Antiskinning additives for autoxidizing coatings

Abstract

Compositions for autoxidizing coatings including autoxidizing binder resins, an organic ligand, at least one transition metal, and an antiskinning additive including a compound that includes a dihydroarene moiety or a methylene cyclohexene moiety. Also disclosed are methods and formulations for making associated compositions, compositions resultant from the curing of such coating compositions, associated kits comprising two or more formulations physically separated from one another, which may be used to provide curable coatings when mixed, formulations including the antiskinning additive for use in autoxidizable coating compositions, and alkyd coating drier and antiskinning additive systems including the antiskinning additive and a drier.

Description

PE963326EP || 7511-A-EPANTISKINNING ADDITIVES FOR AUTOXIDIZING COATINGSCross-Reference to Related Applications

[0001] None.Technical Field

[0002] The invention described herein pertains generally to compounds comprising dihydroarene moieties or methylene cyclohexene moieties, which compounds are used as antiskinning additives that can be added to an autoxidative coating alongside metal driers to reduce skinning while maintaining or improving coating dry time. The invention also provides methods and formulations for making associated compositions, cured coating compositions resultant from the curing of such compositions, coated articles, and associated kits comprising two or more formulations physically separated from one another, which may be used to provide coatings or components of coatings when mixed.Background of the Invention

[0003] Alkyd resins are a well understood and dominant binder in many oxidatively curable commercial and consumer paints and other coatings. Alkyd emulsion paints, in which the continuous phase is aqueous, are also widely available commercially. Alkyd resins are produced by the reaction of polyols with carboxylic acids or anhydrides. To make them susceptible to what is commonly referred to as a drying process, some alkyd resins are reacted with unsaturated triglycerides or another source of unsaturation. Plant and vegetable oils, such as linseed oil, are frequently used as the source of triglycerides. In these drying processes, unsaturated alkene groups can react with oxygen from the air, causing the oils to crosslink and harden. This oxidative curing process, although not actually resultant from or part of physical drying of a coating composition, gives the appearance of drying and is often and herein referred to as such. The length of time required for drying depends on a variety of factors, including the constituents of the alkyd resin and the amount and nature of the solvent - sometimes referred to as the drying oil - or aqueous carrier employed.

[0004] Whilst the autoxidation and polymerization chemistries that occur during the drying of alkyd- based and other oxidatively curable resins will proceed in the absence of catalysis, it is customary to include in such curable resins small, i.e. catalytic, quantities of optionally organic metal salts, often referred to as a class of metal driers, which catalyze the polymerization of unsaturated material, so as to form a three-dimensional network.

[0005] Typical driers for alkyd-based coatings include alkyl carboxylates, frequently C6-C18 carboxylates, of metals such as cobalt, manganese, lead, zirconium, zinc, vanadium, strontium, calcium and iron. Such metal carboxylates are often referred to as metal soaps. Redox-active metals, such as cobalt, manganese, vanadium and iron, enhance radical formation, and thus the oxidative curing process, whilst so-called secondary driers, such as complexes based on strontium,- 1 -55394087-5PE963326EP || 7511-A-EP zirconium and calcium, enhance the action of the redox-active metals and are sometimes called “through driers”, as the enhanced action of redox-active metals they may impart is believed to help ensure even curing of coating films below the film surface (i.e., “through” the coating). Through driers are also often referred to as “secondary driers” or “auxiliary driers.” Often these soaps are based on medium-chain alkyl carboxylates such as 2-methyl-hexanoate. The lipophilic / hydrophilic units in such soaps can be tuned to provide a desired solubility profile of the drier in a given paint or other coatings.

[0006] As well as metal soaps, a variety of metal driers that are redox metal complexes containing organic ligands are used as paint driers, for example manganese compounds comprising 2,2’- bipyridine, 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane, or 1 ,10-phenanthroline ligands or iron compounds comprising a dimethyl-3-methyl-9-oxo-2,4-di(pyridin-2-yl)-7-(pyridin-2-ylmethyl)-3,7- diazabicyclo[3.3.1]nonane-1 ,5-dicarboxylate ligand.

[0007] The formation of a skin or lumpy matter is a problem observed in many coating compositions and formulations, and in particular in alkyd resins, as a consequence of oxidation during storage or transportation. In skinning, oxidative polymerization reactions lead to the skin formation at a coatingair interface often located at the top of a paint can or other coating container (open space in said containers referred to as “head space”) during storage or otherwise before application of a coating. Undesirable skinning can also occur during drying after application, where the coating cures more rapidly at a coating air-interface than in the bulk coating itself. In such instances, poor “through-drying” is observed, and the resultant film has poor mechanical and chemical resistance properties. As alluded to above, the referenced polymerization reactions can be triggered by radicals generated by the action of metal-based driers, for example cobalt-, vanadium-, manganese- or iron-containing driers. In other words, the cause of the skin formation is often associated with the presence of primary metal driers.

[0008] Skin formation during manufacture and storage of air-drying paints and other coatings, in particular of alkyd-based resins, is clearly undesirable. In addition to effects on mechanical and chemical resistance properties, skin formation can lead to material losses and usage problems, such as surface irregularity after application owing to skin particles remaining in the paint or difficulties in accessing useable paint.

[0009] Addition of compounds that quench the radicals formed during the storage or transportation processes reduce the skin-forming tendencies of such compositions and formulations. Many antiskinning agents are therefore antioxidants. However, addition of such antiskinning agents can also slow the drying desired after application, by reducing the activity of the metal driers. Many antiskinning agents that are effective at preventing skinning unacceptably increase coating dry time or degrade mechanical or chemical resistance properties.

[0010] Oximes, and in particular methyl ethyl ketoxi me (MEKO), are known to reduce skin formation considerably, particularly with cobalt-based driers. It is theorized that the oxime may bind to the metal ion during storage of the resin, thereby preventing the metal drier from reacting with oxygen and the substrate for radical formation that otherwise leads to polymerization and skin formation in the can or container. Upon application of the paint or other coating as a thin layer on a surface, the MEKO can - 2 -55394087-5PE963326EP || 7511 -A-EP evaporate. In this way, skinning can be prevented or ameliorated, but the catalyst (such as a metal drier) can still perform its function, after application, as a polymerization catalyst.

[0011] Other antiskinning agents or ways to address the problem of skinning other than those involving the use of oximes such as MEKO, have been described. For example, WO 00 / 11090 describes the use of 1 ,3-diketones, pyrazoles and imidazoles to reduce the skinning properties; WO 2007 / 024592 describes the use of isoascorbate as an antiskinning agent and a co-promoter of metalbased driers; and WO 2008 / 127739 describes the use of hydroxylamine as antiskinning agent. Whilst such additives reduce the tendency towards skinning, they can lead to decreased performance of the metal drier if their degree of incorporation is too great and they do not evaporate sufficiently during the coating (e.g. paint) application.

[0012] Whilst cobalt driers have been employed for many years as paint driers, there is a need to develop alternatives, not least since regulatory authorities in several jurisdictions have suggested imminent reclassification of cobalt metal and cobalt carboxylates as carcinogenic materials. Similarly, MEKO antiskinning agents are subject to regulatory restrictions. In Canada, MEKO concentrations are restricted in indoor alkyd paints available to consumers and have been added to the Environmental Emergency Regulations. The European Commission determined that, in the European Union, MEKO is classified as a Carcinogen Cat. 1B, effective March 1 , 2022, with labeling required at > 0.1% MEKO content (European Commission: ATP 15, part 3, Annex VI). This means that MEKO cannot be utilized in any formulation which meets or exceeds the concentration limits without carcinogen labeling. Other oximes, including 2-pentanone oxime (“2PO”) and cyclohexanone oxime, will likely face similar regulatory pressure in the near future.

[0013] Iron- and manganese-based paint driers in particular have received considerable attention in recent years as alternatives to cobalt-based driers. Alternative driers (to cobalt) may also affect coating dry time, hardness, or other mechanical, protective, and decorative properties relative to coatings reliant on cobalt driers. As discussed above, these effects can be compounded by the sole use of existing antiskinning agents. Various other antiskinning agents have also been examined as alternatives to MEKO and other oximes. Whilst progress has been made in addressing the problem of skinning by these approaches, these each suffer from the disadvantage that, if their degree of incorporation is too great, careful formulation will be essential to avoid drying being too slow. On the other hand, underdosing can lead to enhanced skinning. Either under- or over-dosing of these MEKO alternative antiskinning agents can result in degraded mechanical or protective properties in resultant cured coating films. Such inflexibility in coating formulation is essentially unworkable for modern coating formulators. Changing drier and antiskinning agent systems can also have negative effects on the decorative properties of coatings, for example, by causing a yellowing of the coating upon cure.

[0014] Thus, a need exists in the art for a MEKO-free or reduced MEKO solution that will provide adequate antiskinning effect while maintaining or improving mechanical, protective, and decorative properties and coating dry times. There is a further need in the art for a solution that will provide these properties in a range of coating formulations (including but not limited to cobalt-free or reduced cobalt coating formulations).- 3 -55394087-5PE963326EP || 7511 -A-EPSummary of the Invention

[0015] According to one aspect, the invention provides a binder resin formulation comprising:(i) an autoxidizing binder resin; and(ii) an antiskinning additive formulation, wherein the antiskinning additive formulation comprises a compound including a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is a liquid at 23 ± 1 °C and standard pressure (1 ATM).In embodiments of this aspect, the binder resin formulation may further include at least one organic ligand, a transition metal compound, which may include, for example, manganese, iron, copper, cobalt, or vanadium, but may, in preferred embodiments include iron or manganese.

[0016] According to another aspect, the invention provides a coating composition comprising:(i) at least one autoxidizing (or autoxidizable) binder resin;(ii) at least one organic ligand;(iii) a transition metal compound, which may include, for example, manganese, iron, copper, cobalt, or vanadium, but may, in preferred embodiments include iron or manganese,(iv) at least one antiskinning additive including a compound including a dihydroarene moiety or a methylene cyclohexene moiety, and(v) optionally, additional materials, such as at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosioninhibitor; at least one pigment; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0017] According to another aspect, the invention provides a coating composition consisting essentially of:(vi) at least one autoxidizing (or autoxidizable) binder resin;(vii) at least one organic ligand;(viii) transition metal compound, which may include, for example, manganese, iron, copper, cobalt, or vanadium, but may, in preferred embodiments include iron or manganese,(ix) at least one antiskinning additive including a compound including a dihydroarene moiety or a methylene cyclohexene moiety, and(x) optionally, additional materials, such as at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosioninhibitor; at least one pigment; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one- 4 -55394087-5PE963326EP || 7511 -A-EP antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0018] In some aspects of the invention, the coating composition is provided in kits of two or more components, wherein each component includes a formulation, and each of the at least one autoxidizing binder resin, at least one organic ligand, at least one transition metal compound, at least one antiskinning additive, and optional, additional materials (if present) may be provided in one or more of each formulation. Where the formulations are present in kits, they can be physically separated, such as in separate cartridges, sachets, pouches, tanks, or the like. In some aspects, the invention is embodied in the formulations themselves. The invention includes certain useful formulations including, for example: a binder resin formulation including autoxidizing binder resin that is pre-loaded with transition metal compound, organic ligand, and antiskinning additive; an antiskinning additive formulation including a compound including a dihydroarene moiety or a methylene cyclohexene moiety; an antiskinning additive formulation including a compound including a dihydroarene moiety or a methylene cyclohexene moiety, transition metal compound, and organic ligand; and others. In a further aspect of the invention, the coatings or formulations described herein may further comprise an additional antiskinning agent (in addition to the antiskinning additive).

[0019] In a further aspect, the invention pertains to use of an antiskinning additive formulation as an antiskinning agent for autoxidizing coatings, wherein the antiskinning additive formulation comprises a compound including a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is a liquid at 23 ± 1 °C and standard pressure (1 ATM). In some embodiments of this aspect, the antiskinning additive formulation further comprises an additional antiskinning agent that is different from the compound including a dihydroarene moiety or a methylene cyclohexene moiety.

[0020] In a further aspect, the invention pertains to use of an antiskinning additive formulation as an antiskinning agent for autoxidizing coatings, wherein the antiskinning additive formulation consists essentially of a compound including a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is a liquid at 23 ± 1 °C and standard pressure (1 ATM).

[0021] In further aspects, the invention pertains to methods of use, methods of formation, cured articles, and coated articles relating to and / or formed from the above compositions, kits, and formulations.

[0022] In a further aspect, the invention pertains to a drier and antiskinning additive system including a compound including a dihydroarene moiety or a methylene cyclohexene moiety, a transition metal compound, and an organic ligand.

[0023] These and other aspects of this invention will be evident when viewed in light of the detailed description and appended claims.Detailed Description of the Invention

[0024] We have found that transition metal compounds that comprise iron, manganese, copper, cobalt, or vanadium (often iron or manganese and frequently iron), and at least one organic ligand, - 5 -55394087-5PE963326EP || 7511 -A-EP often capable of chelating at least one such transition metal, through three, four or five nitrogen atoms (metal and ligand altogether referred to herein as “metal driers,” whether complexed together or not formed in a complex), are effective as primary driers at relatively low concentrations for curing autoxidizing coatings in the presence of an antiskinning additive including a compound containing a dihydroarene moiety or a methylene cyclohexene moiety. The compounds of the antiskinning additive are preferably liquid at room temperature (23 ± 1°C) and standard pressure (1 ATM). The addition of the antiskinning additive retains or improves mechanical, protective, and decorative properties of the coating composition upon cure while reducing the tendency of the coating composition to skin during storage or application. The addition of the antiskinning additive in place of alternative antiskinning agents further results in improved or comparable coating dry time relative to coatings containing only some oxime antiskinning agents. This permits reduction or avoidance of both toxic cobalt driers and MEKO antiskinning agents with the resultant compositions exhibiting good storage stability (lack of skinning) and coating dry times while retaining other coating mechanical, protective, and decorative properties relative to cobalt-containing and / or MEKO-containing formulations or other formulations that do not include the inventive antiskinning additive.

[0025] The invention is particularly applicable to coatings that require reduced amounts of cobalt driers and / or MEKO or oxime antiskinning agents whilst functioning effectively. Indeed, the present invention permits the avoidance of cobalt driers and MEKO or oxime antiskinning agents.SELECTED DEFINITIONS

[0026] Terms such as “a,” “an,” and “the” are not intended to refer to only a singular entity but include the general class of which a specific example may be used for illustration. The terms “a,” “an,” and “the” are used interchangeably with the term “at least one.” The phrases “at least one of’ and “comprises at least one of’ followed by a list refers to any one of the items in the list and any combination of two or more items in the list.

[0027] The term “about” is used here in conjunction with numeric values to include normal variations in measurements as expected by persons skilled in the art and is understood to cover a typical margin of error, such as ± 5 % of the stated value.

[0028] As used herein, the term “aliphatic group” shall mean a saturated or unsaturated linear or branched hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.

[0029] As used in this application, the term “approximately” shall mean within 10% of the stated value, except where noted or context dictates otherwise.

[0030] Throughout the description and claims generic groups are often used, for example alkyl, alkoxy, aryl. Unless otherwise specified, the following are preferred group restrictions that may be applied to generic groups found within compounds disclosed herein.

[0031] As used herein, “alkyl” will mean linear and branched Ci -12-alkyl saturated acyclic hydrocarbon monovalent groups; said alkyl group may further optionally include one or more suitable- 6 -55394087-5PE963326EP || 7511 -A-EP substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like.

[0032] As used herein, “alkenyl” will mean linear and branched C2-12 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.

[0033] Unless otherwise stated, as used herein, “aryl” means selected from monovalent homoaromatic groups having a molecular weight preferably under 300.

[0034] Unless otherwise stated, as used herein, “cycloalkyl” means C3-20 monocyclic saturated hydrocarbon monovalent group, or a C7-20 polycyclic saturated hydrocarbon monovalent group.

[0035] Unless otherwise stated, as used herein, “heteroaryl” means selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl ; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to a compound via any atom in the ring of the selected heteroaryl.

[0036] Unless otherwise stated, as used herein, “heterocycloalkyl” means selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4- piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononyl; 1 ,4,8,11 - tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononyl; 1 ,4- diaza-7-oxa-cyclononyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4-dioxanyl; 1 ,4,7-trithia-cyclononyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl is connected via any atom in the ring of the heterocycloalkyl.

[0037] Unless otherwise stated, as used herein, “carboxylate derivative” means the group -C(O)OR, wherein R is selected from: hydrogen; Ci-Ci2-alkyl; phenyl; Ci-Ce-alkyl-CeHs; Li; Na; K; Cs; Mg; and Ca; carbonyl derivative: the group — C(O)R, wherein R is selected from: hydrogen; Ci-Ci2-alkyl; phenyl; Ci-Ce-alkyl-CeHs and amine (to give an amide) selected from the group: — NR'2, wherein each R' is independently selected from: hydrogen; Ci-Ci2-alkyl; Ci-Ce-alkyl-CeHs; and phenyl, wherein when both R' are Ci -Ci 2-alkyl both R' together may form an — NC3 to an — NC5 heterocyclic ring (i.e. a 4-6-membered heterocyclic ring comprising the nitrogen atom of the amine) with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring; and sulfonate: the group — S(O)2OR, wherein R is selected from: hydrogen; Ci-Ci2-alkyl; phenyl; Ci-Ce-alkyl-CeHs; Li; Na; K; Cs; Mg; and Ca.

[0038] 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- 7 -55394087-5PE963326EP || 7511-A-EP atoms wherein the alkyl group may be straight-chain or branched, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenyl hexyl groups.

[0039] As used herein the term “donor ligand” or “organic ligand” or “ligand” or “L” is an organic structure or molecule which will support coordinating atoms, preferably nitrogen coordinating atoms. In the present invention, said at least one donor ligand is preferably a nitrogen donor ligand selected from the group consisting of tridentate, tetradentate, pentadentate and hexadentate nitrogen donor ligands. Oxygen donor ligands and other ligands are also contemplated by the invention.

[0040] The term “crosslinker” refers to a molecule capable of forming a covalent linkage between separate polymers or between two different regions of the same polymer.

[0041] The term “ethylenically unsaturated” with reference to a monomer or chemical group herein refers to a substance having an ethylene linkage capable of forming a link within a polymer material. Exemplary ethylenically unsaturated monomers include esters of acrylic acid (or “acrylate monomers”), vinyl monomers, vinyl acetate monomers, styrene monomers, and other monomers suitable for use in coating and composite materials.

[0042] The term “group” is intended to be a recitation of both the particular moiety, as well as a recitation of the broader class of substituted and unsubstituted structures that includes the moiety. Thus, when the term “group” is used to describe a chemical substituent, the described chemical material includes the unsubstituted group (e.g., the moiety) and that group with O, N, Si, or S atoms, for example, in the chain (as in an alkoxy group) as well as carbonyl groups or other conventional substitution. Where the term “moiety” is used to describe a chemical compound or substituent, only an unsubstituted chemical material is intended to be included. For example, the phrase “alkyl group” is intended to include not only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, isopropyl, t- butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like, but also alkyl substituents bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, “alkyl group” includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls, hydroxy alkyls, sulfoalkyls, etc. On the other hand, the phrase “alkyl moiety” is limited to the inclusion of only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.

[0043] The term “heteroatom” is used herein to refer to an atom other than carbon or hydrogen. Examples of heteroatoms include N, P, S, O, and the like.

[0044] Unless context dictates otherwise, molecular weight, as used herein, refers to weight average molecular weight (“Mw”), measured by gel permeation chromatography using polystyrene standards. According to particular embodiments, Mws are measured according to standard methods such as ISO 13885-1.

[0045] As used herein, the term “polymer” (or associated references to materials as “polymeric”) refers to molecules including organic components and composed of repeating units (polymerized monomers). A polymer, as referred to herein, has a weight average molecular weight of at least 1000.- 8 -55394087-5PE963326EP || 7511 -A-EPThat is, the term “polymer,” as used herein, may include some oligomers by some definitions of the term “oligomer.” Unless otherwise indicated, the terms “polymer” and “polymeric material” include, but are not limited to, organic homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries.

[0046] As used here, the term “or” is generally employed in its usual sense including “and / or” unless the content clearly dictates otherwise. The term “and / or” means one or all of the listed elements or a combination of any two or more of the listed elements.

[0047] The term “structural unit” or “residue” as used herein with reference to a polymer or polymeric material refers to a group that may be derived from a monomer to form at least part of a polymer or polymeric material. In some embodiments, structural units or residues are formed from monomers that are ethylenically unsaturated.

[0048] Whenever the term “substituted” is used herein, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using “substituted” is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e., a compound that is sufficiently robust to survive isolation from a reaction mixture. Where the indicated group is not specified, a person having ordinary skill in the art will be able to select viable substituents that are suitable for the application in question, given the benefit of this disclosure.

[0049] Where percentages by weight are referred to herein (e.g. % w / w, wt % or % by weight), these mean, unless a text or context clearly dictates to the contrary, percentages by weight with respect to the total weight of components within a formulation or composition (i.e., including any liquid weight of a composition or formulation). For example, where a coating composition consists of solvent, alkyd binder, ligand, transition metal compound, pigment, and antiskinning additive and includes 5 % w / w of the pigment, this is with respect to the weight of the of the solvent, alkyd binder, ligand, transition metal compound, pigment, and antiskinning additive in the composition. In another example, where a binder resin formulation consists of solvent, alkyd binder, ligand, transition metal compound, and antiskinning additive and includes 0.01 % w / w of the ligand, this is with respect to the weight of the of the solvent, alkyd binder, ligand, transition metal compound, and antiskinning additive in the composition.

[0050] By a “well-defined complex” is meant herein (as the term is used customarily in the art) a complex that has been isolated such that it is susceptible to characterization (i.e. definition) and analysis (e.g. to determine its structure and degree of purity). In contrast, a complex that is “not well- defined” is one that is prepared without isolation from the medium (e.g. reaction medium) in which it is prepared. Well-defined complexes often consist of a single active component, whereas complexes that are not well-defined often, but not necessarily, comprise more than one active component. For- 9 -55394087-5PE963326EP || 7511-A-EP example, a mixture of mononuclear and dinuclear species may exist or a mixture of different ancillary ligands may be present.

[0051] The recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1 , 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. or 10 or less includes 10, 9.4, 7.6, 5, 4.3, 2.9, 1 .62, 0.3, etc.). Where a range of values is “up to” or “at least” or “at most” a particular value, that value is included within the range.

[0052] The words “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the disclosure, including the claims.

[0053] As summarized above, the present invention is based, in part, on the recognition that complexes of transition metals (particularly, although not necessarily, of iron or manganese and often, although again not necessarily, of iron) and an organic ligand or chelant are effective for accelerating the curing of autoxidizing binder resins in coating compositions. Such complexes or their components whether complexed or not complexed are referred to together herein as metal driers. Such metal driers are particularly effective and provide favorable skinning and other coating properties in the presence of antiskinning additives including a compound including a dihydroarene moiety or a methylene cyclohexene moiety.

[0054] 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.

[0055] 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 clear coats, oils, and binders, which form a continuous coating through the course of autoxidative reactions, typically to form cross-linkages and other bond formations.AUTOXIDIZING BINDER RESIN

[0056] Generically, such coating compositions may be characterized by the presence of autoxidizable (autoxidizing) binder resins, typically (poly) unsaturated resins, that react to form a solid film on a substrate, the resins being initially present in the oxidatively curable 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 autoxidizing binder resins include alkyd-, acrylate-, urethane-, polybutadiene- and epoxy ester-based resins.- 10 -55394087-5PE963326EP || 7511 -A-EP

[0057] Alkyd resins are a particularly important member of the class of autoxidizing binder resins 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).

[0058] Herein, the term “alkyd binder” or “alkyd resin” are used interchangeably. Suitable autoxidizable alkyd resins 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, those 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. The properties are primarily determined by the nature and the ratios of the alcohols and acids used and by the degree of condensation. Exemplary alkyd resins for coatings include long oil and medium oil alkyd resins e.g., derived from 45 wt.% to 70 wt.% of fatty acids, and short oil alkyd resins. To improve the performance of the resins or to allow the resin to function in a water-based coating formulation or water-reducible coating formulation, the composition of the alkyd may be modified. For example, polyurethane- modified alkyds, silicone-modified alkyds, styrene-modified alkyds, acrylic-modified alkyds (e.g. methacrylic modified alkyds), vinylated alkyds, polyamide-modified alkyds, and epoxy-modified alkyds or mixtures thereof are also suitable alkyd resins to be used in embodiments of the present compositions.

[0059] In some embodiments, 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. In some embodiments, the alkyd binder is a short oil alkyd, a medium oil alkyd, a long oil alkyd, a silicone-modified alkyd, a polyurethane-modified alkyd or a combination thereof. Exemplary alkyd resins include Synolac 6883 (solventborne, long oil alkyd, Arkema Coating Resins); Urakyd HS233 Q1-85 (solventborne, long oil alkyd, Synres B.V.); Urakyd AD130 Q-70 (solventborne, long oil alkyd, Synres B.V.); Urakyd AD10 Q-65 (solventborne, long oil alkyd, Synres B.V.); WorleeKyd S 351 (solventborne medium oil alkyd, Worlee); and Synthalat F 334 (solventborne, short oil alkyd, Synthopol Chemie Dr. rer. Pol. Koch GmbH & Co. KG) and other alkyd binders.

[0060] In some further embodiments, the at least one autoxidizable alkyd binder is part of an interpenetrating network (“IPN”) in which crosslinking of the autoxidizable alkyd binder or a second resin or polymer forms a network in which either the second resin or polymer or the autoxidizable alkyd binder, respectively, is entangled. Exemplary such second resins or polymers include resins having (meth)acrylic, vinyl, vinyl acetate, styrene, acrylamido, or polyurethane residues, or mixtures thereof. Suitable second resins or polymers may or may not be capable of crosslinking with the alkyd binder.

[0061] In some embodiments, the amount of alkyd binder in the present coating compositions is at least approximately 10 wt.%, in further embodiments, at least approximately 20 wt. %, in further- 1 1 -55394087-5PE963326EP || 7511 -A-EP embodiments, at least approximately 30 wt. %, and in still further embodiments, at least approximately 40 wt. %. In some embodiments, the amount of alkyd binder in the present coating compositions is at most approximately 98 wt.%, in further embodiments, at most approximately 90 wt. %, in further embodiments, at most approximately 85 wt. %, and in still further embodiments, at most approximately 70 wt. %.

[0062] In preferred embodiments, the autoxidizing binder resin is provided, prior to curing, in a liquid carrier. In some embodiments, the liquid carrier may be water or a solvent.

[0063] In some embodiments, the compositions or formulations of the present disclosure are solventbased or solventborne. By solvent-based or solventborne compositions or formulations is meant herein, consistent with the nomenclature used in the art, compositions or formulations that are based predominately, in their liquid form, on organic (i.e., non-aqueous) solvents (e.g., less than 50 wt. % of solvents in the relevant coating are water). 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. Some embodiments of organic solvents include white spirit and solvents available under the trademarks Shellsol, from Shell Chemicals and Solvesso and Exxsol, from Exxon.

[0064] In some embodiments, the compositions or formulations of the present disclosure are waterbased or waterborne. By water-based or waterborne compositions or formulations is meant herein, coating compositions or formulations that, in their liquid form, include solvents being composed of 50 wt. % or greater of water. Such water-based coating compositions include but are not limited to water- reducible coatings, water-based emulsion coatings (such as alkyd emulsions, which are alkyd formulations dispersed in a continuous water phase with the addition of anionic and / or nonionic surfactants), mechanically dispersed alkyd coatings, and core-shell alkyd hybrid coatings (such as core-shell alkyd-acrylic hybrid coatings).

[0065] In some embodiments, the autoxidizing binder resin of the disclosed compositions or formulations of the present disclosure are water-reducible. By water-reducible compositions or formulations is meant herein, consistent with the nomenclature used in the art, certain coatings reliant on alkyd resins that have been modified (for example, by the inclusion of functional carboxylic acid groups) to allow their solubility or dispersion in a water phase. It is contemplated and perfectly consistent with the art and the above definitions that some water-reducible coatings will also be considered water-based or waterborne coatings.

[0066] In preferred embodiments, in a liquid coating composition or resin formulation, the liquid carrier is present in an amount of at least 2 % w / w, in further embodiments at least 10 % w / w, in further embodiments at least 20 % w / w, in further embodiments at least 30 % w / w, and in still further embodiments at least 40 % w / w. In preferred embodiments, in a liquid coating composition or resin- 12 -55394087-5PE963326EP || 7511 -A-EP formulation, the liquid carrier is present in an amount of at most 95 % w / w, in further embodiments at most 80 % w / w, in further embodiments at most 70 % w / w, in further embodiments at most 65 % w / w, and in still further embodiments at most 50 % w / w. In this context, % w / w indicates percent weight of liquid carrier as a percentage of weight of the full liquid coating composition or resin formulation, as the case may be.

[0067] In some embodiments, liquid carriers of liquid compositions according to the invention contain less than 30 % w / w of water, in further embodiments less than 20 % w / w of water, in still further embodiments less than 10 % w / w of water, and in yet further embodiments less than 5 % w / w of water. In other embodiments, liquid carriers of liquid compositions according to the invention contain greater than 40 % w / w of water, in further embodiments greater than 50 % w / w of water, in still further embodiments greater than 60 % w / w of water, and in yet further embodiments greater than 80 % w / w of water.METAL DRIER

[0068] The metal drier, as referred to herein, refers to a polydentate ligand or chelant and a transition metal whether complexed (well defined or not-well-defined), not complexed, together in one solution or dispersion, or in physically separate formulations. Metal driers comprising one or more of these ligands and one or more suitable transition metals, in particular, iron, manganese, vanadium, cobalt, or copper, more typically iron and manganese, more typically iron, accelerate the curing of alkyd coatings, which acceleration is absent in the absence of suitable transition metal.

[0069] In preferred embodiments, the ligand is a tetradentate, pentadentate or hexadentate nitrogen donor ligand, and may be built up within any organic structure which will support coordinating nitrogen atoms. For example, one can take a ligand such as 1 ,4,7-triazacyclononane (TACN), optionally substituted with further nitrogen coordinating groups, e.g., -CH2-CH2-NH2, -CH2-Py (Py = pyridyl, typically 2-pyridyl), covalently bound to one or more of the nitrogen atoms within the tridentate ligand (e.g., TACN) or aliphatic groups (e.g. one or more of the ethylene diradicals in TACN).

[0070] In other embodiments, the ligand includes one or more of a nitrogen coordinating atom, an oxygen coordinating atom, a phosphorus coordinating atom, a sulfur coordinating atom, or a carbon coordinating atom, or a mixture thereof. Such ligands can have varying denticity and include one, multiples of, or none of the above coordinating atoms. These ligands can similarly be built within any organic structure that will support the coordinating atoms.

[0071] If present, iron ions may be selected from Fe(ll) and / or Fe(lll); manganese ions may be selected from Mn(ll), Mn(lll), and Mn(IV), or vanadium ions selected from V(ll), V(lll), V(IV) and V(V), or mixtures thereof. According to some embodiments, the metal drier comprises the ligand that is a mono- or bidentate complex of one of the foregoing ions, or a mixture thereof.

[0072] The ligand (L) may be provided, for example, in complexes of one or more of the formulae: [MnLCI2]; [FeLCI2]; [FeLCI]CI; [FeL(H2O)](PF6)2; [FeL]CI2, [FeLCI]PF6and [FeL(H2O)](BF4)2 as well as in complexes with iron carboxylates, e.g., iron neodecanoate. It will be understood that the- 13 -55394087-5PE963326EP || 7511 -A-EP counteranions shown in the complexes may coordinate to other transition metal if desired, e.g. cobalt or copper.

[0073] Complexes comprising a ligand may, for example, be of the generic Formula (1 ):[MaLkXn]Ym (1 ) in which:M represents an ion selected those of iron, manganese, vanadium, cobalt, and copper; each X independently represents a coordinating species selected from any mono-, bi-, or tricharged anions and any neutral molecule able to coordinate a metal ion M in a mono-, bi- or tridentate manner; each Y is independently a non-coordinating counterion; a represents an integer from 1 to 10; k represents an integer from 1 to 10; n represents an integer from 1 to 10; m represents an integer from 0 to 20; andL represents a ligand as described further herein, or a hydrate thereof.

[0074] In some embodiments, M in Formula (1 ) represents a transition metal ion selected from Fe(ll), Fe(lll), Fe(IV), Fe(V), Mn(ll), Mn(lll), Mn(IV) and Mn(V).

[0075] According to particular embodiments of Formula (1 ), including those embodiments in which M represents a transition metal ion selected from Fe(ll), Fe(lll), Fe(IV), Fe(V), Mn(ll), Mn(lll), Mn(IV) and Mn(V) alone or in combination (where the context permits):M represents a metal ion selected from Fe(ll), Fe(lll), Mn(ll), Mn(lll), and Mn(IV);X represents a coordinating species selected from, for example, O2-, [R6BO2]2-, R6COO;Y represents a counterion selected, for example, from CIO4; CF3SO3; [B(R6)4]_, [FeCk] ’, PFe-, R6COO', NO3-, R6O; N+R6R7R8R9, Ch, Br, h, F, S2O62; OCN; SON; H2O, BRr, SO42', Li+, Na+, K+, Mg2+, Ca2+;R, R6, R7, R8and R9each independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl; a represents an integer from 1 to 4; k represents an integer from 1 to 10;- 14 -55394087-5PE963326EP || 7511 -A-EP n represents an integer from 1 to 4; and m represents an integer from 1 to 8.

[0076] The nature of the counterion(s) Y are not of great importance. The choice of these may be affected by the solubility of the complex of metal and ligand in a given formulation or composition. For example, counterion(s) Y such as chloride, sulfate or acetate may serve to provide a readily water- soluble complex. When using solvent-based (i.e. non-aqueous) compositions, it may be desirable to use larger, less polar counterions such as 2-ethylhexanoate. Suitable counterion(s) Y (and coordinating species X) may be selected without difficulty by the skilled person.

[0077] According to particular embodiments, X and Y may be independently selected from the group consisting of bromide, iodide, nitrate, sulfate, methoxide, ethoxide, formate, acetate, propionate, 2- ethyl hexanoate, octanoate, neodecanoate (3,3,5,5-tetramethylhexanoate), naphthenate, oxide, and hydroxide. An example of a neutral molecule able to coordinate the metal is acetonitrile, for example, to afford a complex of the formula [ML(CH3CN)2]Cl2.

[0078] It will be understood that counterions Y serve to balance the charge resultant from the complex formed by the metal ion(s) M, coordinating species X and ligand(s) L. Thus, if the charge on the complex is positive, there will be one or more anions Y. Conversely, there will be one or more cations Y if the charge on the complex is negative.

[0079] Below are described exemplary classes of ligands that may form iron, manganese, vanadium, cobalt, or copper complexes of tetradentate, pentadentate or hexadentate nitrogen donor ligands. The below ligands most commonly form such complexes with iron and manganese transition metals.

[0080] If unspecified, the length of an alkyl chain is C1-C12 alkyl and preferably is linear. If unspecified, the length of an alkenyl or alkynyl chain is C2-C12 and preferably is linear. If unspecified an aryl group is a phenyl group.LIGANDS (OR CHELANTS)

[0081] Various aspects of the present invention employ the use of a ligand or chelant, preferably of one of the below forms or classes (said chelants of these preferrable forms and classes referred to herein as “polydentate accelerant ligands”). It will be understood that more than one such chelant may be used in accordance with the various aspects of the invention. Also, one or more of these ligands may be used in combination with a ligand described elsewhere, such as those described in WO 2011 / 083309 A1 . Typically, however, only one type of ligand will be used.- 15 -55394087-5PE963326EP || 7511 -A-EP

[0082] BISPIDON

[0083] The bispidon class are typically in the form of an iron transition metal catalyst. The bispidon ligand is preferably of Formula I or Formula l-A:wherein: each R is independently selected from the group consisting of hydrogen, F, Cl, Br, hydroxyl, Ci-4-alkylO-, -NH-CO-H, -NH-CO-Ci-4alkyl, -NH2, -NH-Ci-4-alkyl, and Ci—4-alkyl;R1 and R2 are independently selected from the group consisting of Ci— 24alkyl , Ce- -aryl, C7-12-ary I alkyl, and a group containing one or two heteroatoms (e.g. N, O or S) capable of coordinating to a transition metal;R3 and R4 are independently selected from the group consisting of hydrogen, Ci— s-alkyl, Ci— 8-alkyl— O— Ci— 8-alkyl, Ci-s-alkyl-O-Ce-io-aryl, Ce- 10-aryl, Ci-s-hydroxyalkyl and - (CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen, C1- 12-alkyl , and Ci—4-alkyl— O— Ci—4-alkyl and n is from 0 to 4;- 16 -55394087-5PE963326EP || 7511 -A-EPX is selected from the group consisting of C=O, -[C(R6)2]y- wherein y is from 0 to3; each R6 is independently selected from the group consisting of hydrogen, hydroxyl, Ci-4-alkoxy and Ci— 4-alkyl ; and each D is independently selected from the group consisting of thiazol-2-yl and thiazol-4- yi.

[0084] Often R3 = R4 and is selected from -C(O) -O-CH3, -C(O) -O-CH2CH3, -C(O)-O-CH2C6H5and CH2OH. Often the heteroatom capable of coordinating to a transition metal is provided by pyridin-2-ylmethyl optionally substituted by Ci— 4alkyl or an aliphatic amine optionally substituted by C1-8- alkyl. Often X is C=O or C(OH)2.

[0085] Typical groups for -R1 and -R2 are -CH3, -C2H5, -C3H7, -benzyl, -C4H9, -C6H13, -CsHi7, -C12H25, and -C18H37 and -pyridin-2-yl. An example of a class of bispidon is one in which at least one of R1 or R2 is pyridin-2-ylmethyl or benzyl or optionally alkyl -substituted amino-ethyl, e.g., pyridin-2- ylmethyl or W,W-dimethylamino-ethyl.

[0086] Two examples of bispidons are dimethyl 2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7- diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate (N2py3o-C1 ) and dimethyl 2,4-di-(2-pyridyl)-3- methyl-7-(N,N-dimethyl-amino-ethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate and the corresponding iron complexes thereof. FeN2py3o-C1 may be prepared as described in WO 02 / 48301 . Other examples of bispidons are those which, instead of having a methyl group at the3-position, have longer alkyl chains (e.g. C4-Ci8-alkyl or Ce-Cis-alkyl chains) such as / 'sobutyl, (n- hexyl) C6, (n-octyl) C8, (n-dodecyl) C12, (n-tetradecyl) C14, (n-octadecyl) C18; these may be prepared in an analogous manner.

[0087] As used in this application, 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.- 17 -55394087-5PE963326EP || 7511 -A-EP

[0088] N4py type

[0089] The N4py type ligands are typically in the form of an iron transition metal catalyst. The N4py type ligands are typically of the formula (II):wherein: each R1 and R2 independently represents R4-R5;R3 represents hydrogen, Ci-s-alkyl, aryl selected from homoaromatic monovalent groups having a molecular weight under 300, or C?-4o-aryl alkyl, or -R4-R5, each R4 independently represents a single bond or a C2-i4-alkylene, C2-6- alkenylene, C2-6-oxyalkylene, C2-6-aminoalkylene, C2-6-alkenyl ether, C2-6-carboxylic ester or C2-6-carboxylic amide, and each R5 independently represents an optionally N-alkyl-substituted aminoalkyl group or an optionally alkyl-substituted heteroaryl: selected from the group- 18 -55394087-5PE963326EP || 7511 -A-EP consisting of pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to R4 via any atom in the ring of the heteroaryl.

[0090] According to some embodiments R1 or R2 represents pyridin-2-yl; or R2 or R1 represents 2- amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-(N,N-di(m)ethyl)amino-ethyl. If substituted, R5 often represents 3-methyl pyridin-2-yl. R3 preferably represents hydrogen, benzyl or methyl.

[0091] Examples of N4Py ligands include N4Py itself ( / '.e. N, N-bis(pyridi n-2-yl-methyl)-bis(pyridi n-2- yl)methylamine which is described in WO 95 / 34628); and MeN4py ( / '.e. N,N-bis(pyridin-2-yl-methyl- 1 ,1-bis(pyridin-2-yl)-1 -aminoethane) and BzN4py (N,N-bis(pyridin-2-yl-methyl-1 ,1-bis(pyridin-2-yl)-2- phenyl-1 -aminoethane) which are described in EP 0909809.

[0092] TACN-type

[0093] The TACN-Nx are preferably in the form of an iron or manganese transition metal catalyst. These ligands are based on a 1 ,4,7-triazacyclononane (TACN) structure but have one or more pendent nitrogen groups that serve to complex with the transition metal to provide a tetradentate, pentadentate or hexadentate ligand. According to some embodiments of the TACN-Nx type of ligand, the TACN scaffold has two pendent nitrogen-containing groups that complex with the transition metal (TACN-N2). TACN-Nx ligands are typically of the formula (III):wherein each R20 is independently selected from: hydrogen, -CY2-R22, Ci -s-alkyl , Cs-s-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononyl; 1 ,4,8,11 - tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia- cyclononyl; 1 ,4-diaza-7-oxa-cyclononyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4- dioxanyl; 1 ,4,7-trithia-cyclononyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl is connected to the ligand via any atom in the ring of the heterocycloalkyl; heteroaryl selected from the group consisting of pyridinyl;55394087-5PE963326EP || 7511-A-EP pyrimidinyl ; pyrazinyl; triazolyl; pyridazinyl; triazinyl ; quinolinyl; isoquinolinyl ; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to the ligand via any atom in the ring of the heteroaryl, aryl selected from homoaromatic monovalent groups having a molecular weight under 300, or C?-4o-aryl alkyl group optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate derivative, carboxamide, sulfonate, amine, alkylamine, and N+(R21)3 ,R21 is selected from hydrogen, Ci-s-alkyl, C2-6-alkenyl, C?-4o-arylalkyl, arylalkenyl, O-s-oxyalkyl, C2-6-oxyalkenyl, Ci-8-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, and C2-6-alkenyl ether,Y is independently selected from H, CH3, C2H5, C3H7 andR22 is independently selected from Ci-8-alkyl-substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to the ligand via any atom in the ring of the heteroaryl.

[0094] R22 is typically selected from optionally alkyl-substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1- yl, quinolin-2-yl groups. R22 is often either a pyridin-2-yl or a quinol i n-2-yl.

[0095] As used herein, TMTACN is 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane illustrated below:

[0096] As used herein, Borchi® Dragon is a product from Borchers containing manganese neodecanoate and TMTACN.

[0097] CYCLAM and Cross-Bridged Ligands

[0098] The cyclam and cross-bridged ligands are preferably in the form of a manganese transition metal catalyst. The cyclam ligand is typically of the formula (IV):wherein:- 20 -55394087-5PE963326EP || 7511 -A-EPQ is independently selected fromR> - N I> - [ CR1CR2CR3R4] - and R> - N I> - [ CR1CR2CR3R4CR5R6]P is 4;R is independently selected from: hydrogen, Ci -6-alkyl ,CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or two R moieties of two Q moieties together form an ethylene bridge; andRl, R2, R3, R4, R5 and Reareindependently selected from: H, C -alkyl, and Ci-4-alkylhydroxy.

[0099] Examples of non-cross-bridged ligands are 1 ,4,8,11 -tetraazacyclotetradecane (cyclam), 1 ,4,8,11 -tetramethyl-1 ,4,8,11 -tetraazacyclotetradecane (Me4cyclam), 1 ,4,7,10-tetraazacyclododecane (cyclen), 1 ,4,7,10-tetramethyl-1 ,4,7,10-tetraazacyclododecane (Me4cyclen), and 1 ,4,7, 10-tetrakis(pyridine-2ylmethyl)-1 ,4,7,10-tetraazacyclododecane (Py4cyclen). With Py4cyclen the iron complex is preferred.

[0100] A preferred cross-bridged ligand is of the formula (V):Wherein:R1is independently selected from H, Ci-20-alkyl , C?-4o-arylalkyl , C2-6-alkenyl or C2-6-alkynyl.

[0101] All nitrogen atoms in the macropolycyclic rings may be coordinated with a transition metal. In formula (V), each R1may be the same. Where each R1is Me, this provides the ligand5.12-dimethyl-1 ,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane (L) of which the complex [Mn(L)Cl2] may be synthesized according to WO98 / 39098. Where each R1 = benzyl, this is the ligand 5,12-dibenzyl-1 .5.8.12-tetraaza-bicyclo[6.6.2]hexadecane (!_’) of which the complex [Mn(L’)Cl2] may be synthesized- 21 -55394087-5PE963326EP || 7511-A-EP as described in WO 98 / 39098. Further suitable crossed-bridged ligands are described in WO98 / 39098.

[0102] TRISPICEN-type

[0103] The trispicens are preferably in the form of an iron transition metal catalyst. The trispicen type ligands are preferably of the formula (VI):R17R17N-X-NR17R17 (VI), wherein:X is selected from -CH2CH2-, -CH2CH2CH2-, and -CH2C(OH)HCH2-; each R17 independently represents a group selected from: -CY2-RI8, Ci-s-alkyl, C3-8- cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4- piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononyl; 1 ,4,8,11-tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononyl; 1 ,4-diaza-7-oxa-cyclononyl; 1 ,4,7,10- tetraazacyclododecanyl; 1 ,4-dioxanyl; 1 ,4,7-trithia-cyclononyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl is connected via any atom in the ring of the heterocycloalkyl; heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to N via any atom in the ring of the heteroaryl, aryl selected from homoaromatic monovalent groups having a molecular weight under 300, and C7-40 arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate derivative, carboxamide, sulfonate, amine, and alkylamine, whereinR18 is independently selected from an optionally substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to -CY2 via any atom in the ring of the heteroaryl;Each Y is independently selected from H, CH3, C2H5, C3H7

[0104] The heteroatom donor group is preferably pyridinyl, e.g. 2-pyridinyl, optionally substituted by -Ci-C4-alkyl.- 22 -55394087-5PE963326EP || 7511 -A-EP

[0105] Other preferred heteroatom donor groups are imidazol-2-yl, 1-methyl-imidazol-2-yl, 4-methyl- imidazol-2-yl, imidazol-4-yl, 2-methyl-imidazol-4-yl, 1 -methyl-imidazol-4-yl, benzimidazol-2-yl and 1 -methyl-benzimidazol-2-yl. Preferably at least two of R17 are CY2-RI 8.

[0106] The ligand Tpen (N, N, N’, N’-tetra(pyridin-2-yl-methyl)ethylenediamine) is disclosed in WO 97 / 48787. Other suitable trispicens are described in WO 02 / 077145 and EP 1001009A.

[0107] Exemplary TRISPICEN-type ligands include dimethyl 2,4-di-(2-pyridyl)-3-methyl-7-(pyridi n-2- ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate, dimethyl 2,4-di-(2-pyridyl)-3-methyl- 7-(N,N-dimethyl-amino-ethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate, 5,12-dimethyl- 1 ,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 5, 12-dibenzyl -1 ,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane, N , N-bis(py ridi n-2-yl -m ethyl - 1 ,1 -bis(py ridi n -2-yl )- 1 -aminoethane, and N,N- bis(pyridin-2-yl-methyl-1 ,1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane.

[0108] OTHER LIGANDS

[0109] Other ligands known to those in the art may also be used, and these are discussed below. Typically, these ligands may be used in pre-formed transition metal complexes, which comprise the ligand.

[0110] Firstly, the ligand may be a bidentate nitrogen donor ligand, such as 2,2’-bipyridine or 1 ,10- phenanthroline, both of which are known in the art as ligands in metal driers. Often 2,2’-bipyridine or 1 ,10-phenanthroline are provided as ligands in manganese- or iron-containing complexes. Other bidentate ligands include bidentate amine-containing ligands. 2-aminomethylpyridine, ethylenediamine, tetramethylethylene-diamine, diaminopropane, and 1 ,2-diaminocyclohexane.

[0111] A variety of bi- to hexadentate oxygen donor-containing ligands, including mixed oxygen- and nitrogen-containing donor ligands, are also known. For example, WO 03 / 029371 A1 describes tetradentate diimines of the formula:RI-C(AI-O)=N-R2-N=C(A2-O)-R3wherein:A1 and A2both are aromatic residues;R1 and R3 are covalently bonded groups, for example hydrogen or an organic group; andR2is a divalent organic radical.

[0112] The use of 1 ,3-diketones as ligands is described in both EP 1382648 A1 and WO 00 / 11090 A1 , EP 1382648 also describing the use of complexes comprising 1 ,3-diketones (or 1 ,3-diimines) and bidentate diamines, including bipyridine and phenanthroline.

[0113] Polymeric ligands may also be used. Some exemplary polymeric ligands are described in PCT publication no. WO2017105365A1 .- 23 -55394087-5PE963326EP || 7511-A-EP

[0114] A variety of metal driers are described in US 2005 / 0245639, including vanadium, manganese, iron, cobalt, cerium and lead complexes, including those containing imidazoles and pyrazoles such as those described in WO 00 / 11090, and aromatic and aliphatic amines.

[0115] Of the non-bispidon type ligands the following are most preferred: 5, 12-dimethyl-1 ,5,8, 12- tetraaza-bicyclo[6.6.2]hexadecane, 5,12-dibenzyl-1 ,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 1 ,4,8,11 -tetraazacyclotetradecane, 1 ,4,8,11 -tetramethyl-1 ,4,8,11 -tetraazacyclotetradecane,1 .4.7.10-tetraazacyclododecane, 1 ,4,7,10-tetramethyl-1 ,4,7,10-tetraazacyclododecane, and1.4.7.10-tetrakis(pyridine-2ylmethyl)-1 ,4,7,10-tetraazacyclododecane, N,N-bis(pyridin-2-yl-methyl)- bis(pyridin-2-yl)methylamine, N , N-bis(py ridi n-2-y I -methy I - 1 ,1 -bis(py ridi n -2-y I)- 1 -aminoethane,N , N-bis(py ridi n-2-yl -m ethyl - 1 ,1 -bis(py ridi n-2-y l)-2-pheny I - 1 -aminoethane and 1 ,4,7-trimethyl-1 ,4,7- tri azacyclononane.

[0116] In some embodiments, the ligand is a bispidon ligand. In some exemplary embodiments, the bispidon ligand is BOC.

[0117] In some embodiments, the ligand is a TACN-type ligand. In some exemplary embodiments, the TACN-type ligand is TMTACN (1 ,4,7-trimethyl-1 ,4,7-triazacyclononane).

[0118] The ligand used in the coating compositions, formulations, methods, kits, and systems described herein can be introduced in an organic solvent, water, or mixtures thereof. The ligand may be added to a composition or formulation comprising the autoxidizing binder resin either just after its production, immediately prior to curing or any time in between. The ligand may be added as a pure material to the binder, or as a solution or dispersion. Adding the ligand as a solution or dispersion can be advantageous in permitting improved and / or easier mixing with the binder resin(s). It may be beneficial to dilute ligand in a suitable solvent before adding to the binder if it is wished to introduce a very small amount of ligand, so greater accuracy of dosing can be achieved. Depending on the properties of the ligand and the desired resin-ligand formulation, some suitable solvents include aliphatic hydrocarbons, such as heptanes, water, alcohols, such as ethanol, isopropylalcohol, ethyleneglycol or propylene glycol, or mixtures thereof. The skilled person will be able to easily formulate such solutions, generally using a solvent such as those described above.TRANSITION METALS

[0119] Transition metals to which the ligands may coordinate to provide complexes (metal driers that can accelerate curing of autoxidizable coating compositions of the invention) may be, according to particular embodiments, iron, manganese, vanadium, cobalt, or copper (preferably iron or manganese), or mixtures of any these. The valency of the metals may range from +1 to +6, often from +2 to +5. Some examples include transition metals selected from the group consisting of Fe(ll), Fe(lll), Fe(IV), Fe(V), Mn(ll), Mn(lll), Mn(IV), and Mn(V), for example transition metals selected from the group consisting of Fe(ll), Fe(lll), Mn(ll), Mn(lll), and Mn(IV).

[0120] The transition metals used in the coating compositions, formulations, methods, and kits described herein can be introduced as solids, in suspension, or in a solution in a variety of liquid carriers in combination with or separate from ligand or antiskinning additive. In some embodiments,- 24 -55394087-5PE963326EP || 7511-A-EP the transition metal may be introduced in the form of a salt. In such embodiments, there is no particular limitation as to the source of the transition metal in a salt. Often, transition metal in salt form is commercially available as a solution, for example in a hydrocarbon or other solution to facilitate dissolution in the curable compositions. However, other solvents may also be used, including alcohols, ketones, and water (or aqueous solutions), especially for chloride, sulfate and acetate salts. Salts as contemplated herein further include hydrates of salts. The invention contemplates use of a mixture of metal salts although a single salt is typically used. It will be understood that there is no particular limitation as to the source of the transition metal. Typically, however, the transition metal is provided via a transition metal compound, which term includes transition metal salts. In embodiments, exemplary transition metal salts are formed from a transition metal and a carboxylate. Where the transition metals are provided in manganese or iron salts, salts may be selected from the group consisting of optionally hydrated MnCIz, FeCIz, FeCH, MnBrz, Mn(NOs)2, Fe(NOs)3, MnSC , FeSC , (Fe)2(SO4)3, Mn(acetylacetonate)2, Fe(acetylacetonate)2, Mn(acetylacetonate)3 Fe(acetylacetonate)3, Mn(R4COO)3 (including Mn (acetate^), Fe(R4COO)3, Mn(R4COO)2 (including Mn(acetate)2) and Fe(R4COO)2 (including Fe(acetate)2, wherein R4 is selected from a Ci-24alkyl. Where the salt comprises two or more R4 groups, these can be the same or different. The alkyl moieties, by which is meant saturated hydrocarbyl radicals, may be straight-chain or comprise branched and / or cyclic portions.

[0121] An appropriate quantity of suitable transition metal compound (e.g. providing a source of one or more of iron, manganese, vanadium, cobalt, and copper) can be added to the compositions and formulations of the invention, for example when introducing other components to form an autoxidatively curable medium.

[0122] The typical molar ratio between transition metal atoms and the ligand is between about 0.1 :1 and about 10:1 , often between about 0.3:1 and about 3:1 . Often, the molar ratio between ligand and transition metal atoms will be approximately between 1 :2 and 1 :1 . However, this need not necessarily be the case. Without being bound to theory, an excess of transition metal atoms may be beneficial in allowing a curing behavior following a different mechanism to that in which a well-defined or not well- defined transition metal complex is involved. Conversely, a stoichiometric excess of ligand may be beneficial to improve regeneration of catalytically active species during curing, which can lead to improved curing performance despite using a lower quantity of transition metal atoms. Using a stoichiometric excess of ligand can also be advantageous by reducing the intensity of colored metals and / or complexes.

[0123] In some embodiments, the metal drier, e.g., as a pre-formed complex of transition metal and ligand, is dissolved in liquid carrier (water or solvent) at a concentration of about 0.001 to about 85 wt.%, e.g., about 0.01 to about 80 wt.%, or about 0.001 to about 10 wt.%, based on the weight of the complex and liquid carrier. Increasing the concentration of the metal drier in the liquid carrier allows a relatively smaller volume of the drier-containing solution or dispersion to be added to the coating composition. This may be desired by the skilled person. A person having ordinary skill in the art will- 25 -55394087-5PE963326EP || 7511-A-EP be able to select the appropriate liquid carrier for a given metal drier and alkyd coating system to provide processability and effective performance.

[0124] The resultant formulation, comprising the metal drier and liquid carrier, 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 and ligand. If the complex is not preformed but formed in-situ (in the drier mixture), a transition metal salt may also be, in some embodiments, dissolved in liquid carrier at a concentration of about 0.001 to about 1 wt.% based on the transition metal ion to water ratio. An appropriate amount of ligand can then be added to form the desired complex. The ligand may also be added prior to the metal.

[0125] In embodiments, after preparation, a solution or dispersion of the metal drier (a metal drier formulation) may then be contacted with, e.g., added to, a coating composition or binder resin formulation.

[0126] In alternative embodiments, depending on reactivity with components of the coating composition, the transition metal compounds and the ligands of the metal drier may be separately added to a coating composition or binder resin formulation (including at least an autoxidizing binder resin and a carrier liquid) to allow formation of a complex in situ in the coating composition or binder resin formulation.

[0127] In embodiments, the coating composition contains one or more metal driers in overall concentration of at least about 0.0002 % MORS, in further embodiments, at least about 0.0003 % MORS, in further embodiments, at least about 0.002 % MORS, in further embodiments, at least about 0.01 % MORS, and in still further embodiments, at least about 0.02 % MORS. In embodiments, the coating composition contains one or more metal driers in overall concentration of at most about 1 .0 % MORS, in further embodiments, at most about 0.5 % MORS, in further embodiments, at most about 0.25 % MORS, in further embodiments, at most about 0.2 % MORS, and in still further embodiments, at most about 0.1 % MORS. Metal driers are present in coatings or formulations in amounts expressed as weight percent of the transition metal based on the weight of binder solids (or resin solids) unless stated otherwise (% MORS). It will be appreciated that this measure may apply either to a fully formulated coating composition or to a binder resin, or some intermediate therebetween, because the measure depends on binder resin solids and metal content only. Similarly, the appropriate amount of transition metal compound or ligand for a formulation that will be added to form a composition or another formulation can be determined to provide a desired concentration in a resulting coating composition or binder resin formulation. The above measure, abbreviated “MORS”, stands for “metal on resin solids”. MORS is calculated in the following way: mdx MCdMORS = SCf100%X mf- 26 -55394087-5PE963326EP || 7511-A-EP with nrid. mass of the drier (or drier solution if in solution), in g; MCd. metal content of the drier (or drier solution if in solution) in %; SCf. solid content (of binder, including any dissolved or dispersed solids) in the formulation, in %; and m . mass of the formulation, in g.ANTISKINNING ADDITIVE

[0128] A characteristic feature of the various aspects of the present invention is the use of an inventive antiskinning additive of one of the below forms or classes. The inventive antiskinning additive comprises a compound including a dihydroarene moiety or a methylene cyclohexene moiety. The compound including a dihydroarene moiety or a methylene cyclohexene moiety is preferably a liquid at 23 ± 1°C and standard pressure (1 ATM).

[0129] By “dihydroarene moiety” is meant a moiety that would result from the hydrogenation of one double bond on an aromatic compound. It is explicitly contemplated herein that the compound including a dihydroarene moiety may be the unsubstituted dihydroarene moiety itself or a substituted dihydroarene moiety. In preferred embodiments, the dihydroarene moiety in unsubstituted form is a six-membered carbon ring of Formula A or Formula B:Formula AFormula B

[0130] Thus, exemplary compounds including a dihydroarene moiety are of Formula X-A or Formula X-B:Formula X-AFormula X-Bwherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSIRsRgRio, -OR11, -NR11R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl,- 27 -55394087-5PE963326EP || 7511-A-EP wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic.

[0131] By “methylene cyclohexene moiety” is meant a moiety that, in unsubstituted form, is a sixmembered carbon ring with a methylene substituent, having Formula C or Formula D:Formula CFormula DIt is explicitly contemplated herein that the compound including a methylene cyclohexene moiety may be the unsubstituted methylene cyclohexene moiety itself or a substituted methylene cyclohexene moiety.

[0132] Thus, exemplary compounds including a methylene cyclohexene moiety are of Formula Xl-C or Formula Xl-D:Formula Xl-CFormula Xl-Dwherein R1-R7 are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSIRsRgRio, -OR11, -NR11R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the- 28 -55394087-5PE963326EP || 7511 -A-EP resulting compound including a methylene cyclohexene moiety is polycyclic.

[0133] Exemplary embodiments of formulas of compounds including a dihydroarene moiety or a methylene cyclohexene moiety according to Formulas X-A, X-B, Xl-C, or Xl-D are provided below in Table A:Table A

[0134] In some exemplary embodiments, the compounds including a dihydroarene moiety or a methylene cyclohexene moiety are selected from the group consisting of a-terpinene, y-terpinene, a- phellandrene, 1 ,3-cyclohexadiene, and 6-terpinene (also known as terpinolene).

[0135] In some exemplary embodiments, the antiskinning additive comprises a compound of Formula X-A or X-B. In further preferred embodiments, the antiskinning additive comprises a compound selected from the group consisting of a-terpinene, y-terpinene, a-phellandrene, and 1 ,3- cyclohexadiene.

[0136] The dihydroarene moiety (or methylene cyclohexene moiety) of the compounds of the antiskinning additives of the disclosed invention, in combination with the other components of the disclosed invention, may provide enhanced antiskinning performance. Without being bound by theory, it is believed that these dihydroarene and methylene cyclohexene structures may be capable of forming semi-stable aromatic structures by reactions with radicals, thereby providing the desired- 29 -55394087-5PE963326EP || 7511-A-EP antiskinning effects in situ. The inventive antiskinning additives provide a good balance of antiskinning effect with maintained, improved, or minimally increased coating dry-time relative to conventional coating compositions containing only conventional antiskinning agents.

[0137] In some preferred embodiments, the inventive antiskinning additive comprises a compound including a dihydroarene moiety or a methylene cyclohexene moiety wherein the compound has a boiling point of at most 210°C at standard pressure (1 ATM), in further embodiments, at most 207.5°C, and in yet further embodiments, at most 200°C.

[0138] In embodiments, the compound of the antiskinning additive may be mixed with a liquid carrier, to provide a formulation, in a concentration of at least 0.5 % w / w (antiskinning additive compound weight as a percent of the total mixture weight), in further embodiments, at least 2 % w / w, in further embodiments at least 4 % w / w, and in still further embodiments at least 8 % w / w. In other embodiments, the compound of the antiskinning additive may be mixed with a liquid carrier, to provide a formulation, in a concentration of at most 99.9 % w / w (antiskinning additive weight as a percent of the total mixture weight), in further embodiments, at most 90 % w / w, in further embodiments at most 80 % w / w, and in still further embodiments at most 70 % w / w. It is explicitly contemplated herein that references to an “antiskinning additive formulation” may refer to either a substantially pure compound including a dihydroarene moiety or a methylene cyclohexene moiety or a mixture of such a compound with other components (such as liquid carrier).

[0139] In embodiments, the antiskinning additive (in pre-dissolved or pre-dispersed formulation, as described above, or in substantially pure form, i.e., including less than 1 % w / w liquid carrier) can be contacted with a coating composition in the coating manufacturing process or can be contacted with one or more other components or formulations of a coating composition (e.g., a source of transition metal, ligand, a combined mixture of transition metal compound and ligand as discussed above, an autoxidizing binder resin, optional additional components, or some mixture of any of these) prior to integration with the other coating components or formulations.

[0140] In embodiments, the coating composition contains one or more compounds of the inventive antiskinning additives in overall concentration of at least about 0.25 wt. %, in further embodiments, at least about 0.3 wt. %, in further embodiments, at least about 0.4 wt. %, in further embodiments, at least about 0.5 wt. %, and in still further embodiments, at least about 0.55 wt. %. In embodiments, the coating composition contains one or more compounds of the inventive antiskinning additives in overall concentration of at most about 5.0 wt.%, in further embodiments, at most about 4.5 wt. %, in further embodiments, at most about 4.0 wt. %, in further embodiments, at most about 2.0 wt. %, and in still further embodiments, at most about 1 .5 wt. %. Throughout the specification, wt. % with respect to antiskinning additive in a coating composition or binder resin formulation is expressed as parts by weight pure antiskinning additive compound (excluding any liquid carrier weight in an antiskinning additive formulation and any additional antiskinning agent weight) in addition to parts by weight liquid coating or binder resin formulation (excluding all antiskinning additive formulation weight). For instance, in a coating composition containing 0.5 g antiskinning additive compound at 0.5 wt. %, the coating composition would include a combined 100 g of other coating components apart from the- 30 -55394087-5PE963326EP || 7511 -A-EP antiskinning additive or antiskinning additive formulation (e.g., binder resin, solvent, pigment, and metal drier, excluding any liquid carrier weight introduced by the antiskinning additive or an antiskinning additive formulation and any weight from any additional antiskinning agent). In a binder resin formulation containing 0.3 g antiskinning additive compound at 0.3 wt. %, the binder resin formulation would include a combined 100 g of other binder resin formulation components apart from the antiskinning additive (e.g., binder resin, solvent, and optional additional components, excluding any liquid carrier weight introduced by the antiskinning additive or an antiskinning additive formulation and any additional antiskinning agent). Wt. % is used analogously with respect to additional antiskinning agents (described in greater detail, below; such additional antiskinning agents differ in composition from the antiskinning additives described in this section) throughout the specification, as well.

[0141] In embodiments, the binder resin formulation contains one or more compounds of the inventive antiskinning additives in overall concentration of at least about 0.3 wt. %, in further embodiments, at least about 0.36 wt. %, in further embodiments, at least about 0.48 wt. %, in further embodiments, at least about 0.6 wt. %, and in still further embodiments, at least about 0.66 wt. %. In embodiments, the binder resin formulation contains one or more compounds of the inventive antiskinning additives in overall concentration of at most about 9.0 wt.%, in further embodiments, at most about 8.1 wt. %, in further embodiments, at most about 7.2 wt. %, in further embodiments, at most about 3.6 wt. %, and in still further embodiments, at most about 2.7 wt. %.

[0142] The antiskinning additive can be added be added to a coating composition or other formulation in any suitable form. Thus, the antiskinning additive can be added as a solid or pure liquid or dissolved or dispersed in a liquid carrier. The antiskinning additive can be added to a coating composition or a formulation at any point during manufacture of the coating composition or formulation, though the antiskinning additive is typically added to a coating composition or binder resin formulation as a “post-add” after other primary components (binder resin, pigment, etc. as the case may be) are added and mixed.COATING COMPOSITIONS, FORMULATIONS, KITS, AND METHODS

[0143] In some embodiments, the invention is directed to a coating composition that includes:(I) at least one autoxidizing binder resin;(ii) at least one ligand, preferably selected from the group consisting of bispidon, N4py- type, TACN-type, cyclam and cross-bridged ligands, and trispicen-type ligands, or a mixture thereof;(iii) transition metal compounds, which may include, for example, compounds of manganese, iron, copper, cobalt, or vanadium, but may, in preferred embodiments include compounds of iron or manganese,(iv) at least one antiskinning additive comprising a compound including a dihydroarene moiety or a methylene cyclohexene moiety, and(v) optionally, additional materials, such as at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one- 31 -55394087-5PE963326EP || 7511 -A-EPUV stabilizer; at least one dispersant; at least one surfactant; at least one corrosioninhibitor; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0144] As discussed above, in coatings, 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.

[0145] A formulation or composition of the invention can, and generally will, be used in the manufacture of a fully formulated oxidatively curable coating composition. By the term “fully formulated oxidatively curable coating composition” is implied, as is known to those of skill in the art, oxidatively curable formulations that comprise additional components over and above the binder (the autoxidatively curable material, which may be alkyd resin), an aqueous or non-aqueous solvent / liquid continuous phase, antiskinning additive, and metal drier intended to accelerate the curing process. Such additional components are generally included to confer desirable properties upon the coating composition, such as color or other visual characteristics such as glossiness or matte-ness), physical, chemical and even biological stability (enhanced biological stability being conferred upon coating compositions by the use of biocides, for example), or modified texture, plasticity, adhesion and viscosity or rheology.

[0146] For example, such optional additional components may be selected from co-solvents, additional antiskinning agents (apart from the antiskinning additives described above; sometimes also referred to as antioxidants), additional metal driers, auxiliary or secondary driers, colorants (including inks and colored pigments), fillers, plasticizers, viscosity modifiers, crosslinkers, UV light absorbers, stabilizers, antistatic agents, flame retardants, lubricants, emulsifiers (in particular where an oxidatively curable coating composition or formulation of the invention is aqueous-based), antifoaming agents, viscosity modifiers, antifouling agents, biocides (e.g. bactericides, fungicides, algaecides and insecticides), anticorrosion agents, antireflective agents, anti-freezing agents, waxes and thickeners. The skilled person is familiar with the incorporation of these and other components into oxidatively curable coating compositions to optimize such compositions’ properties.

[0147] It will be appreciated that some of these optional additional components may possess more than one functional property. For example, some fillers may also function as colorants. The nature of any additional components and the amounts used may be determined in accordance with the knowledge of those of skill in the art and will depend on the application for which the curable coating compositions is intended. Examples of optional additional components are discussed in the following paragraphs, which are intended to be illustrative, not limiting.- 32 -55394087-5PE963326EP || 7511-A-EP

[0148] Some exemplary, optional additional antiskinning agents / antioxidants known in the art of the formulation of coating compositions, include: phenol derivatives, e.g. pyrogallol, 2,6-di-tert- butylhydroxytoluene, 3,4-dihydroxbenzaldehyde, CAS 139-85-5 (available from BLDpharm), 2-iso- propylphenol, CAS 88-69-7 (available from Thermo Scientific), eugenol, CAS 97-53-0 (available from BLDpharm), resveratrol, CAS 501-36-0 (available from BLDpharm), thymol, CAS 89-83-8 (available from Haarmann & Reimer GmbH), guaiacol, CAS 90-05-1 (available from Thermo Scientific), creosol, CAS 93-51-6 (available from Millipore Sigma), butylated hydroxytoluene (BHT), CAS 128-37-0 (available from Vulkanox), propyl gallate, CAS 121 -79-9 (available from Thermo Scientific), methyl gallate, CAS 99-24-1 (available from BLD pharm), 2-sec-butylphenol, CAS 89-72-5 (available from Thermo Scientific), 2-ethoxyphenol, CAS 94-71-3 (available from Thermo Scientific), a-tocopherol, CAS 10191-41-0 (available from Fluka), 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, isoeugenol, 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, methylethylketoxime, and 2-pentanone oxime (2PO); hydroxyacetone, diethylhydroxylamine, 3,5-dimethylpyrazole, ascorbic acid, Hindered Amine Light Stabilisers (HALS), e.g. Tinuvin® 123 (i.e., Bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate) and Tinuvin® 292c (i.e., a blend of Bis (1 , 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate & Methyl 1 , 2, 2, 6, 6- pentamethyl-4-piperidyl sebacate) 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.

[0149] Some formulations or compositions of the invention contain less than 0.5 % by weight of MEKO, in further embodiments, less than 0.1 % by weight of MEKO, in still further embodiments, less than 0.01 % by weight of MEKO, and in yet still further embodiments, less than 0.001 % by weight of MEKO.

[0150] Some formulations or compositions of the invention contain less than 0.5 % by weight of oxime antiskinning agents, in further embodiments, less than 0.1 % by weight of oxime antiskinning agents, in still further embodiments, less than 0.01 % by weight of oxime antiskinning agents, and in yet still further embodiments, less than 0.001 % by weight of oxime antiskinning agents.- 33 -55394087-5PE963326EP || 7511 -A-EP

[0151] In some embodiments, inventive coating compositions or formulations optionally further include “secondary driers”, synonymously “auxiliary driers,” or “through driers,” which include, for example, 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 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 are typically between about 0.01 wt.% and 2.5 wt.% as is known in the art. One having skill in the art will recognize that may be added directly to a fully formulated coating composition or binder resin or may be added to a metal drier formulation prior to addition to a fully formulated coating composition or binder resin. Some exemplary secondary driers include Calcium-Hydrochem (based on Calcium neodecanoate in organic solvents, available from Borchers); and Octa Soligen Zirconium 10 aqua (Zr-2-ethyl hexanoate in organic solvents, available from Borchers) and other secondary driers having similar characteristics to the named above.

[0152] 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.

[0153] Various additional materials and applications as will be known to those having ordinary skill in the art for addition in alkyd or other autoxidizable coating compositions. These materials and applications are also contemplated herein.

[0154] In an aspect of the invention, the coating compositions of the invention comprise at least one compound including a dihydroarene moiety or a methylene cyclohexene moiety (according to any embodiment described above) and at least one additional antiskinning agent. In such embodiments, with the benefit of this disclosure, a person having ordinary skill in the art will recognize that a smaller amount of both any compound including a dihydroarene moiety or a methylene cyclohexene moiety and any additional antiskinning agent will be necessary to provide good antiskinning effect while maintaining or improving coating dry times. In exemplary embodiments of this aspect, the compound including a dihydroarene moiety or a methylene cyclohexene moiety is present in the coating composition in an amount of at least 0.01 wt. %, in further embodiments at least 0.02 wt. %, in yet- 34 -55394087-5PE963326EP || 7511-A-EP further embodiments at least 0.05 wt. %, and in still further embodiments at least 0.2 wt. %. In such exemplary embodiments, the compound including a dihydroarene moiety or a methylene cyclohexene moiety is present in the coating composition in an amount of at most 2.0 wt. %, in further embodiments at most 1 .5 wt. %, in yet further embodiments at most 1 .0 wt. %, and in still further embodiments at most 0.5 wt. %. In such exemplary embodiments, the additional antiskinning agent is present in the coating composition in an amount of at least 0.01 wt. %, in further embodiments at least 0.02 wt. %, in yet further embodiments at least 0.05 wt. %, and in still further embodiments at least 0.1 wt. %. In such exemplary embodiments, additional antiskinning agent is present in the coating composition in an amount of at most 1 .0 wt. %, in further embodiments at most 0.8 wt. %, in yet further embodiments at most 0.5 wt. %, and in still further embodiments at most 0.1 wt. %.

[0155] In a further aspect of the invention, the binder resin formulations of the invention comprise an antiskinning additive including at least one compound including a dihydroarene moiety or a methylene cyclohexene moiety (according to any embodiment described above) and at least one additional antiskinning agent. In such embodiments, with the benefit of this disclosure, a person having ordinary skill in the art will recognize that a smaller amount of both any compound including a dihydroarene moiety or a methylene cyclohexene moiety and any additional antiskinning agent will be necessary to provide good antiskinning effect while maintaining or improving coating dry times. In exemplary embodiments of this aspect, the compound including a dihydroarene moiety or a methylene cyclohexene moiety is present in the binder resin formulation in an amount of at least 0.012 wt. %, in further embodiments at least 0.024 wt. %, in yet further embodiments at least 0.06 wt. %, and in still further embodiments at least 0.24 wt. %. In such exemplary embodiments, the compound including a dihydroarene moiety or a methylene cyclohexene moiety is present in the binder resin formulation in an amount of at most 3.6 wt. %, in further embodiments at most 2.7 wt. %, in yet further embodiments at most 1 .8 wt. %, and in still further embodiments at most 0.9 wt. %. In such exemplary embodiments, the additional antiskinning agent is present in the binder resin formulation in an amount of at least 0.012 wt. %, in further embodiments at least 0.024 wt. %, in yet further embodiments at least 0.06 wt. %, and in still further embodiments at least 0.12 wt. %. In such exemplary embodiments, additional antiskinning agent is present in the binder resin formulation in an amount of at most 1 .8 wt. %, in further embodiments at most 1 .44 wt. %, in yet further embodiments at most 0.5 wt. %, and in still further embodiments at most 0.1 wt. %.

[0156] 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, tanks, containers, packages, equipment or for coil coatings. The thus applied composition may then be allowed to cure. The invention also provides a composition, when cured.- 35 -55394087-5PE963326EP || 7511 -A-EP

[0157] Thus, the invention also provides a method comprising applying to a substrate a coating composition. The thus applied coating composition may then be allowed to cure.

[0158] 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 orwood, 1987, page 39 et seq.).

[0159] 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 coating compositions 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, some compositions of the present invention may be cured by additional heating.

[0160] 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.

[0161] In some embodiments, the invention comprises a kit that may consist of two or three formulations, wherein each formulation includes one or more of an autoxidizing binder resin, a transition metal, a ligand, and an antiskinning additive. The formulations of said kits are physically separated from each other, for instance in separate cartridges, sachets, or the like.

[0162] In some embodiments, the invention comprises a kit that may consist of two or three formulations, wherein each formulation includes one or more of a transition metal, a ligand, and an antiskinning additive. The formulations of said kits are physically separated from each other, for instance in separate cartridges, sachets, or the like.

[0163] In each of the kits of the invention, one or more of the two (or three) formulations may comprise additional components (for example a formulation comprising autoxidizable binder may also comprise a secondary binder resin, a biocide or other coating additive, etc.). The components of such kits are generally combined with one another, whereby to provide a coating composition or a formulation that is useful for providing a coating composition, which coating composition may cure to provide a cured coating. Furthermore, in each of the kits of the invention, the separation of ligand and transition metal components and their combination may yield a complex that is not-well-defined.

[0164] In some embodiments, the invention consists of a formulation, wherein the formulation includes a transition metal compound, a ligand, and an antiskinning additive. Said formulation can be- 36 -55394087-5PE963326EP || 7511-A-EP combined with a binder resin or a binder resin and optional, additional components to yield a fully formulated coating composition.

[0165] In one embodiment, a method for forming a coated substrate or article is provided whereby a coating composition comprising: a metal drier; an autoxidizing binder resin; an inventive antiskinning additive and optional additional components (as described above) is provided. The coating composition is subsequently applied to a substrate or article by conventional methods (e.g., by paint brush or roller) and allowed to cure in the presence of ambient air.

[0166] In some embodiments, a method of contacting is provided whereby components of two or three formulations are contacted with one another, wherein each formulation may include one or more of an autoxidizable binder, a transition metal compound, a ligand, and an antiskinning additive. Each of the autoxidizable binder, transition metal compound, ligand, and antiskinning additive may be the materials as described throughout this disclosure with respect to curable coating materials. There is no particular order in which the method of contacting need be carried out. For example, autoxidizable binder may be contacted with ligand and transition metal and antiskinning additive contacted with that mixture afterwards. Alternatively, transition metal compounds may be contacted with autoxidizable binder and that mixture contacted with the ligand and antiskinning additive afterwards; or ligand, transition metal, and antiskinning additive may be simultaneously contacted with autoxidizable binder. Generally, with the benefit of this disclosure, a person having ordinary skill in the art will recognize that the antiskinning additive is preferably present with the autoxidizing binder resin prior to, at the time of, or shortly after the addition of both transition metal and ligand to avoid undesirable curing and thus skinning of the binder.

[0167] In some embodiments, the invention is a formulation including the inventive antiskinning additive as described above for use as an antiskinning agent in an oxidatively curable coating composition as provided above.

[0168] The kits, compositions, formulations, or systems of the invention may optionally comprise instructions or other guidance as to methods according to which the various components or formulations may be contacted. In this way, the manufacture of coatings, can, for example, after optimizing the nature of the source of transition metal by the preparation of a particular solution or dispersion of a particular transition metal salt, optimize the manner in which formulations containing transition metal complexes and / or antiskinning additive can be prepared. The preparation of an activated resin composition may be by the manufacturer of said coatings who can contact a source of transition metal (e.g., a transition metal compound in solution) with an otherwise fully formulated activated resin formulation. In this way, the manufacturer of the resins, metal drier, or antiskinning additive can provide guidance to the producer of coatings and which optimal dosing can be used.

[0169] Where a formulation of the invention is “substantially absent” a component (e.g., substantially absent transition metal including any one or more of iron, manganese, cobalt, vanadium, or copper or substantially absent ligand), the formulation contains less than 0.01 % by weight of that component. Where a formulation of the invention is “essentially absent” a component, the formulation contains less than 0.0001 % by weight of that component. Where a formulation of the invention is “fully absent” - 37 -55394087-5PE963326EP || 7511-A-EP a component, the formulation contains less than 0.00001 % by weight of that component. Where a formulation of the invention is entirely absent a component, the formulation contains no measurable amount of that component. Ideally, embodiments of the composition of the invention that are essentially absent, substantially absent, fully absent, or entirely absent a component are absent any of the component specified. This may be, in practice, impossible to achieve, however. Accordingly, these are preferably absent the component specified to the greatest extent practicable.

[0170] In some embodiments, particularly those embodiments pertaining to formulations or kits comprising formulations containing fewer than all the essential components of a coating composition (autoxidizable binder resin, metal drier, and antiskinning additive), a given formulation may be essentially absent, substantially absent, fully absent, or entirely absent any of the components not intended to be present that formulation.

[0171] Unless otherwise specified, all measurements herein are made at 23 ± 1°C and 50% relative humidity.

[0172] It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each and every other component, compound, substituent or parameter disclosed herein.

[0173] It is further understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter. Thus, this disclosure is to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is also further understood that any range between the endpoint values within the broad range is also discussed herein.

[0174] Reference throughout this specification to “some approaches” or “an approach” or “one embodiment,” “an embodiment,” “certain embodiments,” or “some embodiments,” etc., means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of such phrases in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

[0175] Certain terminology is used herein for convenience only and is not to be taken as a limitation on the present disclosure.

[0176] Each and every patent and non-patent reference referred to herein is hereby incorporated by reference in its entirety, as if the entire content of each reference was set forth herein in its entirety.

[0177] A particular advantage of the compositions, formulations, and methods of the present invention is the maintenance or improvement of coating dry time and bulk and surface material mechanical properties, protective properties, and decorative properties of a coating while providing - 38 -55394087-5PE963326EP || 7511 -A-EP enhanced storage stability and resistance to skinning. Coating compositions (and associated kits, methods, and formulations therefore) comprising autoxidizing binder resin, transition metal compound, ligand, antiskinning additive, and optional additional materials, provide superior coatings having good dry time and mechanical, protective, and decorative properties relative to compositions that do not include the inventive antiskinning additives.

[0178] The invention and the potential embodiments thereof described in and embraced by the foregoing description may be further understood by reference to the particular clauses set forth below. As such, these clauses are included for illustrative purposes only (e.g., describing potentially preferred embodiments of the invention) and are not intended to limit the foregoing description in any manner.

[0179] In a preferred embodiment, the invention includes a coating composition comprising: a) an autoxidizing binder resin; b) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; c) an antiskinning additive including a compound comprising a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-BFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or the compound is of Formula Xl-C or Formula Xl-D:- 39 -55394087-5PE963326EP || 7511 -A-EPFormula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM), and d) optionally, additional materials, selected from the group consisting of: at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosion-inhibitor; at least one pigment; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0180] In a preferred embodiment, the invention includes a coating composition comprising: a) an autoxidizing binder resin; b) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; c) an antiskinning additive including a compound comprising a dihydroarene moiety, wherein the compound is of Formula X-A or X-B:55394087-5PE963326EP || 7511 -A-EPFormula X-BFormula X-Awherein Ri-Re are each independently H, C1-C12 alkyl, Ce-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1°C and pressure (1 ATM), and d) optionally, additional materials, selected from the group consisting of: at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosion-inhibitor; at least one pigment; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0181] In a preferred embodiment, the invention includes a coating composition comprising: a) an autoxidizing binder resin; b) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; c) an antiskinning additive including a compound comprising a methylene cyclohexene moiety, wherein the compound is of Formula Xl-C or Formula Xl-D:- 41 -55394087-5PE963326EP || 7511 -A-EPFormula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM), and d) optionally, additional materials, selected from the group consisting of: at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosion-inhibitor; at least one pigment; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0182] In a preferred embodiment, the invention includes a coating composition comprising: a) an autoxidizing binder resin; b) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; c) an antiskinning additive including a compound comprising a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is of Formula X-A or Formula X-B:55394087-5PE963326EP || 7511 -A-EPFormula X-BFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSIRsRgRio, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or the compound is of Formula Xl-C or Formula Xl-D:Formula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSIRsRgRio, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such- 43 -55394087-5PE963326EP || 7511-A-EP that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM), and d) an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof e) optionally, additional materials, selected from the group consisting of: at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosion-inhibitor; at least one pigment; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0183] In a preferred embodiment, the invention includes a binder resin formulation comprising: a) an autoxidizing binder resin; b) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type, and c) an antiskinning additive including a compound comprising a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-BFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or- 44 -55394087-5PE963326EP || 7511 -A-EP any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or the compound is of Formula Xl-C or Formula Xl-D:Formula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM).

[0184] In a preferred embodiment, the invention includes a binder resin formulation comprising: a) an autoxidizing binder resin, and b) an antiskinning additive including a compound comprising a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-B- 45 -55394087-5PE963326EP || 7511 -A-EPFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgRw, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or the compound is of Formula Xl-C or Formula Xl-D:Formula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgRw, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM).

[0185] In a preferred embodiment, the invention includes a binder resin formulation comprising: a) an autoxidizing binder resin;55394087-5PE963326EP || 7511-A-EP b) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; c) an antiskinning additive including a compound comprising a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-BFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Ci4 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSIRsRgRio, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or the compound is of Formula Xl-C or Formula Xl-D:Formula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12- 47 -55394087-5PE963326EP || 7511 -A-EP carboxylate derivative, -OSiRsRgRw, -ORn, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM), and d) an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof.

[0186] In a preferred embodiment, the invention includes the use of an antiskinning additive formulation as an antiskinning agent for autoxidizing coatings, the antiskinning additive formulation comprising: a) an antiskinning additive including a compound comprising a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-BFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgRw, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and Rw is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or the compound is of Formula Xl-C or Formula Xl-D:- 48 -55394087-5PE963326EP || 7511 -A-EPFormula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM); b) optionally, an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof; and c) optionally, a liquid carrier.

[0187] In a preferred embodiment, the invention includes the use of an antiskinning additive formulation as an antiskinning agent for autoxidizing coatings, the antiskinning additive formulation comprising: a) an antiskinning additive including a compound comprising a dihydroarene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-B- 49 -55394087-5PE963326EP || 7511 -A-EPFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgRw, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM); b) optionally, an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof; and c) optionally, a liquid carrier.

[0188] In a preferred embodiment, the invention includes the use of an antiskinning additive formulation as an antiskinning agent for autoxidizing coatings, the antiskinning additive formulation comprising: a) an antiskinning additive including a compound comprising a methylene cyclohexene moiety, wherein the compound is of Formula Xl-C or Formula Xl-D:Formula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgRw, -OR11, -NR11 R12, F, Cl, Br, or I,55394087-5PE963326EP || 7511 -A-EP wherein each Rs, g, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM); b) optionally, an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof; and c) optionally, a liquid carrier.

[0189] In a preferred embodiment, any of the above preferred antiskinning additive formulations or binder resin formulations is provided for use in an autoxidizing alkyd coating composition.

[0190] In a preferred embodiment, the invention includes an alkyd coating drier and antiskinning additive system comprising: a) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; b) an antiskinning additive including a compound comprising a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-BFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or the compound is of Formula Xl-C or Formula Xl-D:- 51 -55394087-5PE963326EP || 7511-A-EPFormula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM); c) optionally, an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof, and d) optionally, a liquid carrier.

[0191] In a preferred embodiment, the invention includes an alkyd coating drier and antiskinning agent system comprising: a) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; b) an antiskinning additive including a compound comprising a dihydroarene moiety, wherein the compound is of Formula X-A or Formula X-B:Formula X-B- 52 -55394087-5PE963326EP || 7511 -A-EPFormula X-Awherein Ri-Rs are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgRw, -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic,, and wherein the compound is a liquid at 23 ± 1 °C and pressure (1 ATM); c) optionally, an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof, and d) optionally, a liquid carrier.

[0192] In a preferred embodiment, the invention includes an alkyd coating drier and antiskinning agent system comprising: a) a drier including iron or manganese metal and a ligand of TACN-, Bispidon-, or N4py-type; b) an antiskinning additive including a compound comprising a methylene cyclohexene moiety, wherein the compound is of Formula Xl-C or Formula Xl-D:Formula Xl-DFormula Xl-Cwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgRw, -OR11, -NR11 R12, F, Cl, Br, or I,55394087-5PE963326EP || 7511 -A-EP wherein each Rs, g, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic, and wherein the compound is a liquid at 23 ± 1°C and pressure (1 ATM); c) optionally, an additional antiskinning agent selected from the group consisting of: phenol derivatives, sulphides, phosphites, phosphonites, dioxo compounds, oximes, hindered amine light stabilizers, and mixtures thereof, and d) optionally, a liquid carrier.

[0193] Each of the above preferred embodiments may be “consisting essentially of’ the components described.

[0194] In some preferred embodiments, the coating compositions, binder resin formulations, antiskinning additive formulations, and alkyd coating drier and antiskinning agent systems are essentially absent, substantially absent, fully absent, or entirely absent either copper transition metal ions, vanadium transition metal ions, or both copper transition metal ions and vanadium metal transition metal ions.

[0195] The invention will further be more readily understood by reference to examples, which are included merely for purpose of illustration of certain aspects and embodiments of the present invention and are not intended to limit the invention.EXAMPLES

[0196] Selected T est Methods

[0197] Unless otherwise specified, all values, measurements, and ratings are provided in accordance with the following test methods.

[0198] Dry Times (ST, TF, and DH)

[0199] Dry times in hours were measured on B.K.-type drying recorders (mtv Messtechnik, Germany) in order to find the time required to reach the drying states of set-to-touch (ST, i.e. no longer moving freely through the soft coating but starting to rip the hardening film), tack-free (TF, i.e. no longer ripping the film but still leaving a continuous line on the hardening film) and dry-hard (DH, i.e. not leaving any mark on the film). A film of 100 pm thickness was cast on a glass strip (30x2.4 cm) by using a steel cube applicator. This coated glass strip is then placed on the dry time recorder, a needle put on the film, the recorder set for measurement over 24 hours, and the process started. The starting point where the needle was put onto the film was marked on the glass. The drying time was read from the marks left on the film after 24 hours. Dry times given as “24 h” indicate dry times of > 24 h, as times longer than 24 hours are not determinable by this method. Dry times of greater than 24 hours are generally unacceptable to paint applicators.- 54 -55394087-5PE963326EP || 7511-A-EP

[0200] The coating of all glass plates and the recording of dry time was performed in a climate- controlled room with a temperature of ca. 23°C and a humidity of ca. 50%.

[0201] Skinning Rating

[0202] Skinning of the formulations was rated with numbers from 0 to 3, whereas 0 signifies no skin formation and 3 signifies a skin covering the entire surface of the formulation at the interface between air and formulation thickly enough to prevent any flow of the formulation on pouring as well as any rupture or significant movement, even when the container is turned upside-down. Intermediate values from 0.1 to 1 indicate the beginning of skin formation on the air-formulation interface, around the border, at the container wall, up to a very thin skin covering almost the entire air-formulation interface. A value of 2 indicates a skin covering the entire air-formulation interface, which skin ruptures when the container is turned upside down. Values between 1 .1 and 1 .9 indicate a condition between conditions corresponding to 1 and 2 (e.g., an extremely thin and fragile skin covering the entire airformulation interface or a thicker skin covering almost but not the entire air-formulation interface, wherein the skin ruptures when the container is turned upside down). A value of 2.5 indicates a skin not rupturing but being thin enough to allow significant movement (bowing outward of the skin surface) upon turning the container upside-down.

[0203] The skinning rating was conducted in the following way over a period of 14 days: after storage of the freshly prepared formulation in a plastic cup for one day, the degree of skinning was determined directly before coating (1 d). After coating, the remaining formulation was filled into a glass vial of 8 ml capped with a teflon-sealed screw cap, filled up to a level so that 1 inch of air headspace remained. If any skinning was observed at 1 d, the skin was removed in the transfer of formulation to the glass vial. These glass vials were then placed into an oven of 50° C and remained there for a total storage time of 14 days after preparation of the binder formulation or coating composition (13 days of oven storage time in sealed glass vials). The degree of skinning was determined by visual inspection according to the above method at different intervals (in days from formation, d) until the end of the storage time (14 d).

[0204] Glossary of Selected MaterialsTable B- 55 -55394087-5PE963326EP || 7511-A-EP55394087-5PE963326EP || 7511-A-EP-57-55394087-5PE963326EP || 7511-A-EP-58-55394087-5PE963326EP || 7511-A-EP-59-55394087-5PE963326EP || 7511 -A-EP

[0205] Sample Preparation

[0206] The short and medium oil resins were used pure as received, while the long oil resins were used as the basis for pigmented formulations, Base Paints 1 -4, the components of which are shown below in Tables B1-B4. The components of Base Paints 1 -4 were combined according to standard methods known to those having ordinary skill in the art. Where a particular material is duplicated across multiple rows for the same Table, this indicates that the material was added multiple times during the formation of the Base Paint. Amounts of duplicate materials in the same Table are additive in the total Base Paint formula. For instance, in Table B1 , 174.12 g of Synolac 6883 was added first, and later, an additional 408.60 g of Synolac 6883 was added for a combined total of 582.72 g Synolac 6883 resin in Base Paint 1 .Table B1 : Base Paint 1 - Synolac 6883-based white paint- 60 -55394087-5PE963326EP || 7511 -A-EPTable B2: Base Paint 2 - Urakyd HS233-based white paintTable B3: Base Paint 3 - Urakyd AD130-based white paintTable B4: Base Paint 4 - Urakyd AD10-based white paint- 61 -55394087-5PE963326EP || 7511 -A-EP

[0207] The compounds to be tested as antiskinning agents / additives were obtained from commercial sources and were used as received without further purification. In some cases, diluted solutions were made in propylene glycol (PG) or di(propylene glycol) methyl ether (DPM) to ease the addition of low amounts. In those cases, the concentration ranges for dilution used are listed in Table B, Glossary of Selected Materials, and the concentrations of antiskinning additive / agent added to a given sample is expressed in these Examples as wt. %, which expresses the amount of the pure antiskinning additive / agent in the relevant sample and disregards any diluting solvent (as explained in greater detail, below).

[0208] The formulations to be used for casting films were prepared by first mixing an alkyd binder or one of Base Paints 1-4 with the appropriate amount of a paint drier and mixing these in a speed mixer (SpeedMixer DAC 150.1 FVZ) at 2000 rounds per minute for two minutes. Appropriate drier loading content (expressed in % MORS) is provided in relation to each data set, below. In each instance, drier or drier solution was added in sufficient amount to yield the stated loading (in % MORS). Individual samples were than prepared by weighing a desired amount of compounds to be tested as antiskinning agents / additives, usually in the form of a stock solution in an organic solvent, into a plastic vial, followed by addition of the binder resin containing a paint drier or Base Paint containing a paint drier to the vial. For each sample, antiskinning agent / additive and binder resin containing a paint drier or Base Paint containing a paint drier were added in appropriate amounts to yield the desired antiskinning agent / additive loading (expressed in wt. % throughout these examples, wherein wt. % refers to the parts by weight of the antiskinning additive or antiskinning agent (pure compound, not including antiskinning additive / agent solvent weight) in addition to the parts by weight of the liquid coating composition or liquid binder resin formulation, as the case may be) and a total liquid sample mass of approximately 10 g (excluding the mass of the vial). Mixing was achieved by placing the vial into a speed mixer (SpeedMixer DAC 150.1 FVZ) at 2000 rounds per minute for two minutes.Generally, a homogeneous-looking mixture resulted. This was left under ambient conditions for 24 hours before films were coated. In general, only those formulations that did not show strong skin formation were coated. Reference or control formulations (containing drier but no antiskinning additive) were coated, regardless of the degree of skin formation, however. If a sample showed only a thin skin formation, the skin formation was removed before sample was coated.

[0209] Example Data - Measured dry times and skinning ratings

[0210] In the tables below, the amount of the antiskinning additives / agents is shown as weight % of the pure compounds (excluding any solvent in stock solutions or that introduced by intentional dilution) relative and in addition to the weight of the formulation they were added to (including solvent weight). For example, the sample paint resulting from the addition of a solution of a-Terpinene diluted in DPM to 100 g of Base Paint 1 at 1.385 wt. % would contain 1 .385 g of a-Terpinene and would weigh 101 .385 g plus some additional mass for the diluting DPM.

[0211] Testing with Iron-Based Driers- 62 -55394087-5PE963326EP || 7511 -A-EPTable 1‘Formulation was not coated due to strong skinning after one day.All experiments were performed in Base Paint 1 , containing the drier Borchi OXY-Coat at a loading of 0.0013% MORS.Table 2All experiments were performed in Base Paint 2, containing the drier Borchi OXY-Coat at a loading of 0.001% MORS.Table 3- 63 -55394087-5PE963326EP || 7511 -A-EP‘Formulation was not coated due to strong skinning after one day.All experiments were performed in Base Paint 1 , containing the drier Borchi OXY-Coat at a loading of 0.0013% MORS.Table 4All experiments were performed in a pure medium oil alkyd binder WorleeKyd S 351 , containing the drier Borchi OXY-Coat at a loading of 0.001% MORS.Table 5All experiments were performed in a short oil alkyd binder Synthalat F 334, containing the drier Borchi OXY-Coat at a loading of 0.001% MORS.Table 6All experiments were performed Base Paint 1 , containing the drier Borchi OXY-Coat at a loading of 0.0013% MORS. A1 , or Additive 1 , appears first in the corresponding “Additive” column cell for a given row, and A2, or Additive 2, appears second. Thus, A1 for Table 6, row 3 is 2PO and A2 for Table 6, row 3 is a-terpinene.55394087-5PE963326EP || 7511 -A-EPTable 7Abbreviations: All experiments were performed Base Paint 3, containing the drier Borchi OXY-Coat at a loading of 0.0004% MORS. DEHA was used in the form of Ascinin 1240 (Borchers). A1 , or Additive 1 , appears first in the corresponding “Additive” column cell for a given row, and A2, or Additive 2, appears second.

[0212] Testing with Manganese-based DriersTable 8All experiments were performed in Base Paint 2, containing the drier Dragon at a loading of 0.007% MORS.Table 9All experiments were performed Base Paint 2, containing the drier Dragon at a loading of 0.0125% MORS.- 65 -55394087-5PE963326EP || 7511-A-EPTable 10‘Formulation was not coated due to strong skinning after one day.All experiments were performed in a medium oil alkyd binder WorleeKyd S 351 , containing the drier Dragon at a loading of 0.0125% MORS. DEHA was used in the form of Ascinin 0444. A1 , or Additive 1 , appears first in the corresponding “Additive” column cell for a given row, and A2, or Additive 2, appears second.

[0213] Testing with Cobalt-Based DriersTable 11All experiments were performed Base Paint 1 , containing the drier Co / Zr 69 at a loading of 0.06% MORS Co and 0.09% MORS Zr.Table 12All experiments were performed Base Paint 1 , containing the drier Co / Zr 69 at a Co-loading of 0.06% MORS and Zr-loading of 0.09% MORS. A1 , or Additive 1 , appears first in the corresponding “Additive” column cell for a given row, and A2, or Additive 2, appears second.- 66 -55394087-5PE963326EP || 7511-A-EPTable 13‘Formulation was not coated due to strong skinning after 1 d.All experiments were performed in a medium oil alkyd binder WorleeKyd S 351 , containing the drier Deca-Co-10 at a loading of 0.05% MORS. A1 , or Additive 1 , appears first in the corresponding “Additive” column cell for a given row, and A2, or Additive 2, appears second.Table 14All experiments were performed in short oil alkyd resin Synthalat F 334, containing the drier Deca-Co- 10 at a loading of 0.05% MORS. DEHA used in the form of Ascinin 0444. A1 , or Additive 1 , appears first in the corresponding “Additive” column cell for a given row, and A2, or Additive 2, appears second.

[0214] Preferred embodiments of the subject matter of this application are described herein. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the subject matter described herein to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the present disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.- 67 -55394087-5

Claims

1. PE963326EP || 7511 -A-EPWhat is Claimed is:1 . A binder resin formulation comprising:(I) an autoxidizing binder resin; and(ii) an antiskinning additive formulation, wherein the antiskinning additive formulation comprises a compound including a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is a liquid at 23 ± 1 °C and standard pressure (1 ATM).

2. The binder resin formulation of claim 1 , wherein the compound is of Formula X-A or Formula X-B:Formula X-AFormula X-Bwherein Ri-Rs are each independently H, C1-C12 alkyl, Cs-Cu aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of Ri-Rs may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a dihydroarene moiety is polycyclic, or wherein the compound includes a methylene cyclohexene moiety of Formula Xl-C or FormulaXl-D:Formula Xl-C- 68 -55394087-5PE963326EP || 7511-A-EPFormula Xl-Dwherein R1-R7 are each independently H, C1-C12 alkyl, C6-C14 aryl, C2-C12 alkenyl, C2-C12 carboxylate derivative, -OSiRsRgR , -OR11, -NR11 R12, F, Cl, Br, or I, wherein each Rs, R9, and R10 is independently C1-C10 alkyl, wherein each Rn and R12 is independently H or C1-C10 alkyl, or any adjacent two of R1-R7 may optionally, together be C2-C12 alkanediyl or alkenediyl, such that the resulting compound including a methylene cyclohexene moiety is polycyclic.

3. The binder resin formulation of any claims 1 or 2, wherein the compound is selected from the group consisting of a-terpinene, y-terpinene, a-phellandrene, 1 ,3-cyclohexadiene, 6-terpinene (also known as terpinolene), and mixtures thereof.

4. The binder resin formulation of any claims 1 to 3, wherein the compound is selected from the group consisting of a-terpinene, y-terpinene, a-phellandrene, 1 ,3-cyclohexadiene, and mixtures thereof.

5. The binder resin formulation of any preceding claim, further comprising a transition metal compound in which the transition metal is selected from the group consisting of iron, manganese, vanadium, cobalt and copper.

6. The binder resin formulation of claim 5, wherein the transition metal is present in the binder resin formulation from about 0.0002 % MORS to about 1 .0 % MORS, wherein % MORS refers to % metal on resin solids, wherein MORS is calculated in the following way:with m<j'. mass of the drier (or drier solution if in solution), in g; MCd. metal content of the drier (or drier solution if in solution) in %; SCf. solid content (of binder, including any dissolved or dispersed solids) in the formulation, in %; and m . mass of the formulation, in g.

7. The binder resin formulation of any preceding claim, further comprising an organic ligand.- 69 -55394087-5PE963326EP || 7511 -A-EP8. The binder resin formulation of claim 7, wherein the organic ligand is a bispidon ligand ofFormula (I) or Formula (l-A):wherein: each R is independently selected from the group consisting of hydrogen, F, Cl, Br, hydroxyl, Ci-4-alkylO-, -NH-CO-H, -NH-CO-C1-4 alkyl, -NH2, -NH-C1-4 alkyl, and C1-4 alkyl;R1 and R2areindependently selected from the group consisting of Ci-24-alkyl, Ce-io-aryl, C7- 12-arylalkyl , and a group containing one or two heteroatoms (e.g. N, O or S) capable of coordinating to a transition metal;R3 and R4 are independently selected from the group consisting of hydrogen, Ci-s-alkyl, Ci-8-alkyl— O— Ci-8-alkyl , Ci-s-aryl-O-Ce-io-alkyl, Ce-io-aryl, Ci-s-hydroxyalkyl and - (CH2)nC(O)OR5 wherein R5 is selected from hydrogen, C1-12-alkyl , and C1-4- alkyl— O— Ci-4-alkyl and n is from 0 to 4;X is selected from the group consisting of C=O, -[C(R6)2]y- wherein y is from 0 to3; each R6 is independently selected from the group consisting of hydrogen, hydroxyl, C1-4 alkoxy and C1-4 alkyl; and- 70 -55394087-5PE963326EP || 7511 -A-EP each D is independently selected from the group consisting of thiazol-2-yl and thiazol-4- yh or the ligand is a N4py-type ligand of Formula (II):wherein: each R1 and R2 independently represents -R4-R5;R3 represents hydrogen, Ci-s-alkyl, aryl selected from homoaromatic monovalent groups having a molecular weight under 300, or C7-4o-arylalkyl, or-R4-R5, each R4 independently represents a single bond or a C2-i4-alkylene, C2-6- alkenylene, C2-6-oxyalkylene, C2-6-aminoalkylene, C2-6-alkenyl ether, C2-6-carboxylic ester or C2-6-carboxylic amide, and each R5 independently represents an optionally N-alkyl-substituted aminoalkyl group or an optionally alkyl-substituted heteroaryl selected from the group consisting of pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to R4 via any atom in the ring of the heteroaryl, or the ligand is a TACN-type ligand of Formula (III):wherein: each R20 is independently selected from: hydrogen, -CY2-R22, Ci -s-alkyl , Cs-s-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl;- 71 -55394087-5PE963326EP || 7511 -A-EP morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononyl; 1 ,4,8,11 - tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia- cyclononyl; 1 ,4-diaza-7-oxa-cyclononyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4- dioxanyl; 1 ,4,7-trithia-cyclononyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl is connected to the ligand via any atom in the ring of the heterocycloalkyl; heteroaryl selected from the group consisting of pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to the ligand via any atom in the ring of the heteroaryl, aryl selected from homoaromatic monovalent groups having a molecular weight under 300, or C?-4o-aryl alkyl group optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate derivative, carboxamide, sulfonate, amine, alkylamine, and N+(R21)3 ,R21 is selected from hydrogen, Ci-s-alkyl, C2-6-alkenyl, C7-4o-arylalkyl, arylalkenyl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-8-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, and C2-6-alkenyl ether,Y is independently selected from H, CH3, C2H5, C3H7; andR22 is independently selected from Ci-s-alkyl-substituted heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to the ligand via any atom in the ring of the heteroaryl, or the ligand is a cyclam or cross-bridged ligand of Formula (IV):wherein:Q is independently selected fromand55394087-5PE963326EP || 7511 -A-EPP is 4;R is independently selected from: hydrogen, Ci -6-alkyl , CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or two R moieties of two Q moieties together form an ethylene bridge; andRi , R2, R3, R4, R5 and Re are independently selected from: H, Ci -4-alkyl, and Ci-4-alkylhydroxy, or the ligand is a cross-bridged ligand of the Formula (V):wherein:R1is independently selected from H, C1-20 alkyl, C?-4o-aryl alkyl, C2-6-alkenyl or C2-6-alkynyl, or the ligand is a trispicen-type ligand of formula (VI):R17R17N-X-NR17R17 (VI), wherein:X is selected from -CH2CH2-, -CH2CH2CH2-, and -CH2C(OH)HCH2-; each R17 independently represents a group selected from: -CY2-RI 8, Ci-s-alkyl, C3-8- cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4- piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononyl; 1 ,4,8,11 -tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononyl; 1 ,4-diaza-7-oxa-cyclononyl; 1 ,4,7,10- tetraazacyclododecanyl; 1 ,4-dioxanyl; 1 ,4,7-trithia-cyclononyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl is connected via any atom in the ring of the heterocycloalkyl; heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to N via any atom in the ring of- 73 -55394087-5PE963326EP || 7511-A-EP the heteroaryl, aryl selected from homoaromatic monovalent groups having a molecular weight under 300, and C7-40 arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate derivative, carboxamide, sulfonate, amine, and alkylamine, whereinR18 is independently selected from an optionally substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl is connected to -CY2 via any atom in the ring of the heteroaryl; each Y is independently selected from H, CH3, C2H5, C3H7, or the ligand is a polymeric ligand.

9. The binder resin formulation of claim 8, wherein the organic ligand is selected from the group consisting of dimethyl-3-methyl-9-oxo-2,4-di(pyridin-2-yl)-7-(pyridin-2-ylmethyl)-3,7- diazabicyclo[3.3.1]nonane-1 ,5-dicarboxylate and 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane.

10. The binder resin formulation of any preceding claim, wherein the compound of the antiskinning additive formulation is present in the binder resin formulation from about 0.3 wt. % to about 5.0 wt. %, wherein wt. % is expressed as parts by weight antiskinning additive compound (excluding any solvent weight in the antiskinning additive formulation and, if present, the weight of any additional antiskinning agent) in addition to parts by weight liquid binder resin formulation (excluding all antiskinning additive formulation weight), expressed as a percentage.11 . The binder resin formulation of any of claims 1 to 9, wherein the antiskinning additive formulation further comprises an additional antiskinning agent selected from the group consisting of a phenol derivative, a sulphide, a phosphine, a phosphite, a phosphonite, a dioxo compound, and a hindered amine light stabilizer, and mixtures thereof.

12. The binder resin formulation of claim 11 , wherein the additional antiskinning agent is present in the binder formulation from about 0.012 wt. % to about 1 .8 wt. %, and the compound of the antiskinning additive formulation is present in the binder resin formulation from about 0.012 wt. % to about 3.6 wt. %, wherein wt. % is expressed as parts by weight antiskinning additive compound (excluding any solvent weight in the antiskinning additive formulation and additional antiskinning agent weight) or parts by weight additional antiskinning agent (excluding any solvent weight in the antiskinning additive formulation and antiskinning additive compound weight) in addition to parts by weight liquid binder resin formulation (excluding all antiskinning additive formulation weight), expressed as a percentage.- 74 -55394087-5PE963326EP || 7511 -A-EP13. A coating composition comprising the binder resin formulation of any preceding claim, wherein the autoxidizing binder resin is an alkyd binder.

14. Use of an antiskinning additive formulation as an antiskinning agent for a composition comprising an autoxidizing binder resin, wherein the antiskinning additive formulation comprises a compound including a dihydroarene moiety or a methylene cyclohexene moiety, wherein the compound is a liquid at 23 ± 1°C and standard pressure (1 ATM).

15. The use of claim 14, wherein the compound is as defined in any one of claims 2 to 4.- 75 -55394087-5

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