Cross-linking agent for aqueous alkyd resin

Abstract

The present invention relates generally to hydrocarbyl mercapto crosslinkers comprising at least one hydrolyzable organosilane group that can be added to alkyd coatings, improving at least one physical property of aqueous alkyd coatings as compared to coatings without the addition, as well as compositions, methods, and processes related thereto.

Description

[0001] Cross - reference to related applications

[0002] None Technical field

[0003] The invention described herein generally relates to compounds containing one or more thiol groups, which are used as cross - linkers that can be added to alkyd resin coatings, can improve the hardness of aqueous alkyd resins, and in some cases, to cross - linkers having hydrolyzable organosilanes containing one or more thiol groups. Background art

[0004] Primary paint driers, usually metal carboxylates such as cobalt neodecanoate, are used to catalyze the oxidative drying (curing) of alkyd resins. Generally, these driers are transition - metal - based complexes. Cobalt driers are the most commonly used drying catalysts because they result in highly cross - linked hard films. Highly cross - linked hard films are desirable because they have high scratch resistance, chemical resistance, and corrosion resistance. However, several environmental studies have shown the potential re - classification of cobalt - based alkyd resin driers. Oxy Coat (“BOC”) is a primary drier for alkyd resins. At least three patent families are related to Oxy Coat, which cover variants of catalysts and structures using different delivery forms in the formulation of coatings and composites. It has been found that BOC shows faster curing and less yellowing of the alkyd resin film at much lower concentrations than cobalt. However, it has been found that BOC lacks the formation of a hard film when compared with some cobalt driers.

[0005] Therefore, there is a need for non - cobalt - based driers as alternatives, especially in the field of aqueous alkyd resin coatings. The lack of hardness affects the use of BOC as a cobalt substitute in more demanding applications such as direct metal coating or decorative coatings to provide scratch resistance, improved corrosion resistance, and the ability to quickly stack painted parts.

[0006] It has been determined that when tested in aqueous alkyd resins, organic - solvent - soluble polythiols previously used in solvent - based alkyd resins such as pentaerythritol tetra(3 - mercaptopropionate) (“ME - 4”) are relatively ineffective. It was thought that even though ME - 4 is insoluble in water, once the water phase evaporates, it would still be compatible with the non - polar alkyd resin. However, when no organic solvent is used, the ME - 4 cross - linker shows incompatibility with the alkyd resin.

[0007] Studies have shown that a more effective method of achieving accelerated drying times and improving the hardness of aqueous alkyd resins can be achieved by using cross - linkers having hydrolyzable organosilanes containing one or more thiol groups. Summary of the invention

[0008] The present invention relates to a new class of crosslinking agents for waterborne alkyd resins, the crosslinking agents having a thiol functional group and a silanol functional group that react with the unsaturation of fatty acids, and the silanol functional group being capable of self-condensing to add more crosslinking to the coating in combination with OxyCoat 1101 (“BOC1101”) or Dragon or a vanadium catalyst (such as V-TS).

[0009] In a first embodiment of the present invention, a method of improving at least one physical property of a waterborne alkyd resin is described, the method comprising the steps, in no particular order:

[0010] (a) adding at least one hydrocarbyl mercapto crosslinking agent compound, the at least one mercapto crosslinking agent compound containing at least one thiol group, preferably two or more thiol groups; and at least one hydrolyzable organosilyl group, wherein the hydrolyzable group contains at least one alkoxy group having 1 to 4 carbon atoms or at least one acyloxy group having 1 to 8 carbon atoms;

[0011] (b) adding at least one drier complex, the drier complex comprising:

[0012] (i) at least one transition metal ion selected from vanadium, iron, copper, and manganese; and

[0013] (ii) optionally present at least one polydentate promoter ligand that bonds to the at least one transition metal ion through one or more donor sites, wherein the ligand is a bidentate, tridentate, tetradentate, pentadentate, or hexadentate ligand that coordinates through nitrogen or oxygen donor atoms, respectively; and

[0014] (c) adding the waterborne alkyd resin;

[0015] The combination of (a), (b), and (c) improves at least one physical property of the waterborne alkyd resin, the physical properties being selected from accelerated drying time, improved hardness, and improved corrosion resistance,

[0016] provided that when the at least one transition metal ion is vanadium, no polydentate promoter ligand is added.

[0017] In a second embodiment of the first embodiment, the silane group is selected from 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; or

[0018] the at least one hydrocarbyl mercapto crosslinker compound is selected from (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, triacetoxy(3-mercaptopropyl)silane.

[0019] In a third embodiment of the first or second embodiment, the hydrocarbyl mercapto crosslinker compound has the formula (VI):

[0020]

[0021] In a fourth embodiment of the first embodiment, the hydrocarbyl mercapto crosslinker compound is selected from the following formulas (A) and (B):

[0022]

[0023] wherein formula (A):

[0024] R1, R2 and R3 may be the same or different and represent: a hydrogen atom, or a group selected from: C 1-20 alkoxy, C 3-9 cycloalkoxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkoxy such as cyclopentyloxy or cyclohexyloxy, C 1-6 alkylcarbonyloxy or C 1-6 alkyl-C(O)-O-, G-C 1-20 alkyl and G-C 1-20 alkoxy, where G represents a hydroxyl group, C 1-6 alkoxy or a thiol SH group; or

[0025] ALK represents a C 1-20 alkylene chain in the α-position relative to the silicon atom, which is optionally interrupted or capped,

[0026]

[0027] wherein formula (B):

[0028] p, q, r, s, t and u are 0 or 1;

[0029] x is an integer from 1 to 20, especially from 1 to 10, including the end values;

[0030] m is an integer from 1 to 4, including the end values, and

[0031] n is an integer from 1 to 3, including the end values;

[0032] R’1, R’2, R’3, R’4 and R’5 may be the same or different and represent:

[0033] (i) a group the same as R1, R2 and R3 as defined above,

[0034] (ii) a trisubstituted siloxanyl group R a R b R c Si - O -, where R a , R b and R c may be the same or different and represent a group the same as R1, R2 and R3 as defined above, or

[0035] (iii) a group R′ a R′ b R′ c Si - O - Si(R′ d )(R′ e ) - ALK″ -, where ALK″ is as defined above for ALK, and R′ a , R′ b , R′ c , R′ d and R′ e may be the same or different and represent: a hydrogen atom, a hydroxyl group, a C 1-4 alkoxy group, a C 1-4 alkyl group, or a group R” a R” b R” c Si - O -, where R” a , R” b and R” c may be the same or different and represent a hydrogen atom or a C 1-4 alkyl group;

[0036] ALK and ALK' may be the same or different and represent a group as defined above for ALK;

[0037] X and X' may be the same or different and represent:

[0038] (i) a σ - bond,

[0039] (ii) a heteroatom such as oxygen, or an NR group, where R represents a hydrogen atom or a C 1-4 alkyl group;

[0040] And preferably, in formula (B),

[0041] when s is 0, X does not represent a bond,

[0042] when m is 1, then p, q and r are 1,

[0043] when m is 2, then p is 0, q and r are 1,

[0044] when m is 3, then p and q are 0 and r is 1,

[0045] when m is 4, then p, q and r are 0,

[0046] when n is 1, then t and u are 1,

[0047] when n is 2, then t is 1 and u is 0, and

[0048] when n is 3, then t and q are 0.

[0049] In a fifth embodiment of any one of the first to fourth embodiments, the at least one transition metal ion is selected from the following group:

[0050] Vanadium-containing driers, wherein the vanadium is selected from V(II), V(III), V(IV) or V(V) compounds,

[0051] Iron-containing driers, wherein the iron is selected from Fe(II) or Fe(III) compounds,

[0052] Manganese-containing driers, wherein the manganese is selected from Mn(II), Mn(III) or Mn(IV) compounds, and

[0053] Copper-containing driers, wherein the copper is selected from Cu(I) and Cu(II).

[0054] In a sixth embodiment of any one of the first to fifth embodiments of the present invention, the at least one drier complex is BOC, that is, iron(1+), chloro[9,9-dihydroxy-3-methyl-2,4-bis(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-, chloride (1:1) as shown in formula (I).

[0055]

[0056] In a seventh embodiment of any one of the first to fifth embodiments of the present invention, the at least one drier complex is selected from vanadyl p-toluenesulfonate represented by the following formula (III) and vanadyl dodecylbenzenesulfonate represented by the following formula (IV):

[0057]

[0058] In the eighth embodiment of the first embodiment of the present invention, a product of the result of the method of any one of the foregoing embodiments 1 to 7.

[0059] In a ninth embodiment of any one of the first to seventh embodiments, the at least one hydrocarbyl mercapto silane crosslinker compound contains at least one thiol group and at least one silanol functional group, the thiol group having a thiol functionality that reacts with the unsaturation of the waterborne alkyd resin, and the silanol functional group self-condensing to add more crosslinking to the waterborne alkyd resin.

[0060] In a tenth embodiment of the present invention, a waterborne alkyd resin is described, which comprises:

[0061] (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 hydrolyzable organosilyl group, wherein the hydrolyzable group contains at least one alkoxy group having 1 to 4 or 1 to 8 carbon atoms such as methoxy, ethoxy, isopropoxy or butoxy, or at least one acyloxy group such as acetoxy. The organosilyl group compound can be a group 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,

[0062] (b) at least one drier complex, the drier complex comprising:

[0063] (i) at least one transition metal ion selected from vanadium, iron, copper and manganese; and

[0064] (ii) optionally present at least one polydentate promoter ligand that bonds to the at least one transition metal ion through one or more donor sites, wherein the ligand is a bidentate, tridentate, tetradentate, pentadentate or hexadentate ligand that coordinates through nitrogen or oxygen donor atoms respectively; and

[0065] (c) a waterborne alkyd resin;

[0066] Provided that when the at least one transition metal ion is vanadium, no polydentate promoter ligand is added.

[0067] In the eleventh embodiment of the tenth embodiment of the present invention, the hydrocarbyl mercapto crosslinking agent compound is selected from (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, triacetoxy(3-mercaptopropyl)silane, and a mercapto-functional silicone material of formula (VI).

[0068] In the twelfth embodiment of the eleventh embodiment of the present invention, the hydrocarbyl mercapto crosslinking agent compound has the formula (VI):

[0069]

[0070] In the thirteenth embodiment of the tenth embodiment of the present invention, the mercapto crosslinking agent compound is selected from the following formulas (A) and (B):

[0071]

[0072] Wherein formula (A):

[0073] R1, R2, and R3 may be the same or different and represent: a hydrogen atom, or a group selected from the following: C 1-20 alkoxy, C 3-9 cycloalkoxy, an optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkoxy such as cyclopentyloxy or cyclohexyloxy, C 1-6 alkylcarbonyloxy or C 1-6 alkyl-C(O)-O-, G-C 1-20 alkyl and G-C 1-20 alkoxy, wherein G represents a hydroxyl group, C 1-6 alkoxy or a thiol SH group; or

[0074] ALK represents a C 1-20 alkylene chain at the α-position relative to the silicon atom, which is optionally interrupted or terminated

[0075]

[0076] Wherein formula (B):

[0077] p, q, r, s, t, and u are 0 or 1;

[0078] x is an integer from 1 to 20, particularly from 1 to 10, including the end values;

[0079] m is an integer from 1 to 4, including the end values, and

[0080] n is an integer from 1 to 3, including the end values;

[0081] R’1, R’2, R’3, R’4, and R’5 may be the same or different and represent:

[0082] (i) A group the same as R1, R2 and R3 as defined above,

[0083] (ii) A trisubstituted siloxane group R a R b R c Si-O-, where R a 、R b and R c may be the same or different and represent a group the same as R1, R2 and R3 as defined above,

[0084] (iii) The group R′ a R′ b R′ c Si-O-Si(R′ d )(R′ e )-ALK″-, where ALK″ is as defined above for ALK, and R′ a 、R′ b 、R′ c 、R′ d and R′ e may be the same or different and represent: a hydrogen atom, a hydroxyl group, a C 1-4 alkoxy group, a C 1-4 alkyl group, or the group R” a R” b R” c Si-O-, where R” a 、R” b and R” c may be the same or different and represent a hydrogen atom or a C 1-4 alkyl group;

[0085] ALK and ALK' may be the same or different and represent a group as defined above for ALK;

[0086] X and X' may be the same or different and represent:

[0087] (i) A σ bond,

[0088] (ii) A heteroatom such as oxygen, or an NR group, where R represents a hydrogen atom or a C 1-4 alkyl group; and preferably, in formula (B):

[0089] When s is 0, X does not represent a bond,

[0090] When m is 1, then p, q and r are 1,

[0091] When m is 2, then p is 0, q and r are 1,

[0092] When m is 3, then p and q are 0 and r is 1,

[0093] When m is 4, then p, q, and r are 0,

[0094] When n is 1, then t and u are 1,

[0095] When n is 2, then t is 1 and u is 0, and

[0096] When n is 3, then t and q are 0.

[0097] In a fourteenth embodiment of the tenth to thirteenth embodiments of the present invention, the at least one transition metal ion is selected from:

[0098] A vanadium-containing drier, wherein the vanadium is selected from V(II), V(III), V(IV), or V(V) compounds,

[0099] An iron-containing drier, wherein the iron is selected from Fe(II) or Fe(III) compounds, and

[0100] A manganese-containing drier, wherein the manganese is selected from Mn(II), Mn(III), or Mn(IV) compounds, and

[0101] A copper-containing drier, wherein the copper is selected from Cu(I) and Cu(II).

[0102] In a fifteenth embodiment of the tenth to fourteenth embodiments of the present invention, the at least one drier complex is:

[0103] BOC, that is, iron(1+), chloro[9,9-dihydroxy-3-methyl-2,4-bis(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-, chloride (1:1), as shown in the following formula (I):

[0104]

[0105] Vanadyl p-toluenesulfonate, as shown in the following formula (III):

[0106]

[0107] Or

[0108] Vanadyl dodecylbenzenesulfonate, as shown in the following formula (IV):

[0109]

[0110] These and other objects of the present invention will be apparent when considering the detailed description and the appended claims. Detailed Description

[0111] The best mode for carrying out the present invention will now be described in order to illustrate the best mode known to the applicant at the time of filing the present invention. The examples are illustrative only and are not meant to limit the present invention as defined by the scope and spirit of the claims.

[0112] Unless the context clearly indicates otherwise, "and" indicates a conjunctive relationship; "or" indicates a disjunctive relationship; when a statement is expressed in a disjunctive relationship and is followed by "or both" or "a combination thereof", both the conjunctive and disjunctive relationships are covered.

[0113] As used in this application, unless otherwise specified, the term "about" is within 10% of the stated value.

[0114] The present invention has a wide range of uses related to various solvent and water-based coating compositions, which term is broadly interpreted herein. Examples of coating compositions include clear or colored varnishes, topcoats, filling pastes, glazes, emulsions, and floor coverings such as linoleum floor coverings. Embodiments of the present invention relate to solvent and water-based paints and inks, particularly paints, such as high-specification paints for household use and paints for general industrial applications.

[0115] Accordingly, the term "oxidatively curable coating composition" as used herein is intended to include various colored (e.g., pigments or inks) and colorless materials, including oils and binders, which form a continuous coating through an oxidative reaction process typically forming crosslinks and other bond forms. Generally, such coating compositions may be characterized by the presence of a usually (poly)unsaturated resin, which reacts to form a solid film on a substrate, and the resin initially exists in the oxidatively curable solvent-based coating composition in the form of a liquid dissolved in an organic solvent or a solid dispersed in a continuous liquid phase. The reaction that forms the desired coating upon curing is caused by an oxidation-initiated polymerization reaction. Examples of oxidatively curable coating compositions include those based on alkyd resins, acrylate resins, polyurethane resins, polybutadiene resins, and epoxy ester resins. Typically, the curable (e.g., alkyd resin) portion of the curable composition accounts for about 1 - about 90% by weight of the total weight of the oxidatively curable solvent-based coating composition, e.g., about 20 wt% - about 70% of the total weight of the oxidatively curable solvent-based coating composition.

[0116] Alkyd resins are particularly important members of the class of oxidatively curable coating compositions and are a well-studied class of resins to which the present invention can be applied. Hereinafter, embodiments of the present invention are described with reference to the use of alkyd resins (also referred to as alkyd-based resins or alkyd-based binders). While these represent particularly important embodiments of the present invention, the present invention is not limited thereto. For clarity: The present invention is applicable to a wide range of oxidatively curable coating compositions, typically those containing at least 1 or 2 wt% of unsaturated compounds (e.g., containing unsaturated (non-aromatic) carbon-carbon double or triple bonds).

[0117] As used herein, the terms "alkyd binder" or "alkyd resin" are used interchangeably. Suitable auto-oxidizable alkyd resins for use in the present invention are generally the esterification reaction products of polyols with polyacids (or their anhydrides) and unsaturated fatty acids (or their glycerides), said unsaturated fatty acids being derived from, for example, linseed oil, tung oil, tall oil, and other drying or semi-drying oils. Alkyd resins are well known in the art and do not need to be further described herein. Their properties are mainly determined by the nature and proportion of the alcohols and acids used and the degree of condensation. Suitable alkyd resins include long-oil and medium-oil alkyd resins, such as those derived from, for example, 45 wt.% to 70 wt.% fatty acids. To improve the properties of the resin, the composition of long-oil and medium-oil alkyds can be modified. For example, polyurethane-modified alkyd resins, silicone-modified alkyd resins, styrene-modified alkyd resins, acrylic-modified alkyd resins (such as (meth)acrylic acid-modified alkyd resins), vinylated alkyd resins, polyamide-modified alkyd resins, and epoxy-modified alkyd resins or mixtures thereof are also alkyd resins suitable for use in the compositions of the present invention.

[0118] Preferably, the at least one auto-oxidizable alkyd binder is selected from medium-oil or long-oil unmodified alkyd resins, silicone-modified alkyd resins, polyurethane-modified alkyd resins, or combinations thereof. Most preferably, the alkyd binder is a long-oil (unmodified) alkyd resin, a silicone-modified alkyd resin, a polyurethane-modified alkyd resin, or combinations thereof.

[0119] Based on the total weight of the composition, the amount of alkyd binder in the compositions of the present invention can generally be from about 20 wt.% to 98 wt.%, such as from about 30 wt.% to about 90 wt.%, preferably from about 35 wt.% to 70 wt.%.

[0120] As used herein, the term "drying agent" (also synonymously referred to as "desiccant" when in solution) refers to an organometallic compound that is soluble in organic solvents and binders. They are added to unsaturated oils and binders in order to significantly reduce their drying time, i.e., the transition of their film to the solid phase. Drying agents can be obtained in solid or solution form. Suitable solvents are organic solvents and binders, sometimes including water. Unless otherwise stated, drying agents are present in an amount expressed as the weight percentage of metal based on the weight of the binder solid (or resin).

[0121] As used herein, the term "drying agent composition" refers to a mixture of drying agents claimed in the present invention. The drying agent composition according to the present invention can comprise several drying agent compounds. The inventors have found that the selection of the drying agents of the present invention in coating compositions improves the drying rate of the coating compositions.

[0122] Where weight percentages (wt.% or % w / w) are mentioned in this text, unless the context clearly indicates to the contrary, this means the weight percentage relative to the solid coating film obtained by curing (i.e., the components of the oxidative-curing solvent-based coating composition used to provide the coating upon curing). Thus, for an oxidative-curing alkyd resin coating composition, the weight percentages in this text are based on the total weight of the composition components that are incorporated into the alkyd resin coating once cured to form the alkyd resin coating. For example, the composition obtained by carrying out the method according to the first aspect or the second aspect of the present invention typically contains from about 0.0001 to about 1% w / w, such as from about 0.0005 to about 0.5% w / w, or from about 0.01 to about 1% w / w, such as from about 0.05 to about 0.5% w / w of water, based on the components of the composition from the coating upon curing.

[0123] The oxidative-curing solvent-based composition herein refers to a composition based on an organic (i.e., non-aqueous) solvent in accordance with the nomenclature used in the art. Examples of suitable solvents include aliphatic (including cycloaliphatic and branched) hydrocarbons such as hexane, heptane, octane, cyclohexane, cycloheptane, and isoparaffins; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; alcohols such as isopropyl alcohol, n-butanol, and n-propanol; glycol monoethers such as monoethers of ethylene glycol and diethylene glycol; monoether glycol acetates such as 2-ethoxyethyl acetate; and mixtures thereof. Isomeric variants are included. Thus, the term hexane includes mixtures of hexanes. According to an embodiment of the present invention, the solvent is a hydrocarbon-based (i.e., hydrocarbon) solvent, such as an aliphatic hydrocarbon-based solvent, such as a solvent containing a mixture of hydrocarbons. Examples include paint solvent oils and solvents obtained from Shell Chemicals under the trade name Shellsol and Solvesso and from Exxon under the trade name Exxsol.

[0124] One of the transition metal ions used in the present invention is vanadium. The valence of the metal can be from +2 to +5. An embodiment of the present invention is a mixture of transition metal ions. In the case of providing a vanadium drier, this is typically a V(II), (III), (IV), or (V) compound, and in the case of providing an iron drier, this is typically an Fe(II) or Fe(III) compound. When providing a manganese drier, it is typically a Mn(II), (III), or (IV) compound.

[0125] To enhance the activity of the transition metal ions, so-called promoting compounds are also included, such as carboxylic acids or pentadentate amines. As the language implies, a carboxylic acid or polydentate amine promoter ligand is a compound capable of coordinating with a transition metal ion through more than one donor site within the ligand and is used to accelerate the drying (curing process) of the oxidative-curing coating composition after application.

[0126] According to some embodiments of the present invention, the multidentate amine promoter ligand is a bidentate, tridentate, tetradentate, pentadentate or hexadentate ligand coordinated through nitrogen and / or oxygen donor atoms. In a specific embodiment of the present invention, the ligand is a bidentate, tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligand, particularly a tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligand. However, the present invention is not limited thereto. Examples of various multidentate promoter ligands are discussed below.

[0127] The metal drier as described herein, for example as a preformed complex of one or more transition metal ions and one or more multidentate promoter ligands, is typically dissolved in water at a concentration of about 0.001 to about 10 wt.%, such as 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 small volume of the aqueous solution containing the metal drier to be added to the coating composition. This may be desirable to those skilled in the art. The actual amount of the metal drier depends on 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 the desired complex is 560 and contains one iron ion (mw 56), and a 0.1% level of iron is mentioned, the amount of the compound dissolved in water is 1% (w / w) or 10 grams / kg of water. If the complex is not preformed but formed in situ, the metal salt will also typically be dissolved in water at a concentration of about 0.001 to about 1 wt.%, based on the ratio of the metal ion to water. Then an appropriate amount of the multidentate promoter ligand can be added to form the desired complex.

[0128] After preparation, the solution of the metal drier can then be contacted with the coating composition, for example added to the coating composition.

[0129] Based on the weight of the oxidation-curing coating, the resulting composition containing the metal drier and typically 0.0001 - 1% water is usually a solution, i.e., a single homogeneous phase. However, it can also be an emulsion or a dispersion, for example containing discontinuous regions of an aqueous solution containing the transition metal drier.

[0130] As used in this application, the term "adhesive solution (alkyd resin)" refers to one of the following: SYNAQUA 4804 (aqueous short-oil alkyd resin, Arkema); SYNAQUA 2070 (aqueous medium-oil alkyd resin, Arkema); Beckosol AQ101 (aqueous long-oil alkyd resin, Polyont Composites USA Inc.); WorléeKyd S 351 (solvent-based medium-oil alkyd resin, Worlée); and TOD 3AK0211Y (water-dilutable alkyd resin, TOD, China) and other adhesive solutions having similar properties to the above. In a more general sense, "alkyd resin" refers to a synthetic resin made by a condensation reaction (releasing water) between a polyol (such as glycerol) and a dibasic acid (or phthalic anhydride). It is the non-volatile part of the paint vehicle. After drying, it binds the pigment particles to the paint film as a whole.

[0131] As used herein, BOC is iron(1+), chloride [9,9-dihydroxy-3-methyl-2,4-bis(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-, chloride (1:1), as shown in the following formula (I).

[0132]

[0133] As used in this application, "Borchers Deca Cobalt7 aqua" is Deca Co 7a, in a water-dispersible oil, Borchers; synonymously, cobalt neodecanoate (cobalt(2+); 7,7-dimethyloctanoate) (see formula II).

[0134]

[0135] As used herein, the term ("V-TS") is vanadyl p-toluenesulfonate, as shown in the following formula (III).

[0136]

[0137] As used herein, the term ("V-DS") is vanadyl p-dodecylbenzenesulfonate, as shown in the following formula (IV).

[0138]

[0139] As used in this application, the term "secondary drier", synonymous with "auxiliary drier", means Calcium-Hydrochem (calcium neodecanoate in an organic solvent, Borchers), and Octa Soligen Zirconium 10aqua (zirconium 2-ethylhexanoate in an organic solvent, Borchers), and other secondary driers having similar properties to the foregoing. Additionally, one or more auxiliary driers can be added to a fully formulated oxidation-curing coating composition. Such auxiliary driers can be additional components optionally present within the formulations of the present invention, but are generally not present in the formulations of the present invention. Such auxiliary driers include fatty acid soaps of zirconium, bismuth, barium, cerium, calcium, lithium, strontium, and zinc. Generally, the 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 reduce the adsorption effect of the primary drier on solid particles typically present in oxidation-curing coating compositions. If desired, other non-metal-based auxiliary driers can also be present. As is known in the art, the concentration of auxiliary driers in an oxidation-curing coating composition (or the formulations of the present invention) is typically from about 0.01 wt.% to 2.5 wt.%.

[0140] The coating composition can also contain one or more additives that are conventionally present in curable coating compositions, such as, but not limited to: UV stabilizers, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, antifouling agents, fungicides, bactericides, algaecides, insecticides, extenders, plasticizers, antifreeze agents, waxes, and thickeners.

[0141] In certain embodiments, the coating composition of the present invention contains at least one colorant. The colorant component of the coating composition can include one or more inorganic or organic, transparent or non-transparent pigments. Non-limiting examples of such pigments are titanium dioxide, iron oxide, mixed metal oxides, bismuth vanadate, chromium oxide green, ultramarine, carbon black, lamp black, monoazo and diazo pigments, anthraquinones, isoindolinones, isoindolines, quinophthalones, phthalocyanine blue and phthalocyanine green, dioxazines, quinacridones, and diketopyrrolopyrroles; 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, talc, kaolin, etc. The amount of pigment used to form the coating composition should be understood to vary depending on the application of the composition and can be zero when a transparent composition is desired.

[0142] The composition according to the present invention can be used as a clear varnish or can contain pigments. Examples of pigments suitable for use are metal oxides, such as titanium dioxide or iron oxide, or other inorganic or organic pigments.

[0143] The coating composition may also contain one or more additives, such as UV stabilizers, cosolvents, dispersants, surfactants, inhibitors, fillers, antistatic agents, flame retardants, lubricants, defoamers, extenders, plasticizers, antifreeze agents, waxes, thickeners, thixotropic agents, etc. In addition, the coating composition according to the present invention may optionally contain various antioxidants and anti-skinning agents known in the field of formulation of coating compositions, such as: phenol derivatives, such as pyrogallol, 2,6-di-tert-butyl-p-cresol, hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate- 1076 (available from Ciba SC), bis(2-mercapto-ethyl)-(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) sulfide- 1035 (available from Ciba SC), monomethyl ether of hydroquinone, allylphenol, 4-acetoxystyrene, isoeugenol, lauryl gallate; sulfides, such as phenothiazine, dodecyl sulfide, bis(dodecyl) thiodipropionate; phosphines, such as trimethylphosphine, tri-n-octylphosphine, triphenylphosphine; phosphites, such as trimethyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, ethyl-bis(2,4-di-tert-butyl-6-methylphenyl) phosphite- 38 (available from Ciba SC), tris(2,4-di-tert-butylphenyl) phosphite- 168 (available from Ciba SC), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite- 626 (available from General Electric); phosphonites, such as tetra(2,4-di-tert-butylphenyl)(1,1-biphenyl)-4,4'-diylbisphosphonite- P-EPQ (available from Ciba SC); dicarbonyl compounds, such as 2,4-pentanedione, dibenzoylmethane, 2,4-hexanedione, 1,3-cyclohexanedione, oxopropanoic acid, diethyl 2-methyl-3-oxosuccinate, oxaloacetic acid; oximes, such as methyl ethyl ketoxime, butyraldoxime, cyclohexanone oxime; hydroxyacetone, diethylhydroxylamine, 3,5-dimethylpyrazole, ascorbic acid, hindered amine light stabilizers (HALS), such as 123 and 292 (available from Ciba SC), 2,3-butylene glycol, dibenzoyloxybutene, zinc dibenzyl dithiocarbamate, vitamin E, vitamin E acetate, hypophosphorous acid, 2-butylbenzofuran, 3,4-dihydro-2-ethoxy-2H-pyran, dodecyl mercaptan, dicyclopentadiene.

[0144] The curable coating compositions according to various aspects of the present invention can be used as decorative coatings, for example, 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, textiles, glass, ceramics or metals. The curable coating compositions according to various aspects of the present invention can be used as industrial coatings, for example, applied to metal substrates such as for automotive parts, bridges, equipment or for coil coatings. The compositions so applied can then be cured. The present invention also provides the compositions upon curing.

[0145] Accordingly, the present invention also provides a method which comprises applying the composition to a substrate. The composition so applied can then be cured.

[0146] The coating compositions of the present invention can be applied to substrates using any known method. Non-limiting examples of such application methods are coating (e.g., with a paint pad or a doctor blade, or by brushing or rolling), spraying (e.g., air spraying, airless spraying, thermal spraying and electrostatic spraying), flow coating (e.g., dip coating, curtain coating, roll coating and reverse roll coating) and electrophoretic deposition. (See generally R. Lambourne, Editor, Paint and Surface Coating: Theory and Practice, Eilis Horwood, 1987, page 39 et seq.).

[0147] The coating compositions of the present invention can be applied and fully cured under ambient temperature conditions of about -10°C to 50°C. Curing of the polymer compositions according to the present invention can generally be carried out very rapidly and can generally be carried out at temperatures of -10°C to +50°C, particularly 0°C to 40°C, more particularly 3°C to 25°C. However, the compositions of the present invention can be cured by additional heating.

[0148] The coating compositions of the present invention can be used as a single layer coating, as a topcoat, a basecoat in a two-layer system, or as one or more layers of a multi-layer system comprising a clear topcoat coating composition, a colorant layer and a basecoat coating composition, or as a primer layer. Typical opaque systems can include: 1 or 2 primer layers and 1 or 2 topcoat layers (3 layers in total). Another opaque system can include: 1 primer layer, 1 intermediate coat layer and 1 topcoat layer. Examples of clear systems can include 1 dip primer layer and 3 topcoat layers or 3 topcoat layers for maintenance work.

[0149] As used herein, unless otherwise specified, the term "alkyl" refers to straight-chain and branched-chain saturated acyclic hydrocarbon monovalent groups; said alkyl may also optionally contain one or more suitable substituents independently selected from amino, halogen, hydroxy, mercapto, haloalkyl, alkoxy, etc. Specific non-limiting examples of straight-chain or branched-chain alkyl are C 1-20Alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and stearyl. It should be recognized that oxygen, sulfur or nitrogen can be inserted into the alkyl.

[0150] As used herein, unless otherwise specified, the term "alkenyl" refers to straight-chain and branched-chain unsaturated acyclic hydrocarbon monovalent groups; the alkenyl may also optionally contain one or more suitable substituents independently selected from amino, halogen, hydroxy, mercapto, haloalkyl, alkoxy, etc. Specific non-limiting examples of straight-chain or branched-chain alkenyls are those having 2 to 30 carbon atoms, where the position of the double bond can vary, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl. Again, it should be recognized that oxygen, sulfur or nitrogen can be inserted into the alkenyl.

[0151] As used herein, unless otherwise specified, the term "alicyclic" refers to a monocyclic or polycyclic saturated hydrocarbon monovalent group having 3 to 10 carbon atoms, or a C 7-10 Polycyclic saturated hydrocarbon monovalent group. Specific non-limiting examples of alicyclic alkyl or cyclic alkyl that may have substituents are cycloalkyls having 5-7 carbon atoms, such as cyclopentyl, cyclohexyl and cycloheptyl, and alkylcycloalkyls having 6-11 carbon atoms, where the position of the alkyl can vary, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylcycloheptyl and diethylcycloheptyl. Again, it should be recognized that oxygen, sulfur or nitrogen can be inserted into the alicyclic.

[0152] As used herein, unless otherwise specified, the terms "aromatic" and "aryl" denote any monocyclic or polycyclic aromatic monovalent hydrocarbon group having 6 to 30 carbon atoms, including fused benzo-C 4-8 Cycloalkyl (the latter as defined above), all of said groups being optionally substituted with one or more substituents independently selected from halogen, amino, haloalkyl, hydroxy, mercapto and nitro.

[0153] As used herein, unless otherwise specified, the term "heterocycle" refers to a monocyclic or polycyclic, saturated or mono-unsaturated or poly-unsaturated monovalent hydrocarbon group having 2 to 15 carbon atoms and containing one or more heteroatoms in one or more rings, each of said rings having 3 to 10 atoms (and optionally further containing one or more heteroatoms attached to one or more carbon atoms of said ring), for example in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and / or one or more heteroatoms of said ring, each said heteroatom independently selected from nitrogen, oxygen, sulfur, selenium and phosphorus, and also includes groups in which the heterocycle is fused to one or more aromatic rings, for example in the form of a benzo-fused, dibenzo-fused or naphtho-fused heterocyclic group, including all possible isomeric forms thereof, wherein each carbon atom of said heterocycle may independently be substituted by a substituent selected from the group consisting of: halogen, nitro, C 1-7 alkyl (as defined above, especially methyl), C 3-7 alkenyl, trifluoromethyl, C 3-10 cycloalkyl, aryl, arylalkyl, alkylaryl, hydroxy, mercapto, alkoxy (as defined above, especially methoxy), aryloxy, arylalkoxy, thioC 1-7 alkyl, thioC 3-10 cycloalkyl, thioaryl, arylalkylthio, cyano, carboxylic acid or its ester; depending on the degree of unsaturation in each said ring, the heterocyclic group may be subdivided into heteroaromatic (or "heteroaryl") groups and non-aromatic heterocyclic groups; when the heteroatom of the non-aromatic heterocyclic group is nitrogen, the latter may be substituted by a substituent selected from C 1-7 alkyl, C 3-10 cycloalkyl, aryl, arylalkyl and alkylaryl (each said group as defined herein).

[0154] As used herein, unless otherwise specified, the term "alkoxy" refers to a substituent in which the alkyl is attached to an oxygen atom by a single bond.

[0155] As used herein, unless otherwise specified, the term "halo" or "halogen" refers to any atom selected from fluorine, chlorine, bromine and iodine.

[0156] As used herein, unless otherwise specified, the term "arylalkyl" refers to an aliphatic saturated hydrocarbon monovalent group to which an aryl (as defined above) is attached, and wherein said aliphatic group or aryl may optionally be substituted by one or more substituents independently selected from halogen, amino, hydroxy, mercapto, alkyl, haloalkyl and nitro. Specific examples of arylalkyl are those having 7 - 40 carbon atoms, wherein the alkyl may be straight-chain or branched-chain, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl.

[0157] As used herein, unless otherwise specified, the term "alkylaryl" refers to an aryl group (as defined above) to which a monovalent aliphatic saturated hydrocarbon group is attached, and wherein said aliphatic group or aryl group may optionally be substituted with one or more substituents independently selected from halogen, amino, hydroxy, mercapto, alkyl, trifluoromethyl, and nitro. Specific non-limiting examples of unsubstituted or alkyl-substituted aryl groups are aryl groups having 6 to 18 carbon atoms, such as phenyl, diphenyl, and naphthyl, and alkylaryl groups having 7 to 40 carbon atoms, wherein the alkyl group may be straight-chain or branched-chain 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. The alkylaryl group may additionally have substituents, including functional groups such as alkoxy, hydroxy, cyano, nitro, halide, carboxylic acid, and the like.

[0158] As used herein, unless otherwise specified, the term "acyl" refers to a substituent derived from an acid such as an organic monocarboxylic acid, carbonic acid, carbamic acid (yielding a carbamoyl substituent), or the corresponding thioacid or imino acid (yielding a ureido substituent), wherein the acid molecule includes an aliphatic, aromatic, or heterocyclic group. A more specific "acyl" group within the above definition refers to a carbonyl (oxo) group adjacent to an alkyl, cycloalkyl, aryl, arylalkyl, or heterocyclic group, all of which are as defined herein.

[0159] As used herein, unless otherwise specified, the term "heterocyclic" refers to a monocyclic or polycyclic, saturated or monounsaturated or polyunsaturated monovalent hydrocarbon group having 2 to 15 carbon atoms and containing one or more heteroatoms in one or more rings, each of said rings having 3 to 10 atoms (and optionally further containing one or more heteroatoms attached to one or more carbon atoms of said ring), such as in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and / or one or more heteroatoms of said ring, each said heteroatom independently selected from nitrogen, oxygen, sulfur, selenium, the heterocyclic group including all its possible isomeric forms, wherein each carbon atom of said heterocyclic may independently be substituted with a substituent selected from the group consisting of: halogen, nitro, C 1-7 alkyl (as defined above, especially methyl), C 3-7 alkenyl, trifluoromethyl, C 3-10 cycloalkyl, hydroxy, mercapto, C 1-7 alkoxy (as defined above, especially methoxy), thioC 1-7 alkyl, thioC 3-10A cycloalkyl group, a cyano group, a carboxylic acid or an ester group, depending on the degree of unsaturation in each said ring, and the heterocyclic group can be subdivided into heteroaromatic (or "heteroaryl") groups and non-aromatic heterocyclic groups; when the heteroatom of the non-aromatic heterocyclic group is nitrogen, the latter can be substituted by a substituent selected from C 1-7 alkyl, C 3-10 cycloalkyl, aryl, arylalkyl and alkylaryl (each of said groups as defined herein).

[0160] As used herein, unless otherwise specified, the term "alkoxy" refers to a substituent in which an alkyl group is attached to an oxygen atom by a single bond.

[0161] As used herein, unless otherwise specified, the term "halo" or "halogen" refers to any atom selected from fluorine, chlorine, bromine and iodine.

[0162] As used herein, unless otherwise specified, the term "acyl" refers to a substituent derived from an acid such as an organic monocarboxylic acid, carbonic acid, carbamic acid (yielding a carbamoyl substituent) or a thioacid or imino acid corresponding to said acid (yielding a ureido substituent), wherein the acid molecule includes an aliphatic, aromatic or heterocyclic group. A more specific "acyl" group within the above definition refers to a carbonyl (oxo) group adjacent to an alkyl, cycloalkyl, aryl, arylalkyl or heterocyclic group, all of which groups are as defined herein.

[0163] As used herein, unless otherwise specified, the term "mercapto" or "thiol" or "sulfhydryl" refers to the SH group.

[0164] In this work, two waterborne alkyd resins (short oil and long oil) were used. For this test, 0.5% of Borchi Oxy Coat 1101 (BOC 1101) was added based on resin solids, while 5% of crosslinker ME-4 based on resin solids was added in combination with 0.5% of BOC 1101 based on resin solids, as in the following table formulation. The numbers shown in the formulation table represent mass in grams (g). The numbers shown in the hardness results represent hardness in seconds.

[0165] Table I. Synaqua 4804 formulation, using BOC 1101 vs. combination of BOC 1101 with ME-4 crosslinker

[0166] Table II. Beckosol AQ 101 formulation, using BOC 1101 vs. combination of BOC 1101 with ME-4 crosslinker

[0167]

[0168] Table III with BOC 1101 catalyst, with or without polythiol crosslinker ME-4, Synaqua 4804 and BECKOSOL AQ 101 Hardness

[0169]

[0170] During sample preparation, some sedimentation was observed, probably due to the incompatibility of ME-4 with water. In Table III, it can be seen that when combined with BOC1101, the addition of ME-4 did not significantly increase the hardness. The improvement did not match the performance previously observed in solvent-based alkyd resins. Without being limited to any one theory or mode of operation, it is assumed that this may be due to the incompatibility of ME-4 in the aqueous medium. The focus of the study shifted to polythiol miscible or water-compatible thiol compounds. Crosslinkers in aqueous alkyd resins are more challenging than those in solvent-based alkyd resins because other parameters are considered, such as surfactant structure and dosage, crosslinker stability in the aqueous medium, and alkyd resin and pH considerations.

[0171] What was observed is that the crosslinker that gives the best results in terms of hardness and drying time in combination with the oxidation catalyst is not a polythiol, but a hydrolyzable organosilane containing one or more thiol groups. In order for the crosslinker to improve the hardness and drying time in aqueous alkyd resins, it needs to contain two different functional groups:

[0172] (a) A thiol functional group that reacts with the unsaturation of fatty acids; and

[0173] (b) Silanol, which can self-condense to add more crosslinking to the coating.

[0174] It was observed that once hydrolyzed, the hydrolyzable organosilane compound containing one or more thiol groups in combination with BOC1101, Dragon or vanadium catalyst (V-TS) improved the hardness and drying time, and to some extent improved the corrosion resistance of the coating.

[0175] Several water-soluble, hydrolyzable or emulsion forms of thiol compounds were used. The crosslinkers used are shown in Table IV.

[0176] The hydrocarbyl mercapto crosslinker compound should contain at least one mercapto group, preferably two or more mercapto groups; and at least one hydrolyzable organosilane group, wherein the hydrolyzable group contains at least one alkoxy group having 1 to 4 or 1 to 8 carbon atoms, such as methoxy, ethoxy, isopropoxy or butoxy, or at least one acyloxy group, such as acetoxy. The organosilane group compound can be a group 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. This combination of functional groups improves the crosslinking of the coating through two modes of action: the formation of organosilicon (or oligosiloxane) by the condensation of several crosslinker molecules, thereby forming a new compound with multiple mercapto end groups, and the radical addition reaction between the mercapto and the unsaturation of the alkyd resin.

[0177] Description and structure of the polythiols used in Table IV.

[0178]

[0179] Formula (VI)

[0180]

[0181] Sample preparation

[0182] Pour all the components of the specific formulation into a 50 ml polypropylene mixing cup. Then place the polypropylene mixing cup in a DAC150.1 FVZ high-speed mixer and mix at 2000 rpm for 2 minutes. After mixing, store the sample in the laboratory at room temperature for 24 hours before any testing.

[0183] Unless otherwise specified, OXY-Coat 1101 (BOC 1101) and The loading level (w) of Dragon is 1% based on resin solids and is determined according to the relationship provided in Equation 1 below:

[0184]

[0185] where α is the fraction of the resin solids content (e.g., 0.5 is used for 50%), m 树脂 is the mass of the resin used, m BOC 1101或Borchi Dragonis the mass of the selected drier (BOC 1101 or Borchi Dragon, including any solvent mass). In the exemplary case of a loading level of 1 wt.% BOC 1101 or Borchi Dragon based on resin solids, w is 1.

[0186] Unless otherwise specified, the loading levels a of certain catalysts (including Deca Cobalt 7aqua and vanadium catalysts (V-TS and V-DS) are expressed as metals based on resin solids and are determined according to the relationship expressed in Equation 2:

[0187]

[0188] where α is the solids content of the resin, expressed as a fraction, m 树脂 is the mass of the resin, m 催化剂 is the mass of the selected catalyst (excluding any solvent mass), and β is the fraction of the metal content of the selected catalyst (excluding solvent mass). In Equation 2, the loading level a is expressed as a fraction of metal based on resin solids, but can be converted to a percentage of metal based on resin solids.

[0189] For Deca Cobalt 7aqua, β = 7%.

[0190] For V-TS, β = 9.4%.

[0191] Unless otherwise specified, the loading level y of the crosslinker used is based on resin solids and is determined according to the relationship expressed in Equation 3:

[0192]

[0193] where α is the solids content of the resin, expressed as a percentage (e.g., 0.5 for 50%), m 树脂 is the mass of the resin used, and m 交联剂 is the mass of the selected crosslinker compound (excluding any solvent mass). In the exemplary embodiments throughout the examples, y is 5%, 10%, or 15% crosslinker compound based on resin solids. As applied in Equation 3, a loading level of 5% corresponds to a y value of 5.

[0194] Unless otherwise specified, all values in the formulation table refer to mass in grams (g), values in the hardness table are in seconds (s), and values in the drying time table are in hours (h).

[0195] Drying time record:

[0196] To monitor the drying time of the coating, a B.K drying recorder was used. The solution was applied onto a glass strip using a 100 μm manual film applicator. The drying recorder ran for 24 h. After 24 h, the drying time was evaluated using a scale (configured according to the 24 h horizontal speed). Six samples were tested simultaneously. Each sample was repeated twice. The measurements were carried out in a climate control chamber at 23 °C and 50% humidity. Then the surface dry (ST), touch dry (TF) and through dry (DH) times were evaluated.

[0197] Pendulum hardness measurement:

[0198] The pendulum hardness was measured using a TQC Sheen pendulum hardness tester. It defines the hardness by the method as described in ISO1522. The principle of the method is that the damping time of the pendulum oscillating on the sample indicates the hardness. A glass calibration plate (VF2063, 250 + / - 10 seconds - method) was used to calibrate the TQC tester. The SP0505 pendulum was used. These measurements were carried out in a climate control chamber at 23 °C and 50% humidity. Before the hardness measurement, the coated panel (100 μm wet film thickness) was stored in this climate chamber. The hardness was measured at three different points on the coated plate after 1 day, 7 days and 14 days of drying time.

[0199] Q-FOG cyclic corrosion test:

[0200] The cyclic corrosion test exposes the test samples to a series of different environments in repeated cycles. The cycles were carried out at 35 °C according to ASTM B117. The salt spray solution used was an NaCl solution, 5 wt.% in water, pH ~ 7. The test was carried out for 288 hours. The samples were coated on metal plates (100 μm wet film thickness) and dried at ambient temperature for 14 days before the test. The edges of each plate were protected with tape to avoid corroding unwanted areas. A cross was formed in the middle of the metal plate using a cutting tool. Then the damaged plates were placed in the Q-Fog machine for 288 hours. After 288 hours in the Q-FOG machine, the corrosion resistance of each plate was visually evaluated. In addition, an adhesion test after aging was carried out on these plates.

[0201] Cross-cut adhesion test:

[0202] The adhesion test was carried out using a cross-cut adhesion test kit CC3000. The adhesion was visually evaluated and classified according to ASTM D3359 grading.

[0203] Preparation of hydrolyzed (3-mercaptopropyl) trimethoxysilane (ME-Si-H):

[0204] 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 0.1 M HCl (0.4 g) solution was added to the vial. The vial was stirred until the medium became homogeneous. The prepared ME-Si-H solution was used directly fresh in the aqueous adhesive.

[0205] Preparation of vanadium catalyst solution (V-TS):

[0206] Prof. and the patent of the Borchers group describe the use of vanadium(IV) sulfonate as a drier to cure alkyd resins, including vanadium(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 compound bearing anion of sulfonic acid as counterion, WO2021 / 260037A1, 2021).

[0207] V-TS (CAS-Nr. 512833-85-1, vanadium-based drier, 9.4% V (by mass, excluding solvents), from Prof. Jan University of Pardubice, Czech Republic; usually used as a stock solution of approximately 10% vanadium drier compound and 1.99% acetic acid in water.

[0208] Table V. Preparation of white pigment Synaqua 4804

[0209] Item No. Component Mass (g) 1 Deionized water 14 2 Byk 022 0.4 3 Disperbyk 190 1.3 4 Tiona 595 50 5 Borchi Gel 0625 1 6 Deionized water 3.5 7 Tego Glide 450 0.6 8 Synaqua 4804 119.9 9 Deionized water 5.3 10 Aquaflow NHS-300 1.9 11 Edaplan LA-452 0.6

[0210] Items 1 to 4 in Table V were placed in a double-walled container and dispersed using a Dispermat LC dissolver blade. The mixture was stirred at 2500 - 3000 rpm for 5 minutes, then the stirring rate was reduced to 1000 rpm. Items 5 to 7 were added and the stirring speed was increased to 4500 - 5000 rpm. The mixture was stirred for 25 minutes. After 25 minutes, the stirring rate was changed to 1000 - 1500 rpm, then Item 9 was added and stirred for 2 minutes. Then Items 8, 10, and 11 were added to the container and stirred at the same stirring rate for 10 minutes. Finally, the preparation was filtered using a 125 μm filter.

[0211] Table VI. Transparent Coating Preparation for TOD 3AK 0211Y (TOD 3AK 0211Y CC)

[0212] Item No. Component Mass (g) 1 TOD 3AK0211Y (72% solids) 50 2 N,N-Dimethylethanolamine 1 3 Ethylene glycol monobutyl ether 2.5 4 Deionized water 60 5 20% Sodium nitrite aqueous solution 0.8 6 Borchi Gel 1375 0.1 7 Borchi Gel 0620 (50% in water) 0.2

[0213] Place items 1 to 3 of Table VI in a double-walled container and stir with a propeller blade for 5 minutes. While stirring, slowly add item 4 to the container. Finally, add items 5, 6, and 7 to the mixture and stir the total preparation for 20 minutes.

[0214] Table VII. White Pigment Concentrate (WPC)

[0215]

[0216] Place items 1 to 5 of Table VII in a glass bottle and add 1.5 - 2 mm glass beads to the broken bottle (100 g). Close the glass bottle and then place it in a disperser LAU - Disperser DAS - 200 to grind the pigment concentrate for 1 hour. After grinding for 1 hour, filter the pigment concentrate to remove the glass beads.

[0217] Table VII.I White Coating Preparation TOD3 AK0211Y WC

[0218] Item No. Component Mass (g) 1 WPC 30 2 TOD 3AK 0211Y CC 70

[0219] To prepare TOD 3AK0211Y WC, mix items 1 and 2 of Table VIII.

[0220] Glossary

[0221]

[0222] In the following table providing the preparation content, unless otherwise specified, all components are expressed in mass (g).

[0223] Screen different water-soluble thiol compounds in an aqueous alkyd resin using BOC 1101 as an oxidation catalyst compared to a cobalt-based catalyst, as shown in the following table.

[0224] Table IX. Aqueous Synaqua4804 Short Oil Alkyd Resin Preparation Used in Combination with a Thiol Crosslinker (5% Based on Resin Solids) and a Main Drying Agent

[0225] Sample Name 1 2 3 Synaqua 4804 (~50% solids) 5 5 5 ME-Si-H (~45%, in HCl and water) 0.28 BOC 1101 0.025 0.025 Deca Co 7 0.036

[0226] Table X. Of Synaqua 4804 Resin Hardness, using a combination of BOC 1101 based on 1% of resin solids or Deca Co 7 based on 0.1% of metal in resin solids and a mercaptan crosslinking agent (5% based on resin solids).

[0227]

[0228] Table XI. Drying time of Synaqua 4804 resin, 5% based on resin solids, using a drier BOC based on 1% of resin solids or Deca Co 7 based on 0.07% of metal in resin solids in combination with a mercaptan crosslinking agent (5%, based on resin solids).

[0229]

[0230] In Tables X and XI, it can be seen that the addition of the combination of ME-Si-H and BOC 1101 improves the hardness and drying time compared to using BOC 1101 alone.

[0231] Table XII. Influence of catalyst selection. Aqueous Synaqua4804 short oil alkyd resin formulations used in combination with ME-Si-H (5%, based on resin solids) and different driers.

[0232] Sample Name 1 2 3 4 5 6 Synaqua 4804 (~50% solids) 5 5 5 5 5 5 ME-Si-H (~45%, in HCl and water) 0.28 0.28 BOC 1101 0.025 Deca Co 7 0.036 Borchi Dragon 0.025 0.025 V-TS (stock solution) 0.025 0.025

[0233] Table XIII. Hardness of aqueous Synaqua 4804 short oil alkyd mercaptan compounds, 5% based on resin solids, using drier BOC 1101 and Borchi Dragon based on 1% of resin solids or Deca Co7 based on 0.1% of metal in resin solids and V-TS based on 0.01% of metal in resin solids.

[0234]

[0235] Table XIV. Drying time of Synaqua 4804 short oil alkyd mercaptan compounds, 5% based on resin solids, using drier BOC 1101 and Borchi Dragon based on 1% of resin solids or DecaCo 7 based on 0.01% of metal in resin solids and V-TS based on 0.01% of metal in resin solids.

[0236] Drying time (h) 1 2 3 4 5 6 ST 1 1 1 5.5 0.5 0.25 TF 16 24 10 11 1.75 3.5 DH 24 24 24 24 4.25 7.5

[0237] It was observed in Tables XIII and XIV that the addition of a crosslinking agent containing at least one mercaptan functional group in combination with a manganese or vanadium catalyst combination improved the hardness value and drying time of the coating.

[0238] Table XV. Synaqua 4804 formulation. Influence of the ME-Si-H dosage (crosslinking agent based on 5% to 15% of resin solids).

[0239] Sample Name 1 2 3 4 5 Synaqua 4804 (~50% solids) 5 5 5 5 5 ME-Si-H (~45%, in HCl and water) 0.28 0.5 0.83 BOC 1101 0.025 0.025 0.025 0.025 Deca Co 7 0.036

[0240] Table XVI. Of Synaqua 4804 Hardness. Influence of the ME-Si-H dosage (crosslinking agent based on 5% to 15% of resin solids).

[0241] Hardness (s) 1 2 3 4 5 After 1 day 15.3 16.7 25.2 23.8 29.5 After 7 days 28 28 33.6 37.8 46.2 After 14 days 32.2 42 36.3 49 53.2

[0242] Table XVII. Drying time of Synaqua 4804. Influence of the ME-Si-H dosage (crosslinking agent based on 5% to 15% of resin solids).

[0243] Drying time (h) 1 2 3 4 5 ST 1 0.75 0.75 0.5 0.5 TF 8.75 12.5 2.25 1.5 1.5 DH 12 24 5 2.25 2

[0244] It was observed that the dosage of ME-Si-H affected the hardness value. It was noted that even at a dosage based on 5% of resin solids, the drying time was significantly affected. Even a dosage based on 10% of resin solids was sufficient to have a significant effect on hardness. It was determined that the dosage of ME-Si-H based on resin solids was maintained at 15% for studying the influence on the oil length of alkyd resins.

[0245] Table XVIII. Short-oil alkyd resin formulations of Synaqua 4804 with and without pigments, using BOC 1101, V-TS catalyst, and ME-Si-H based on 15% of resin solids.

[0246]

[0247] Table XIX. Of the short-oil alkyd resins of Synaqua 4804 with and without pigments Hardness, using BOC1101, V-TS catalyst, and ME-Si-H based on 15% of resin solids.

[0248] Hardness (s) 1 2 3 4 5 6 7 8 9 10 1 day 16.8 16.8 14 32.3 25.2 16.8 15.3 6.9 26.7 12.6 7 days 28 33.6 29.4 49.1 64.4 21 28 15.4 36.4 39.3 14 days 29 44.9 30.9 53.3 74.4 22.4 32.2 18.2 36.4 40.7 30 days 40 73 57.5 71.6 109.3 32.3 61.8 26.6 57.6 77.1

[0249] Table XX. Drying time of the short-oil alkyd resins of Synaqua 4804 with and without pigments, using BOC1101, V-TS catalyst, and ME-Si-H based on 15% of resin solids.

[0250] Drying time (h) 1 2 3 4 5 6 7 8 9 10 ST 0.75 0.75 1 0.5 2.5 0.5 0.5 0.5 0.5 2.5 TF 11 19 8 1.5 10.5 4 10 13 1.5 9 DH 16.5 24 14 2.25 15 18 24 24 3.5 13

[0251] Table XXI. Medium-oil alkyd resin formulation in Beckosol AQ 206, using BOC 1101, V-TS catalyst, and ME-Si-H based on 15% of resin solids.

[0252] Sample Name 1 2 3 4 5 Beckosol AQ 206 (55% solids) 10 10 10 10 10 ME-Si-H (~45%, in HCl and water) 1.833 1.833 BOC 1101 0.055 0.055 Deca Co 7 0.079 V-TS (stock solution) 0.055 0.055

[0253] Table XXII. Hardness of Medium-Oil Alkyd Resin in Beckosol AQ 206, using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids. using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids.

[0254] Hardness 1 2 3 4 5 1 day 16.8 18.2 5.5 26.6 15.4 7 days 19.6 29.4 12.5 33.7 40.6 14 days 21 35.1 16.8 35.1 47.6 30 days 29.4 59.0 28.0 50.5 74.3

[0255] Table XXIII. Drying Time of Medium-Oil Alkyd Resin in Beckosol AQ 206, using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids.

[0256] Drying time (h) 1 2 3 4 5 ST 0.5 0.75 1 0.75 0.5 TF 16 14 13 2.5 8.5 DH 20 19 24 5.5 24

[0257] Table XXIV. Long-Oil Alkyd Resin Formulation of Beckosol AQ 101, using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids.

[0258] Sample Name 1 2 3 4 5 Beckosol AQ 101 (55% solids) 10 10 10 10 10 ME-Si-H (~45%, in HCl and water) 1.833 1.833 BOC 1101 0.055 0.055 Deca Co 7 0.079 V-TS (stock solution) 0.055 0.055

[0259] Table XXV. Hardness of Long-Oil Alkyd Resin in Beckosol AQ 101 using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids.

[0260] Hardness (s) 1 2 3 4 5 1 day 6.9 4.1 7 14 14 7 days 7 7 8.4 15.4 18.2 14 days 7 8.4 7 16.8 21 30 days 9.8 15.4 12.6 19.5 30.8

[0261] Table XXVI. Drying Time of Long-Oil Alkyd Resin in Beckosol AQ 101, using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids.

[0262] Drying time (h) 1 2 3 4 5 ST 0.5 0.5 0.25 0.5 1.5 TF 5.5 11.5 14 1.5 2.5 DH 24 24 24 2 9.5

[0263] Table XXVII. 3AK0211Y Alkyd Resin Formulation with and without Pigment, using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids.

[0264]

[0265] Table XXVIII. Hardness of 3AK0211Y Alkyd Resin using BOC 1101, V-TS catalyst, and 15% ME-Si-H based on resin solids.

[0266] Hardness (s) 1 2 3 4 5 6 7 8 9 10 1 day 7 5.5 4.2 18.2 8.5 6.9 5.6 4.1 19.6 8.4 7 days 5.5 11.2 7 21 16.8 7 11.2 5.5 21 12.6 14 days 9.7 15.4 12.6 23.8 30.8 9.8 15.4 8.4 23.8 21 30 days 14 25.2 28.1 32.2 53.3 16.8 23.9 15.4 30.6 33.7

[0267] Table XXIX. Drying times of alkyd resins AK0211Y, using BOC 1101, V-TS catalyst, and 15% of ME-Si-H based on resin solids.

[0268] Drying time (h) 1 2 3 4 5 6 7 8 9 10 ST 0.75 0.75 0.5 0.5 0.75 0.5 0.5 1 0.5 0.5 TF 24 24 24 9 24 19 24 24 1.5 13 DH 24 24 24 24 24 24 24 24 24 24

[0269] Table XXX. Medium-oil alkyd resin formulation of Synaqua 2070, using BOC 1101, V-TS catalyst, and 15% of ME-Si-H based on resin solids.

[0270] Sample Name 1 2 3 4 5 Synaqua 2070 (55% solids) 10 10 10 10 10 ME-Si-H (~45%, in HCl and water) 1.83 1.83 BOC 1101 0.055 0.055 Deca Co 7 0.079 V-TS (stock solution) 0.055 0.055

[0271] Table XXXI. Medium-oil alkyd resin of Synaqua 2070 Hardness, using BOC 1101, V-TS catalyst, and 15% of ME-Si-H based on resin solids.

[0272] Hardness (s) 1 2 3 4 5 1 day 5.5 9.8 5.6 18.2 Precipitation 7 days 7 19.6 5.6 25.2 Precipitation 14 days 8.4 32.2 5.6 25.2 Precipitation 30 days 12.6 56.2 11.1 36.5 Precipitation

[0273] Table XXXII. Drying times of medium-oil alkyd resin of Synaqua 2070, using BOC 1101, V-TS catalyst, and 15% of ME-Si-H based on resin solids.

[0274] Drying time (h) 1 2 3 4 5 ST 0.5 0.75 0.5 0.5 Precipitation TF 13 16 6 1.5 Precipitation DH 22 24 21 4 Precipitation

[0275] Independent of the oil length of the selected waterborne alkyd resin, the combination of ME-Si-H with BOC 1101 or V-TS catalyst was observed to result in an increase in the hardness of the coating. In some cases, an improvement in the drying time of the coating was also observed.

[0276] Comparison of ME-Si-H crosslinker with silane thiol-functionalized emulsion

[0277] To understand whether the improvement in hardness values could be due to the presence of silicon atoms in the crosslinker, a silane thiol-functionalized emulsion was used as a crosslinker and compared with the ME-Si-H crosslinker. A commercially available emulsion KM-9769 (33% solids emulsion) from Shin Etsu was tested.

[0278] Table XXXIII. Short-oil alkyd resin formulation of Synaqua 4804, using BOC 1101 and silane thiol emulsion, compared with ME-Si-H.

[0279] Sample Name 1 2 3 4 5 6 7 8 9 Synaqua 4804 (50% solids) 10 10 10 10 10 10 10 10 10 ME-Si-H (~45%, in HCl and water) 0.56 1.13 KM-9769 (33% solids) 0.75 1.51 T-Cure 0.75 T-Cure hydrolyzed, 50% in water 1.5 BOC 1101 0.05 0.05 0.05 0.05 0.025 0.025 0.05 0.05 Deca Co 7 0.071

[0280] Table XXXIV. Hardness of Synaqua 4804 short oil alkyd resin compared to ME-Si-H, using BOC 1101 and mercaptosilane emulsion.

[0281] Hardness (s) 1 2 3 4 5 6 7 8 9 1 day 23.8 23.8 21 23.8 28 25.2 23.8 21.1 22.5 7 days 30.9 32.2 23.8 22.4 28 33.6 37.8 28 30.9 14 days 30.8 44.9 25.2 23.8 30.9 36.3 49 30.9 33.7

[0282] Table XXXV. Drying time of Synaqua 4804 short oil alkyd resin compared to ME-Si-H, using BOC 1101 and mercaptosilane emulsion.

[0283] Drying time (h) 1 2 3 4 5 6 7 8 9 ST 0.75 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1 TF 8 15 2 1.5 1.5 1.5 1.5 16 3 DH 12.5 24 4 2.5 2 2.25 2 24 12

[0284] It can be assumed that, in addition to the reaction of the mercapto groups on the fatty acids of the alkyd resin, the self-condensation of the silanol groups is also the reason for the increase in hardness when using the ME-Si-H crosslinker, and not just due to the presence of silicon atoms.

[0285] Corrosion resistance test

[0286] The mercaptosilane emulsion and ME-Si-H were tested in the white paint formulation TOD 3AK0211Y to study the effect of the crosslinker on the corrosion resistance of the paint.

[0287] Table XXXVI. Corrosion resistance test of TOD 3AK0211Y WC alkyd resin compared to ME-Si-H, using BOC1101 and mercaptosilane emulsion.

[0288] Sample Name 1 2 3 4 5 TOD 3AK0211Y WC (22% solids) 40 40 40 40 40 ME-Si-H (approx. 50%, in water and HCl) 0.88 2.64 KM-9769 (33% solids) 1.33 BOC 1101 0.088 0.088 0.088 0.088 Deca Co 7 0.10

[0289] Table XXXVII. Hardness of TOD 3AK0211Y WC alkyd resin for corrosion resistance test compared to ME-Si-H, using BOC 1101 and mercaptosilane emulsion.

[0290] Hardness (s) 1 2 3 4 5 1 day 9.8 8.4 8.4 12.6 21 7 days 9.8 15.4 11.2 15.4 22.4 14 days 11.2 18.2 11.2 18.2 26.6

[0291] Table XXXVIII. Drying time of TOD 3AK0211Y WC alkyd resin for corrosion resistance test compared to ME-Si-H, using BOC 1101 and mercaptosilane emulsion.

[0292] Drying time (h) 1 2 3 4 5 ST 24 24 24 2 1 TF 24 24 24 20 8 DH 24 24 24 24 13

[0293] After 288 hours in a QFOG machine, the corrosion resistance of a series of coated panels of TOD3AK0211Y was evaluated using a combination of the crosslinker and BOC 1101.

[0294] Table XXXIX. Visual evaluation of corrosion resistance in TOD 3AK0211Y WC alkyd resin compared to ME-Si-H, using BOC 1101 and silane thiol emulsion.

[0295] Visual assessment of corrosion Expt.1 Expt.2 Expt.3 Expt.4 Expt.5 Corrosion grade Ref 1 0 1 1 Adhesion 1B 4B 5B 4B 4B

[0296] The rating of corrosion resistance is carried out as follows: 0 = the same as BOC 1101; 1 = better than BOC 1101; and Ref = BOC 1101.

[0297] Sample 1 containing 1% of BOC 1101 based on resin solids is used as a reference for evaluation. The adhesion test is rated according to ASTM D3359, where 5B indicates the best adhesion and 0B indicates the worst. Except for the KM 97-69 sample, the use of a combination of crosslinker and BOC 1101 helps to increase the corrosion resistance and adhesion of the coated plate.

[0298] The addition of crosslinker in water is more challenging because, contrary to solvent-based coatings, other components (such as surfactants or thickeners) and physicochemical properties (pH medium, viscosity or interdiffusion of polymer chains, particle stability) should be considered. Without being limited to any theory or mode of operation, it is believed that the combination of hydrolyzed thiol silane with BOC 1101, vanadium or manganese catalyst results in an improvement in hardness and a reduction in drying time. Surprisingly, the best results are not obtained when using polythiol, but when using a compound having silanol and thiol functional groups. Once hydrolyzed, (3-mercaptopropyl)trimethoxysilane has a thiol functional group and a silanol functional group. The silanol part of the crosslinker enables it to be compatible with water, while the more hydrophobic thiol part will be able to react with the unsaturation of the non-polar alkyd resin. The crosslinking can be enhanced by the self-condensation of the silanol groups. It is believed that the "surfactant" behavior of hydrolyzed (3-mercaptopropyl)trimethoxysilane is the key to this performance, thus making the two different media compatible.

[0299] It is also believed that the following mercapto silane compounds may have applicability: silicon-containing compounds containing thiol functional groups, i.e., organic compounds containing one or more hydrolyzable silanes and one or more "free" thiol functional groups SH.

[0300] A specific embodiment of the present invention relates to a non-polymeric silicon-containing compound comprising one or more thiol functional groups. More particularly, the silicon-containing compound comprising one or more thiol functional groups according to the present invention contains 1 to 15 silicon atoms per molecule, preferably 1 silicon atom per molecule. The silicon-containing compound comprising one or more thiol functional groups according to the present invention particularly contains 1 to 12 SH thiol groups per molecule, preferably 1 to 2 SH groups per molecule. As examples of the silicon-containing compound comprising one or more thiol functional groups of the present invention, silicon-containing compounds belonging to the following formulas (A) and (B) can be mentioned:

[0301]

[0302] wherein formula (A):

[0303] R1, R2 and R3 may be the same or different and represent: a hydrogen atom, or a group selected from: C 1-20 alkoxy, C 3-9 cycloalkoxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkoxy such as cyclopentyloxy or cyclohexyloxy, C 1-6 alkylcarbonyloxy or C 1-6 alkyl-C(O)-O-, G-C 1-20 alkyl or G-C 1-20 alkoxy, wherein G represents a hydroxyl group, C 1-6 alkoxy or thiol SH group; and

[0304] ALK represents a C 1-20 alkylene chain in the α-position relative to the silicon atom, which is optionally interrupted and / or terminated,

[0305]

[0306] wherein formula (B):

[0307] p, q, r, s, t and u are 0 or 1;

[0308] x is an integer from 1 to 20, particularly from 1 to 10, including the end values;

[0309] m is an integer from 1 to 4, including the end values, and

[0310] n is an integer from 1 to 3, including the end values;

[0311] R'1, R'2, R'3, R'4 and R'5 may be the same or different and represent:

[0312] (i) a group the same as R1, R2 and R3 as defined above,

[0313] (ii) Trisubstituted siloxy group R a R b R c Si - O -, where R a 、R b and R c may be the same or different and represent the same groups as R1, R2 and R3 defined above,

[0314] (iii) Group R′aR′bR′c Si - O - Si(R′d)(R′e)-ALK″-, where ALK″ is as defined above for ALK, and R′a, R′b, R′c, R′d and R′e may be the same or different and represent: a hydrogen atom, a hydroxyl group, a C 1-4 alkoxy group, a C 1-4 alkyl group, or a group R” a R” b R” c Si - O -, where R” a 、R” b and R” c may be the same or different and represent a hydrogen atom or a C 1-4 alkyl group;

[0315] ALK and ALK' may be the same or different and represent the groups defined above for ALK;

[0316] X and X' may be the same or different and represent:

[0317] (i) A σ - bond,

[0318] (ii) A heteroatom such as oxygen, or an NR group, where R represents a hydrogen atom or a C1 - 4 alkyl group; and preferably, in formula (B):

[0319] When s is 0, X does not represent a bond,

[0320] When m is 1, then p, q and r are 1,

[0321] When m is 2, then p is 0, q and r are 1,

[0322] When m is 3, then p and q are 0 and r is 1,

[0323] When m is 4, then p, q and r are 0,

[0324] When n is 1, then t and u are 1,

[0325] When n is 2, then t is 1 and u is 0, and

[0326] When n is 3, then t and q are 0.

[0327] Preferably, the silicon-containing compound comprising one or more thiol functional groups according to the present invention is a silicon-containing compound of formula (A).

[0328] To illustrate the best mode known to the applicant at the time, the best mode for carrying out the present invention has been described. The examples are illustrative only and are not meant to limit the present invention, as measured by the scope and advantages of the claims. The present invention has been described with reference to preferred and alternative embodiments. Obviously, others will envision modifications and variations after reading and understanding the specification. It is intended to cover all such modifications and variations as long as they fall within the scope of the appended claims or their equivalents.

Claims

1. A method for improving at least one physical property of an aqueous alkyd resin, the method comprising the following steps, without considering the order: (a) adding at least one hydrocarbyl mercapto silane crosslinker compound, the at least one mercapto silane crosslinker compound comprising at least one thiol group, preferably two or more thiol groups; and at least one hydrolyzable organosilane group, wherein the hydrolyzable group comprises at least one alkoxy group having 1 to 4 carbon atoms or at least one acyloxy group having 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 vanadium, iron, copper, and manganese; and (ii) optionally present at least one polydentate promoter ligand that bonds to the at least one transition metal ion through one or more donor sites, wherein the ligand is a bidentate, tridentate, tetradentate, pentadentate, or hexadentate ligand that coordinates through nitrogen or oxygen donor atoms respectively; and (c) adding the aqueous alkyd resin; (a), (b), and (c) in combination improve at least one physical property of the aqueous alkyd resin, the physical property being selected from accelerating drying time, improving hardness, and improving corrosion resistance, provided that when the at least one transition metal ion is vanadium, no polydentate promoter ligand is added.

2. The method according to claim 1, wherein the organosilane group is selected from 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, and mixtures thereof.

3. The method according to claim 1 or 2, wherein the hydrocarbyl mercapto crosslinker compound has formula (VI):

4. The method according to claim 1, wherein the hydrocarbyl mercapto silane crosslinker compound is selected from the following formulas (A) and (B): wherein formula (A): R1, R2, and R3 may be the same or different and represent: a hydrogen atom, or a group selected from the following: C 1-20 alkoxy, C 3-9 cycloalkoxy, an optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkoxy such as cyclopentyloxy or cyclohexyloxy, C 1-6 alkylcarbonyloxy or C 1-6 alkyl-C(O)-O-, G-C 1-20 alkyl and G-C 1-20 alkoxy, where G represents a hydroxyl group, C 1-6 alkoxy or a thiol SH group; or ALK represents a C in the α-position relative to a silicon atom 1-20 an alkylene chain, which is optionally interrupted or terminated, wherein formula (B): p, q, r, s, t, and u are 0 or 1; x is an integer from 1 to 20, particularly from 1 to 10, including the end values; m is an integer from 1 to 4, including the end values, and n is an integer from 1 to 3, including the end values; R’1, R’2, R’3, R’4, and R’5 may be the same or different and represent: (i) a group the same as R1, R2, and R3 as defined above, (ii) The trisubstituted siloxanyl group R a R b R c Si-O-, where R a 、R b and R c may be the same or different and represent the same groups as R1, R2 and R3 defined above, (iii) Group R′ a R′ b R′ c Si - O - Si(R′ d )(R′ e ) - ALK″ -, where ALK″ is as defined above for ALK, and R′ a 、R′ b 、R′ c 、R′ d and R′ e can be the same or different and represent: a hydrogen atom, a hydroxyl group, a C 1-4 alkoxy group, a C 1-4 alkyl group, or a group R” a R” b R” c Si - O -, where R” a 、R” b and R” c can be the same or different and represent a hydrogen atom or a C 1-4 alkyl group; ALK and ALK' may be the same or different and represent a group as defined above for ALK; X and X' may be the same or different and represent: (i) a σ bond, (ii) heteroatoms such as oxygen, or NR groups, where R represents a hydrogen atom or C 1-4 alkyl; and preferably, in formula (B): when s is 0, X does not represent a bond, 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.

5. The method according to any one 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 V(II), V(III), V(IV) or V(V) compounds, An iron-containing drier, wherein the iron is selected from Fe(II) or Fe(III) compounds, A manganese-containing drier, wherein the manganese is selected from Mn(II), Mn(III) or Mn(IV) compounds, and A copper-containing drier, wherein the copper is selected from Cu(I) or Cu(II).

6. The method according to any one of claims 1 to 5, wherein the at least one drier complex is BOC, that is, iron(1+), chloro[9,9-dihydroxy-3-methyl-2,4-bis(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-, chloride (1:1) as shown in the following formula (I) 7. The method according to any one of claims 1 to 5, wherein the at least one drier complex is selected from vanadyl p-toluenesulfonate shown in the following formula (III) and vanadyl dodecylbenzenesulfonate shown in the following formula (IV):

8. The product of the method according to any one of claims 1 to 7.

9. The method according to any one of claims 1 to 7, wherein the at least one hydrocarbyl mercapto silane crosslinking agent compound contains: At least one thiol group having a thiol functional group that reacts with the unsaturation of the aqueous alkyd resin, and At least one silanol functional group that self-condenses to add more crosslinking to the aqueous alkyd resin.

10. An aqueous alkyd resin, comprising: (a) At least one hydrocarbyl mercapto silane crosslinking agent 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 hydrolyzable organosilyl group, wherein the hydrolyzable group comprises at least one alkoxy group having 1 to 4 carbon atoms or at least one acyloxy group having 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 vanadium, iron, copper and manganese; and (ii) Optionally present at least one polydentate promoter ligand that bonds to the at least one transition metal ion through one or more donor sites, wherein the ligand is a bidentate, tridentate, tetradentate, pentadentate or hexadentate ligand coordinated through nitrogen or oxygen donor atoms respectively; and (c) An aqueous alkyd resin; Provided that when the at least one transition metal ion is vanadium, no polydentate promoter ligand is added.

11. The aqueous alkyd resin according to claim 10, wherein the hydrocarbyl mercapto silane crosslinking agent compound comprises (3-mercaptopropyl)trimethoxysilane.

12. The aqueous alkyd resin according to claim 10, which comprises a hydrocarbyl mercapto silane crosslinking agent compound of formula (VI):

13. The aqueous alkyd resin according to claim 10, wherein the hydrocarbon group mercapto-silane crosslinking agent compound is selected from the following formulas (A) and (B): Wherein formula (A): R1, R2 and R3 may be the same or different and represent: a hydrogen atom, or a group selected from the following: C 1-20 alkoxy, C 3-9 cycloalkoxy, optionally substituted aryl such as phenyl or naphthyl, aryloxy such as phenoxy, cycloalkyl such as cyclopentyl or cyclohexyl, cycloalkoxy such as cyclopentyloxy or cyclohexyloxy, C 1-6 alkylcarbonyloxy or C 1-6 alkyl-C(O)-O-, G-C 1-20 alkyl and G-C 1-20 alkoxy, where G represents a hydroxyl group, C 1-6 alkoxy or a thiol SH group; or ALK represents a C in the α-position relative to a silicon atom 1-20 an alkylene chain, which is optionally interrupted or terminated, Wherein formula (B): p, q, r, s, t and u are 0 or 1; x is an integer from 1 to 20, particularly from 1 to 10, including the end values; m is an integer from 1 to 4, including the end values, and n is an integer from 1 to 3, including the end values; R’1, R’2, R’3, R’4 and R’5 may be the same or different and represent: (i) a group the same as R1, R2 and R3 as defined above, (ii) trisubstituted siloxanyl group R a R b R c Si-O-, where R a 、R b and R c may be the same or different and represent the same groups as R1, R2 and R3 defined above, (iii) Group R' a R' b R' c Si - O - Si(R' d )(R' e ) - ALK″ -, where ALK″ is as defined above for ALK, and R' a 、R' b 、R' c 、R' d and R' e may be the same or different and represent: a hydrogen atom, a hydroxyl group, a C 1-4 alkoxy group, a C 1-4 alkyl group, or a group R” a R” b R” c Si - O -, where R” a 、R” b and R” c may be the same or different and represent a hydrogen atom or a C 1-4 alkyl group; ALK and ALK' may be the same or different and represent a group as defined for ALK above; X and X' may be the same or different and represent: (i) a σ bond, (ii) heteroatoms such as oxygen, or NR groups, where R represents a hydrogen atom or C 1-4 alkyl; and wherein preferably, in formula (B): When s is 0, X does not represent a bond, 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.

14. The aqueous alkyd resin according to any one of claims 10 to 13, wherein the at least one transition metal ion is selected from the following group: A vanadium-containing drier, wherein vanadium is selected from V(II), V(III), V(IV) or V(V) compounds, An iron-containing drier, wherein iron is selected from Fe(II) or Fe(III) compounds, A manganese-containing drier, wherein manganese is selected from Mn(II), Mn(III) or Mn(IV) compounds, and A copper-containing drier, wherein copper is selected from Cu(I) and Cu(II).

15. The aqueous alkyd resin according to any one of claims 10 to 14, wherein the at least one drier complex is BOC, namely iron(1+), chloro[9,9-dihydroxy-3-methyl-2,4-bis(2-pyridyl-kN)-7-[(2-pyridyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1,4-dicarboxylic acid dimethyl ester-kN3,kN7]-, chloride (1:1) as shown in the following formula (I): And, the at least one drier complex is selected from vanadyl p-toluenesulfonate shown in the following formula (III) and vanadyl p-dodecylbenzenesulfonate shown in the following formula (IV):

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