the table formulation below. The numbers displayed in formulation tables represented mass and the unit was gram (g). The numbers, displayed in hardness results tables, represented Konig hardness and the unit was seconds (s).

[0074] Table I. Formulation of Synaqua 4804 using BOC 1101 vs. BOC 1101 in combination with ME-4 crosslinker

[0075] Table II. Formulation of Beckosol AQ 101 using BOC 1101 vs. BOC 1101 in combination withME-4 crosslinker

[0076] Table III. Koning hardness of Synaqua 4804 and BECKOSOL AQ 101 using BOC 1101 catalyst with or without polythiol crosslinker ME-4

[0077] During the sample preparation, some sedimentation was observed, probably due to the incompatibility of the ME-4 with the water. In Table III, it could be seen that the addition of ME-4 did not significantly increase the hardness when combined with BOC 1101. The improvement was not matching the performance that had been previously observed in solvent-based alkyds. Without being limited to any one theory or mode of operation, it was hypothesized that this could be due to the incompatibility of the ME-4 in aqueous media. The focus of the research shifted to polythiol miscible or water compatible thiol compounds. The crosslinker in water-born alkyds was more challenging than in solvent-born alkyds as other parameters entered into accounts such as surfactant structures and dosage, stability of the crosslinker in aqueous media and alkyd and pH considerations.

[0078] What was observed was that the crosslinker giving the best results for hardness and dry time in combination with oxidative catalyst was not a polythiol but was a hydrolysable organosilane containing one or more thiol groups. In order for the crosslinker to improve hardness and dry time in water born alkyd, it needed to contain two different functionalities:(a) a thiol function that would react with the unsaturation of the fatty acid; and(b) a silanol that could self-condense to add more crosslinking to the coating

[0079] It was observed that once hydrolyzed, the hydrolysable organosilane compound containing one or more thiol groups in combination with BOC 1101 , Borchi® Dragon or Vanadium catalyst (V-TS)improved hardness and dry time and, to some extent, as well as improving the corrosion resistance of the coating.

[0080] Several thiol compounds were used which were water soluble, hydrolysable or in emulsion form. The crosslinkers used are shown in Table IV.

[0081] The hydrocarbyl mercapto crosslinker compound, should at least contain one thiol group, preferably two or more thiol groups; and at least one hydrolysable organosilane group in which the hydrolysable group contains at least an alkoxy group with 1 to 4 or 1 to 8 carbon atom such as methoxy, ethoxy, isopropoxy or butoxy groups or at least an acyloxy such as acetoxy groups. The organosilane group compound could be groups such as 3-(triethoxysilyl)propyl, 4-(triethoxysilyl)butyl, 2-methyl-3-(triethoxysilyl)propyl, 3-(trimethoxysilyl)propyl, 3-triacetoxysilylpropyl, 3- (diethoxymethylsilyl)propyl, 3-(diethoxyethylsilyl)propyl, 3-(dimethoxymethylsilyl)propyl or 3- (diacetoxymethylsilyl)propyl, triacetoxysilylalkyl, or diacetoxymethylsilylalkyl groups. This combination of functional groups improves the crosslinking of the coating by two modes of action: the formation of silicones (or oligosiloxanes) by condensation of several crosslinker molecules, thereby forming new compounds with multiple thiol end groups, as well as a free radical addition reaction between the thiol and unsaturation of the alkyd.

[0082] Table IV. Description and structures of polythiols used.Chemical name CAS number Structure Abbr.Pentaerythritol tetrakis(3-mercaptopropionate) ME-47575-23-7(3-Mercaptopropyl) trimethoxysilane 4420-74-0 ME-SiNoShin Etsu KM-9769 33% silicon thiol emulsion structure KM-9769 availableChemical name CAS number Structure Abbr.CoatOsil* T-cureFormula (VI)

[0083] Sample Preparation

[0084] All the ingredients of a specific formulation were poured into a 50 ml polypropylene mixing cups. The polypropylene mixing cups were then placed in a DAC 150.1 FVZ speed mixer and mixed at 2000 rpm speed for 2 minutes. After the mixing, the samples were stored in the laboratory, at room temperature for 24 hours prior any testing.

[0085] Unless otherwise stated, the loading level (w) of Borchi® OXY - Coat 1101 (BOC 1101 ) and Borchi® Dragon was 1 % based on resin solids and was determined in accordance with the relationship provided in Equation 1 below: amresinx w^BOC or Borchi Dragon ~ 100

[0086] Where a is the fraction solid content of the resin (for example, using 0.5 for 50%), mresinthe mass of the resin used, and mBOC1101 or Borchi Dragonthe mass of the selected drier (BOC 1101 or Borchi Dragon including any solvent mass). In an exemplary case where the loading level is 1% wt. of BOC 1101 or Borchi Dragon on resin solids, w is 1 .

[0087] Unless otherwise stated, the loading level, a, of certain catalysts, including Borchers® Deca Cobalt 7 aqua and Vanadium catalysts (V-TS and V-DS), is provided as metal on resin solids, and determined according to the relationship expressed in Equation 2

[0088] Where a is the solid content of the resin as a fraction, mresinthe mass of the resin, mCatalystthe mass of the selected catalyst (excluding any solvent mass), and / ? the metal content fraction of the selected catalyst (excluding solvent mass). In Equation 2, the loading level, a, is expressed as a fraction of metal on resin solids but can be converted to a percent of metal on resin solids.

[0089] For Borchers® Deca Cobalt 7 aqua, / ? = 7%.

[0090] For V-TS, / ? = 9.4 %.

[0091] Unless otherwise stated, the loading level of crosslinker used, y, was based on resin solid and determined according to the relationship expressed in Equation 3:

[0092] Where a is the solid content of the resin as a percent (for example, using 0.5 for 50%), mresinthe mass of the resin used, and mcrosslinkerthe mass of the selected crosslinker compound (excluding any solvent mass). In exemplary embodiments throughout the examples, y is 5%, 10%, or 15% crosslinker compound on resin solids. As applied in equation 3, a loading level of 5% corresponds to a y value of 5.

[0093] Unless otherwise stated, all the values of formulation Tables refers to mass in gram (g), the values of hardness Tables are in seconds (s) and the values of dry time are in hours (h).

[0094] Dry time recording:

[0095] To monitor the drying time of the coatings, B.K drying recorders were used. The solution was coated on a glass stripes using a manual film applicator of 100 pm. The drying recorder was run for 24h. After 24h, drying time was assessed with the graduation scale (according to traverse 24h speed configuration). 6 samples were tested simultaneous. Each sample was repeated twice. The measurement was performed in a climate-controlled room at 23°C and 50% humidity. The Set to touch (ST), Tack free (TF) and Dry hard (DH) times were then evaluated.

[0096] Konig pendulum hardness measurement:

[0097] The pendulum hardness was measured using a TQC Sheen Pendulum Hardness Tester. It defined hardness by the Konig method as described in ISO 1522. Konig method worked on the principle that the damping time of a pendulum oscillating on a sample indicated the hardness. The TQC tester was calibrated using a glass calibration panel (VF2063, 250 + / - 10 seconds - Konig method). SP0505 Konig Pendulum was used. These measurements were performed in the climate- controlled room at 23°C and 50% humidity. The coated panels (100 pm wet film thickness) were stored in this climate room prior the hardness measurement. The hardness was measured on three different points of the coated plate, after 1 day, 7 days and 14 days dry time.

[0098] Q-FOG cycling corrosion test:

[0099] Cycling corrosion tests exposed test specimens to a series of different environment in a repetitive cycle. The cycles were done according to ASTM B117, at 35°C. The salt spray solutionused was a NaCI solution, 5 wt.% in water, pH ~7. The test was run for 288 hours. The samples were coated on metal panels (100 pm wet film thickness) and dried at ambient temperature for 14 days prior the test. The edges of each panel were protected with tape to avoid corrosion of undesired areas. A cross was made, using a cutting tool, in the middle of the metal panels. The damaged panels were then place in the Q-Fog machine for 288h. After 288h in the Q-FOG machine, the corrosion resistance was assessed visually for each panel. Also, a post weathering adhesion test was performed on these panels.

[0100] Cross cut adhesion test:

[0101] The adhesion test was performed using a crosscut adhesion test kit CC3000. The adhesion was assessed visually and classified according to ASTM D3359 ranking.

[0102] Preparation of the (3-Mercaptopropyl)trimethoxysilane hydrolyzed (ME-Si-H):

[0103] In a typical experiment, (3-Mercaptopropyl)trimethoxysilane (4 g) was placed in a vial and deionized water (4.22 g) was added to the vial. A solution of 0.1 M HCI (0.4 g) was added to the vial. The vial was stirred until the media became homogenous. The prepared solution of ME-Si-H was directly used fresh into the water born binder.

[0104] Preparation of Vanadium catalyst solution (V-TS):

[0105] A patent by the group of Prof. Honzicek and Borchers describes the use of vanadyl sulfonates as driers for the curing of alkyds, including oxidovanadium(IV) p-toluenesulfonate pentahydrate (“V- TS”) (M. Klussmann, J. Simpson Neil, J. A. N. Honzicek, P. Kalenda, J. Vinklarek, I. V. A.Charamzova, Paints containing driers based on vanadium compounds bearing anions of sulfonic acids as counter ions, WO 2021 / 260037 A1 , 2021)

[0106] V-TS (CAS-Nr. 512833-85-1 , a vanadium-based drier, 9.4% V (by mass, excluding solvent), courtesy of Prof. Jan Honzicek, University of Pardubice, Czech Republic; generally used as a stock solution of approximately 10% vanadium drier compound and 1.99% acetic acid in water.

[0107] Table V. White pigment Synaqua 4804 formulation.

[0108] Position 1 to 4, of Table V, were placed in a double walled container and were dispersed using a Dispermat LC Dissolver blade. The mixture was stirred for 5 minutes at 2500 - 3000 rpm and the stirring rate was then reduced to 1000 rpm. Addition of positions 5 to 7 and increased of the stirring speed to 4500-5000 rpm. The mixture was stirred for 25 minutes After 25 minutes, the stirring rate was changed to 1000 to 1500 rpm, then position 9 was added and stirred for 2 minutes. Position 8, 10 and 11 were then added to the container and stirred for 10 minutes at the same stirring rate. The formulation was finally filtrated using a 125 pm filter.

[0109] Table VI. Clear coat formulation of TOD 3AK 0211Y (TOD 3AK 0211 Y CC).

[0110] Position 1 to 3, of Table VI, were placed in a double walled container and stirred with a propeller blade for 5 minutes, while stirring, position 4 was added slowly into the container. Finally, position 5, 6 and 7 were added to the mixture and the total formulation was stirred for 20 minutes.

[0111] Table VIL White pigment concentrates (WPC).

[0112] Position 1 to 5, of Table VII, were placed in a glass bottle and glass beads of 1 .5-2 mm were added into the bottle (100 g). The glass bottle was closed and then placed in a disperser, LAU- Disperser DAS-200, for grinding of the pigment concentrate for 1 hour. After 1 hour grinding, the pigment concentrate was filtered to remove the glass beads.

[0113] Table VIII. White coat formulation TOD 3AK0211Y WC.

[0114] For the preparation of TOD 3AK 0211Y WC, position 1 and 2 from Table VIII were mixed.

[0115] Glossary

[0116] In the following tables providing formulation content, where not specified, all ingredients are given in mass (g).

[0117] The screening of different water-soluble thiol compounds in water-borne alkyd resins using BOC 1101 as oxidative catalysts compared to cobalt-based catalysts is illustrated in the following tables.

[0118] Table IX. Formulation of water borne Synaqua 4804 short oil alkyd used in combination with thiol crosslinker (5% on resin solid) and primary driers.

[0119] Table X. Konig hardness of Synaqua 4804 resin, using drier BOC 1101 1 % on resin solids or Deca Co 7 0.1% metal on resin solids in combination with thiols crosslinker (5% on resin solid).

[0120] Table XI. Dry time of Synaqua 4804 resin and 5% on resin solids, using drier BOC 1% on resin solid or Deca Co 7 0.07% metal on resin solids used in combination with thiol crosslinker (5% on resin solid).

[0121] In Tables X and XI, it could be seen that the addition ME-Si-H in combination with BOC 1101 , gave an improvement on hardness and dry time compared to BOC 1101 used alone.

[0122] Table XII. Influence of the catalyst choice. Formulation of water borne Synaqua 4804 short oil alkyd used in combination with ME-Si-H (5% on resin solid) and different driers.

[0123] Table XIII. Konig hardness of water borne Synaqua 4804 short oil alkyd thiol compound 5% on resin solid, using driers BOC 1101 and Borchi Dragon 1% on resin solid or Deca Co 7 0.1% metal on resin solids and V-TS 0.01 % metal on resin solids.

[0124] Table XIV. Dry time of Synaqua 4804 short oil alkyd thiol compound 5% on resin solid, using driers BOC 1101 and Borchi Dragon 1% on resin solid or Deca Co 7 0.01% metal on resin solids andV-TS 0.01 % metal on resin solids.

[0125] It was observed, in Tables XIII and XIV, that the addition of a crosslinker containing at least one thiol function was giving improvement in hardness values and dry time of the coating in combination with a manganese or vanadium catalyst.

[0126] Table XV. Formulation of ME-Si-H in Synaqua 4804. Influence of dosage (5% to 15% of crosslinker on resin solid).

[0127] Table XVI. Konig hardness ME-Si-H in Synaqua 4804. Influence of dosage (5% to 15% of crosslinker on resin solid).

[0128] Table XVII. Dry time of ME-Si-H in Synaqua 4804. Influence of dosage (5% to 15% of crosslinker on resin solid).

[0129] It was observed that the dosage of ME-Si-H was influencing the hardness values. It was noted that even with a dosage of 5% on resin solid, the dry time was highly impacted too. Even 10% on resin solid was already sufficient to have a significant impact on hardness. It was decided that the dosage of ME-Si-H was kept at 15% on resin solid for the study of the influence on the oil length of the alkyd.

[0130] Table XVIII. Formulation in Synaqua 4804 short oil alkyd, with and without pigments, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0131] Table XIX. Konig hardness of Synaqua 4804 short oil alkyd, with and without pigments, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0132] Table XX. Dry time of Synaqua 4804 short oil alkyd, with and without pigments, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0133] Table XXL Formulation in Beckosol AQ 206 medium oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0134] Table XXII. Konig hardness of Beckosol AQ 206 medium oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0135] Table XXIII. Dry time of Beckosol AQ 206 medium oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0136] Table XXIV. Formulation in Beckosol AQ 101 long oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0137] Table XXV. Konig hardness of Beckosol AQ 101 long oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0138] Table XXVI. Dry time of Beckosol AQ 101 long oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0139] Table XXVII. Formulation in 3AK0211Y alkyd, with and without pigments, using BOC 1101 , V- TS catalyst and ME-Si-H 15% on resin solid.

[0140] Table XXVIII. Konig hardness of 3AK0211Y alkyd, using BOC 1101 , V-TS catalyst and ME- Si-H 15% on resin solid.

[0141] Table XXIX. Dry time of 3AK0211Y alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0142] Table XXX. Formulation in Synaqua 2070 medium oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0143] Table XXXI. Konig hardness of Synaqua 2070 medium oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0144] Table XXXII. Dry time of Synaqua 2070 medium oil alkyd, using BOC 1101 , V-TS catalyst and ME-Si-H 15% on resin solid.

[0145] Independently of the oil length of the water born alkyd chosen, it was observed that the combination of ME-Si-H with BOC 1101 or V-TS catalysts allowed the hardness of the coating to rise. In some cases, an improvement of the dry time of the coating was also observed.

[0146] Comparison of ME-Si-H crosslinker to silicon thiol functionalized emulsions

[0147] To understand if the improvement of hardness values could be due to the presence of the silicon atom in the crosslinkers, silicon thiol functionalized emulsions were used as crosslinkers and compared to the ME-Si-H crosslinker. The commercially available emulsion from the company Shin Etsu was tested, KM-9769 (33% solid emulsion).

[0148] Table XXXIII. Formulation in Synaqua 4804 short oil alkyd, using BOC 1101 , and silicon thiol emulsion compared to ME-Si-H.

[0149] Table XXXIV. Konig hardness of Synaqua 4804 short oil alkyd, using BOC 1101 , and silicon thiol emulsion compared to ME-Si-H.

[0150] Table XXXV. Dry time of Synaqua 4804 short oil alkyd, using BOC 1101 , and silicon thiol emulsion compared to ME-Si-H.

[0151] It could be assumed that the self-condensation of silanol groups in addition to the reaction of the thiol group on the fatty acid of the alkyd, was responsible for the hardness increase when using ME-Si-H crosslinker and was not only due to the presence of the silicon atom.

[0152] Corrosion resistance test

[0153] The emulsion of silicon thiol and ME-Si-H were tested in the white coat formulation TOD 3AK0211Y to study the influence of the crosslinkers on the corrosion resistance of the coatings.

[0154] Table XXXVI. Formulation for corrosion resistance test in TOD 3AK0211Y WC alkyd, using BOC 1101 , and silicon thiol emulsion compared to ME-Si-H.

[0155] Table XXXVII. Konig hardness for corrosion resistance test in TOD 3AK0211Y WC alkyd, using BOC 1101 , and silicon thiol emulsion compared to ME-Si-H.

[0156] Table XXXVIII. Dry time of for corrosion resistance test in TOD 3AK0211Y WC alkyd, using BOC 1101 , and silicon thiol emulsion compared to ME-Si-H.

[0157] A series of Coated panels of TOD 3AK0211Y after 288h in the QFOG machine were evaluated for corrosion resistance using crosslinker in combination with BOC 1101.

[0158] Table XXXIX. Corrosion resistance evaluation visual in TOD 3AK0211Y WC alkyd, using BOC 1101 , and silicon thiol emulsion compared to ME-Si-H.

[0159] The rating of the corrosion resistance was done on the following way: 0 = same as BOC 1101 ; 1 = better than BOC 1101 ; and Ref = BOC 1101.

[0160] Sample 1 containing BOC 1101 1% on resin solid, was taken as the reference for the evaluation. The rating for the adhesion test was done according to the ASTM D3359 where 5B represented the best adhesion and 0B the worse. Except from KM 97-69 sample, the use of the crosslinker in combination with BOC 1101 helped increasing the corrosion resistance and adhesion of the coated panels.

[0161] In water, the addition of a crosslinker was more challenging as other components (such as surfactants or thickeners) and physico-chemistry (pH media, viscosity or inter polymer chain diffusion, particle stability) should be considered as opposed to solvent born coatings. Without being limited to any one theory or mode of operation, it is believed that the combination of a hydrolyzed thiol silane with BOC 1101 , vanadium or manganese catalysts, leads to improvement in hardness and decreasein dry time. Surprisingly the best results were not when a polythiol was used but when a compound with a silanol and a thiol functionality was used. Once hydrolyzed, the (3-mercaptopropyl) trimethoxysilane possessed a thiol functionality and a silanol functionality. The silanol part of the crosslinker enabled it to be water compatible, while the thiol part, more hydrophobic, would be able to react with the unsaturation of the apolar alkyd. The crosslinking may have been augmented with the self-condensation of silanol groups. It is believed that the “surfactant” behavior of the hydrolyzed (3- mercaptopropyl) trimethoxysilane was the key to such performance thus compatibilizing two different media.

[0162] It is also believed that the following mercapto silane compounds may have applicability: siliceous compounds comprising a thiol function, namely an organic compound comprising one or more hydrolysable silanes and one or more “free” thiol functions SH.

[0163] One particular embodiment of the invention concerns nonpolymeric siliceous compounds comprising a thiol function or functions. More particularly, the siliceous compounds comprising a thiol function or functions according to the invention contain from 1 to 15 silicon atom(s) per molecule, and preferably 1 silicon atom per molecule. The siliceous compounds comprising a thiol function or functions according to the invention contain in particular 1 to 12 -SH thiol group(s) per molecule, and preferably 1 to 2 -SH groups per molecule. By way of example of siliceous compounds comprising a thiol function or functions according to the invention, mention may be made of the siliceous compounds belonging to formulae (A) and (B) below:in which formula (A):Ri, 2 and R3, which may be identical or different, represent: a hydrogen atom, or a group chosen from C1-20 alkoxy, C3-9 cycloalkyloxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkyloxy such as cyclo pentyl oxy or cyclohexyloxy, C1-6 alkylcarbonyloxy or Ci-e alkyl-C(O)-O-, G-C1-20 alkyl, or G-C1-20 alkoxy with G representing a hydroxyl, C1-6 alkoxy, or thiol SH group; andALK represents a C1-20 alkylene chain, which is optionally interrupted and / or terminated, in the a-position with respect to silicon atom.in which formula (B): p, q, r, s, t and u are 0 or 1 ; x is an integer between 1 and 20, limits included, in particular between 1 and 10, limits included; m is an integer between 1 and 4, limits included, and n is an integer between 1 and 3, limits included;R'i, R'2, R S, R'4 and R's, which may be identical or different, represent:(i) the same groups as Ri, R2 and R3 as defined above,(ii) a trisubstituted siloxane group RaRbRcSi-O- with Ra, Rb and Rc, which may be identical or different, representing the same groups as R1, R2 and R3 as defined above,(iii) a group R'aR'bR'cSi-O-Si (R'd)(R'e)-ALK"-, with ALK" being as defined for ALK above, and R'a, R'b, R'c, R'd and R'e, which may be identical or different, representing: a hydrogen atom, a hydroxyl group, a (C1-4) alkoxy group, a (Ci-4)alkyl group, or a group R"aR"bR"cSi-O-, with R"a, R"b and R"c, which may be identical or different, representing a hydrogen atom or a (Ci-4)alkyl group;ALK and ALK' , which may be identical or different, represent a group as defined for ALK above;X and X', which may be identical or different, represent:(i) a o bond,(ii) a heteroatom such as oxygen, or an NR group with R representing a hydrogen atom or a (C1-4) alkyl group; and wherein preferably, in formula (B):X does not represent a bond when s is zero, when m is 1 , then p, q and r are 1 ,when m is 2, then p is 0, and q and r are 1 , when m is 3, then p and q are 0 and r is 1 , when m is 4, then p, q and r are 0, when n is 1 , then t and u are 1 , when n is 2, then t is 1 and u is 0, and when n is 3, then t and q are 0.

[0164] Preferably, the siliceous compounds comprising a thiol function or functions according to the invention are those of formula (A).

[0165] The best mode for carrying out the invention has been described for purposes of illustrating the best mode known to the applicant at the time. The examples are illustrative only and not meant to limit the invention, as measured by the scope and merit of the claims. The invention has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims

What is Claimed is:1 . A process to improve at least one physical property of a water-borne alkyd resin comprising the steps, without regard to order, of:(a) adding at least one hydrocarbyl mercapto silane crosslinker compound, the at least one mercapto silane crosslinker compound containing at least one thiol group, preferably two or more thiol groups; and at least one hydrolysable organosilane group in which the hydrolysable group contains at least one alkoxy group having from 1 to 4 carbon atoms or at least one acyloxy group having from 1 to 8 carbon atoms;(b) adding at least one drier complex, the drier complex comprising:(i) at least one transition metal ion selected from the group consisting of vanadium, iron, copper and manganese; and(ii) at least optionally one polydentate accelerant ligand which bonds to the at least one transition metal ion by way of one or more donor sites wherein the ligand is a bi-, tri-, tetra-, penta- or hexa-dentate ligand coordinating through nitrogen or oxygen donor atoms respectively; and(c) adding the water-borne alkyd resin; the combination of (a), (b) and (c) improving at least one physical property of the water-borne alkyd resin, the physical property selected from the group consisting of accelerated dry time, improved hardness and improved corrosion resistance with the proviso that when the at least one transition metal ion is vanadium, no polydentate accelerant ligand is added.

2. The process of claim 1 wherein the organosilane group is selected from the group consisting of 3- (triethoxysilyl)propyl, 4-(triethoxysilyl)butyl, 2-methyl-3-(triethoxysilyl)propyl, 3- (trimethoxysilyl)propyl, 3-triacetoxysilylpropyl, 3-(diethoxymethylsilyl)propyl, 3- (diethoxyethylsilyl)propyl, 3-(dimethoxymethylsilyl)propyl or 3-(diacetoxymethylsilyl)propyl, triacetoxysilylalkyl, and diacetoxymethylsilylalkyl groups, and mixtures thereof.The process of claim 1 or 2 wherein the hydrocarbyl mercapto crosslinker compound is of formula (VI):The process of claim 1 wherein the hydrocarbyl mercapto silane crosslinker compound is selected from the group consisting of formulae (A) and (B) below:in which formula (A):Ri, R2 and R3, which may be identical or different, represent: a hydrogen atom, or a group chosen from C1-20 alkoxy, C3-9 cycloalkyloxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkyloxy such as cyclopentyloxy or cyclohexyloxy, C1-6 alkylcarbonyloxy or C1-6 alkyl- C(O)-O-, G-C 1-20 alkyl, and G-C1-20 alkoxy with G representing a hydroxyl, C1-6 alkoxy, or thiol SH group; orALK represents a C1-20 alkylene chain, which is optionally interrupted or terminated, in the a-position with respect to the silicon atomin which formula (B): p, q, r, s, t and u are 0 or 1 ; x is an integer between 1 and 20, limits included, in particular between 1 and 10, limits included; m is an integer between 1 and 4, limits included, and n is an integer between 1 and 3, limits included;R'i, R'2, R S, R'4 and R's, which may be identical or different, represent:(i) the same groups as Ri, R2 and R3 as defined above,(ii) a trisubstituted siloxane group RaRbRcSi-O- with Ra, Rb and Rc, which may be identical or different, representing the same groups as R1, R2 and R3 as defined above,(iii) a group R'aR'bR'cSi-O-Si (R'd)(R'e)-ALK"-, with ALK" being as defined for ALK above, and R'a, R'b, R'c, R'd and R'e, which may be identical or different, representing: a hydrogen atom, a hydroxyl group, a (C1-4) alkoxy group, a (Ci-4)alkyl group, or a group R"aR"bR"cSi-O-, with R"a, R"b and R"c, which may be identical or different, representing a hydrogen atom or a (Ci-4)alkyl group;ALK and ALK', which may be identical or different, represent a group as defined for ALK above;X and X', which may be identical or different, represent:(i) a o bond,(ii) a heteroatom such as oxygen, or an NR group with R representing a hydrogen atom or a (C1-4) alkyl group; and wherein preferably, in formula (B):X does not represent a bond when s is zero,when m is 1 , then p, q and r are 1 , when m is 2, then p is 0, and q and r are 1 , when m is 3, then p and q are 0 and r is 1 , when m is 4, then p, q and r are 0, when n is 1 , then t and u are 1 , when n is 2, then t is 1 and u is 0, and when n is 3, then t and q are 0. The process of any of claims 1 to 4 wherein the at least one transition metal ion is selected from the group consisting of: a vanadium-containing drier wherein the vanadium is selected from the group consisting of V(ll), V(lll), V(IV) or V(V) compounds, an iron-containing drier wherein the iron is selected from the group consisting of Fe(ll) or Fe(lll) compounds, a manganese-containing drier wherein the manganese is selected from the group consisting of Mn(ll), Mn(lll) or Mn(IV) compounds, and a copper-containing drier wherein the copper is selected from the group consisting of Cu(l) or Cu(ll). The process of any of claims 1 to 5 wherein the at least one drier complex is BOC, namely iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2-pyridinyl-kN)methyl]- 3,7-diazabicyclo[3.3.1]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1) illustrated below as Formula (I)The process of any of claims 1 to 5 wherein the at least one drier complex is selected from the group consisting of is oxidovanadium p-toluenesulfonate, illustrated below as formula (III)and oxidovanadium p-dodecylbenzenesulfonate, illustrated below as formula (IV)The product of the process of any of claims 1 to 7. The process of any of claims 1 to 7 wherein the at least one hydrocarbyl mercapto silane crosslinker compound containing at least one thiol group has a thiol functional group that reacts with the unsaturation of the water-borne alkyd resin andat least one silanol functional group that self-condenses to add more crosslinking to the water-borne alkyd resin. A water-borne alkyd resin which comprises:(a) at least one hydrocarbyl mercapto silane crosslinker compound, the at least one hydrocarbyl mercapto silane compound comprising at least one thiol group, preferably two or more thiol groups and at least one hydrolysable organosilane group in which the hydrolysable group contains at least one alkoxy group having from 1 to 4 carbon atoms or at least one acyloxy group having from 1 to 8 carbon atoms; and(b) at least one drier complex, the drier complex comprising:(i) at least one transition metal ion selected from the group consisting of vanadium, iron, copper and manganese; and(ii) at least optionally one polydentate accelerant ligand which bonds to the at least one transition metal ion by way of one or more donor sites wherein the ligand is a bi-, tri-, tetra-, penta- or hexa-dentate ligand coordinating through nitrogen or oxygen donor atoms respectively; and(c) a water-borne alkyd resin; with the proviso that when the at least one transition metal ion is vanadium, no polydentate accelerant ligand is added. The water-borne alkyd resin of claim 10 wherein the hydrocarbyl mercapto silane crosslinker compound comprises (3-mercaptopropyl) trimethoxysilane.The water-borne alkyd resin of claim 10 comprising a hydrocarbyl mercapto silane crosslinker compound of formula (VI):water-borne alkyd resin of claim 10 wherein the hydrolysable mercapto silane crosslinker compound is selected from the group consisting of formulae (A) and (B) below:in which formula (A):Ri, R2 and R3, which may be identical or different, represent: a hydrogen atom, or a group chosen from C1-20 alkoxy, C3-9 cycloalkyloxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkyloxy such as cyclopentyloxy or cyclohexyloxy, C1-6 alkylcarbonyloxy or C1-6 alkyl- C(O)-O-, G-C 1-20 alkyl, and G-C1-20 alkoxy with G representing a hydroxyl, C1-6 alkoxy, or thiol SH group; orALK represents a C1-20 alkylene chain, which is optionally interrupted or terminated, in the a-position with respect to the silicon atomin which formula (B): p, q, r, s, t and u are 0 or 1 ; x is an integer between 1 and 20, limits included, in particular between 1 and 10, limits included; m is an integer between 1 and 4, limits included, and n is an integer between 1 and 3, limits included;R'i, R'2, R'3, R'4 and R's, which may be identical or different, represent:(i) the same groups as R1, R2 and R3 as defined above,(ii) a trisubstituted siloxane group RaRbRcSi-O- with Ra, Rb and Rc, which may be identical or different, representing the same groups as R1, R2 and R3 as defined above,(iii) a group R'aR'bR'cSi-O-Si (R'd)(R'e)-ALK"-, with ALK" being as defined for ALK above, and R'a, R'D, R'C, R'd and R'e, which may be identical or different, representing: a hydrogen atom, a hydroxyl group, a (C1-4) alkoxy group, a (Ci-4)alkyl group, or a group R"aR"bR"cSi-O-, with R"a, R"b and R"c, which may be identical or different, representing a hydrogen atom or a (Ci-4)alkyl group;ALK and ALK', which may be identical or different, represent a group as defined for ALK above;X and X', which may be identical or different, represent:(i) a o bond,(ii) a heteroatom such as oxygen, or an NR group with R representing a hydrogen atom or a (C1-4) alkyl group; and wherein preferably, in formula (B):X does not represent a bond when s is zero, when m is 1 , then p, q and r are 1 , when m is 2, then p is 0, and q and r are 1 , when m is 3, then p and q are 0 and r is 1 , when m is 4, then p, q and r are 0, when n is 1 , then t and u are 1 , when n is 2, then t is 1 and u is 0, and when n is 3, then t and q are 0. water-borne alkyd resin of any of claims 10 to 13 wherein the at least one transition metal ion is selected from the group consisting of: a vanadium-containing drier wherein the vanadium is selected from the group consisting of V(ll), V(lll), V(IV) or V(V) compounds, an iron-containing drier wherein the iron is selected from the group consisting of Fe(ll) or Fe(lll) compounds, a manganese-containing drier wherein the manganese is selected from the group consisting of Mn(ll), Mn(lll) or Mn(IV) compounds, anda copper-containing drier wherein the copper is selected from the group consisting of Cu(l) and Cu(ll). The water-borne alkyd resin of any of claims 10 to 14 wherein the at least one drier complex is BOC, namely iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2- pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1) illustrated below as Formula (I)and the at least one drier complex is selected from the group consisting of is oxidovanadium p- toluenesulfonate, illustrated below as formula (III)and oxidovanadium p-dodecylbenzenesulfonate, illustrated below as formula (IV)

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