US 20160304747A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0304747 A1 Ang et al. (43) Pub. Date: Oct. 20, 2016

(54) DRIER COMPOSITION AND USE THEREOF (52) U.S. Cl. CPC ...... C09F 9/00 (2013.01); C09D 167/08 (71) Applicant: PPG EUROPE B.V., Uithoorn (NL) (2013.01) (72) Inventors: Tjian Hong Ang, Almere (NL); John Weijnen, Alphen aan den Rijn (NL) (57) ABSTRACT (21) Appl. No.: 15/101,653 The invention relates to a drier composition for an autoxi (22) PCT Filed: Dec. 3, 2014 dizable alkyd based coating composition, comprising: a) at (86). PCT No.: PCT/EP2014/076431 least one Fe complex comprising Fe and at least one nitrogen donor ligand, wherein said at least nitrogen donor ligand is S 371 (c)(1), selected from the group comprising tridentate, tetradentate, (2) Date: Jun. 3, 2016 pentadentate and hexadentate nitrogen donor ligands; b) at (30) Foreign Application Priority Data least one metal salt of a carboxylic acid, wherein the metal is selected from the group comprising: Mn, Ce, V, and Cu, Dec. 3, 2013 (EP) ...... PCT/EP2013/075430 preferably Mn; and c) at least one ligand comprising at least one moiety selected from the group comprising 14.7-tri Publication Classification azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, imi dazolyl pyrazolyl, porphyrinyl, aliphatic, cycloaliphatic, (51) Int. Cl. and aromatic amines. The present invention also relates to C09F 9/00 (2006.01) coating composition comprising the drier composition, and C09D 67/08 (2006.01) the uses thereof. US 2016/0304747 A1 Oct. 20, 2016

DRER COMPOSITION AND USE THEREOF genic materials has prompted the development of cobalt-free metal driers for alkyds. Hence there is an increasing demand FIELD OF THE INVENTION for alternative, non-cobalt based driers. 0001. The invention relates to a drier system for a coating 0006 Recently developed curing agents for air-drying composition, preferably for an autoxidizable alkyd based alkyd resins based on iron complexes containing tetraden coating composition. tate, pentadentate or hexadentate nitrogen donor ligands (as disclosed in WO2008.003652) show a highly efficient drying behavior under ambient conditions, and higher initial white BACKGROUND OF THE INVENTION ness and lower yellowing tendency compared to other 0002 Architectural, air-drying coating compositions technologies. However, these driers suffer from the disad Such as paints, lacquers and varnishes commonly comprise vantage that their catalytic activity is difficult to control three main components: an autoxidizable binder polymer, leading to untimely skin formation during storage. which is the film-forming component, a solvent, which is the 0007. A liquid coating composition containing resins carrier for the non-volatile components, and driers or sic based on unsaturated fatty acids and metal driers, when catives, which influence the drying speed of the composi exposed to air, will rapidly convert into a drying polymeric tion. Autoxidizable binder polymers can be diluted in an matrix. For the formation of Surface skin on air-drying organic solvent Such as white spirit or hydrogenated white coatings by oxidative polymerization processes oxygen is spirit. Alternatively, autoxidizable binder polymers can be required. Even in a closed container, in which the ullage (or dispersed in water. headspace) between the product surface and the closed lid is 0003) Autoxidizable alkyd resins are long-established Sufficiently large, a tough rubber-like skin on the Surface of binder polymers for film-forming coating compositions the liquid coating material will develop. Skinning in the acknowledged for their esthetic properties, low surface paint container during storage results in loss of quality and tension (which enables the wetting of and adhesion on a quantity of the coating product. Removal of the skin is both wide variety of Substrates and facilitates pigment wetting), awkward and time consuming and results in a waste of a applicability by various techniques, and cost-effectiveness. Substantial amount of paint. Moreover, the concentration of Because of these properties, alkyd resins are the most widely driers found in the skin is disproportionate and removal will used air drying binders in coating compositions. Autoxidiz lead to a prolongation of drying time of the remaining able alkyd resins comprise drying or semi-drying unsatu coating material. rated fatty acids or oils, which are generally attached to the 0008 To prevent untimely oxidative drying leading to polyester backbone of polyols and polycarboxylic acids. skinning of the alkyd paint and to improve the stability When the coating composition is applied to a substrate, the during storage anti-skinning agents are included in the drying process starts by solvent evaporation and the binder formulation. Oximes, and in particular methyl ethyl ketox polymers undergo autoxidation and Subsequently form ime (MEKO), are known to reduce skin formation consid cross-links between the polymer chains resulting in a Solid erably, particularly in alkyd formulations containing cobalt and coherently dried film. Autoxidation is a free radical based driers. Although the mechanism associated with the chain process that takes place when alkyd resins are exposed anti-skinning performance of oximes is still not accepted to air. Autoxidation is a free radical chain process which can unanimously, the prevailing hypotheses concerns the asso be subdivided into three stages: chain initiation, propaga ciation of the oxime to the free coordination sites of the tion, and termination. Once free radicals are formed, they metal carboxylate thereby Suppressing the activity of the react in a chain and convert the unsaturated moieties of catalyst. During storage in a closed container the weak metal alkyd resins in interpolymer crosslinks. The drying process Oxime complex will stay intact. However, after opening of of autoxidizable architectural coating compositions takes the can or paint application, the complex will dissociate and place at ambient temperatures ranging from 0 to 40° C. the relative volatile oxime will be released into the surround whereby the presence of oxygen is essential. Since the ing atmosphere. Without being bold on the theory, it is drying process proceeds slowly, the chemical conversion of Supposed that on an iron multidentate ligand complex there alkyd resins is habitually catalyzed by salts of metal ions as are insufficient free coordination sites left for methyl ethyl catalytic oil drying agents. These salts of metal ions act as ketoxime to associate and Suppress the catalytic activity. driers or siccatives. 0009. In WO2012093250 it was shown that MEKO as 0004. These metal salts, containing either alkaline met sole anti-skinning agent in alkyd formulations containing als, alkaline-earth metals, transition metals or rare earth iron-hexadentate ligand complex as drier, was ineffective to metals, affect the autoxidation of the binder with air and/or prevent skin formation on the Surface of the paint formula catalyze cross-linking of the unsaturated fatty acid chains. tion during storage. WO2012093250 describes the use of an The drying time can consequently be reduced from days to aqueous solution of iron salts and a polydentate accelerant hours. The presence of efficient driers is therefore essential ligand in an oxidatively curable coating formulation to for the drying of air-drying coating compositions. reduce the skin formation of such as a formulation. How 0005 Primary driers based on cobalt are the most widely ever, the example section shows that even this approach does used because of their good performance at ambient tem not provide properties similar to a traditional Co-based drier perature. However, because of the Suspected carcinogenicity system. of cobalt carboxylates it is desired to find alternative drier 0010. Substances which have been ascribed as anti-skin compounds that show an equal or even better drying per ning agents include Substituted phenols, hydroquinones, formance than that of cobalt driers and can replace cobalt aliphatic and aromatic amines, tin compounds, aZones, based driers completely in alkyd based oxidatively air C-hydroxyketones, hydroxylamines, B-dicarbonyl com drying coatings. The anticipated imminent reclassification of pounds, natural antioxidants such as tocopherol and cobalt metal and cobalt carboxylates as Class 1B carcino isoascorbates, solvents as dipentene and oximes. These US 2016/0304747 A1 Oct. 20, 2016

organic substances inhibit the reaction of the drier with colorations, which makes the use of these materials imprac atmospheric oxygen by binding the oxygen or by complex tical in cases where clear Varnishes, light colored lacquers, ing the drier metal. etc., are involved. 0011 Especially diethyl hydroxylamine and combina (0020 U.S. Pat. No. 6.224,659 discloses the use of tin(II) tions thereof have been documented for their ability to and tin(IV) carboxylates as anti-skinning agents for oxida inhibit or slow the propensity for skinning at the air-alkyd tively drying binders. Although chemically showing simi interphase. larities with metal driers, these tin carboxylates are not 0012 DE-A 1519 103 discloses the use of N,N-dialky catalytically active in the oxidatively drying process but in lated hydroxylamines Such as diethyl hydroxylamine as contrast retard the drying to an objectionable degree. anti-skinning agents. Diethyl hydroxylamine has found use 0021. Thus, there exists a need to improve the drying as an anti-skinning agent. Although diethyl hydroxyl amine performance of non-cobalt primary drier compositions while is more volatile compared to MEKO, this substance com at the same time also improving their anti-skinning proper pound binds more strongly to cobalt driers than MEKO and ties without the excessive use of additional anti-skinning as Such does not dissociate at the same rate, which results a agents. poorer drying performance. Attempts have been made to balance this negative effect by the addition of an accelerator SUMMARY OF THE INVENTION to promote the drying process. 0022. The inventors have surprisingly found that a spe 0013 U.S. Pat. No. 6,730,157 describes an anti-skinning cific combination of a selected Fe-drier and a manganese, agents composed of organic hydroxylamines and 6-dicarbo cerium, Vanadium or copper drier with specific ligands nyl compounds or organic hydroxylamines and formic acid reduces the skinning tendency of an alkyd-based coating derivatives. composition Substantially and that additional anti-skinning agent (beside an optional ketoxime) is not needed. Since 0014 WO2008127739 describes a non-oxime anti-skin additional anti-skinning agent is not required, this eliminates ning composition including an organic oxygen Scavenger as drying retardation caused by any additional anti-skinning diethylhydroxylamine and a drying accelerator as triphenyl agent. As a result, the reduced skinning tendencies are phosphite and strontium carboxylate. accompanied by concomitantly faster drying times. 0015. In US20050272841 anti-skinning agents contain 0023 The present invention provides novel drier combi ing mixtures of organic hydroxylamines as diethyl hydrox nations suitable for oxidatively air-drying alkyd based coat ylamine and alkyl amines and/or alkyl alkanolamines are ing formulations, which drier combinations show a drying disclosed. Combining the alkyl amines and/or alkyl alkano activity at least comparable or superior to cobalt based driers lamines with hydroxylamines should avoid the disadvan while simultaneously providing reduced skinning tenden tages of hydroxylamines alone as severe delays in drying cies. The present invention additionally provides alkyd and often also reduction of film hardness values. based coating compositions that comprise the aforemen 0016 WO2007027460 describes anti-skinning agents for tioned novel drier combinations. oxidatively drying coatings comprising mixtures of organic 0024. According to a first aspect, the present invention or inorganic oxygen scavengers as diethyl hydroxylamine relates to a drier composition for an autoxidizable alkyd and nitrogen-containing aromatic compounds. The nitrogen based coating composition, comprising: containing aromatic compound acts as a drier promoter for 0.025 a) at least one Fe complex comprising Fe and at the metal drier in the air drying coating. least one nitrogen donor ligand, wherein said at least 0017 US2007022910 discloses an anti-skinning agent nitrogen donor ligand is selected from the group com comprising a synergistic combination of a hydroxylamine as prising tridentate, tetradentate, pentadentate and hexa diethyl hydroxylamine and a hydroquinone. Because of the dentate nitrogen donor ligands; synergistic effect, a reduced oxygen scavenger concentration 0026 b) at least one metal salt of a carboxylic acid, allows for acceptable through drying. wherein the metal is selected from the group compris 0018. The primary drawback to these systems composed ing Mn, Ce, V, and Cu; and of organic hydroxylamines such as diethyl hydroxylamine is 0027 c) at least one ligand comprising at least one that they bind to metal driers more strongly than MEKO and moiety selected from the group comprising 14.7-tri concomitantly do not dissociate at the same rate, resulting is azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, a poorer drying performance. Also the combinations of imidazolyl, pyrazolyl, porphyrinyl, aliphatic, cycloali organic hydroxyl amines and drying accelerators or other phatic, and aromatic amines. Substances to promote the drying process and to accelerate 0028. According to a second aspect, the invention also the hardness build-up, has not led to acceptable curing times. relates to a coating composition, comprising: One of the ambitions of the paint market is to reduce the 0029 a) at least one autoxidizable alkyd based binder; down time during maintenance work and facilitate fast and reoccupation of the residence which makes that anti-skin 0030 b) a drier composition according to the first ning materials based on this technology have not been aspect of the invention. Successful because at dosing quantities where adequate 0031. According to a third aspect, the invention also anti-skinning performance is achieved, the drying perfor relates to the use of the coating composition according to the mance is Substantially compromised. second aspect in a varnish, lacquer, paint, stain, enamel, 0019 U.S. Pat. No. 2,715,072 describes 2-tertairy-alkyl printing ink or floor covering. 4-alkoxyphenol as anti-skinning agents in drying oil com 0032. According to a fourth aspect, the invention also positions. However, phenol derivatives tend to cause severe relates Substrate having applied thereon a coating composi retardation of the drying time and induce undesirable dis tion according to the second aspect. US 2016/0304747 A1 Oct. 20, 2016

0033 Preferred embodiments of the invention are dis the value to which the modifier “about” refers is itself also closed in the detailed description and appended claims. In specifically, and preferably, disclosed. the following passages different aspects of the invention are 0040. The recitation of numerical ranges by endpoints defined in more detail. Each aspect so defined may be includes all integer numbers and, where appropriate, frac combined with any other aspect or aspects unless clearly tions Subsumed within that range (e.g. 1 to 5 can include 1. indicated to the contrary. In particular, any feature indicated 2, 3, 4 when referring to, for example, a number of elements, as being preferred or advantageous may be combined with and can also include 1.5, 2, 2.75 and 3.80, when referring to, any other feature or features indicated as being preferred or for example, measurements). The recitation of end points advantageous. also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range DETAILED DESCRIPTION OF THE recited herein is intended to include all Sub-ranges Subsumed INVENTION therein. 0041 Unless otherwise defined, all terms used in disclos 0034. When describing the compositions of the inven ing the invention, including technical and Scientific terms, tion, the terms used are to be construed in accordance with have the meaning as commonly understood by one of the following definitions, unless a context dictates other ordinary skill in the art to which this invention belongs. By wise. means of further guidance, definitions for the terms used in 0035. As used in the specification and the appended the description are included to better appreciate the teaching claims, the singular forms “a”, “an,” and “the include both of the present invention. All publications referenced herein singular and plural referents unless the context clearly are incorporated by reference thereto. dictates otherwise. By way of example, “a binder” means 0042. As used herein the term “nitrogen-donor ligand’ or one binder or more than one binder. “ligand’ or “L” is an organic structure or molecule which 0036. The terms “comprising”, “comprises” and “com will Support coordinating nitrogen atoms. In the present prised of as used herein are synonymous with “including. invention, said at least one nitrogen-donor ligand is selected “includes” or “containing”, “contains, and are inclusive or from the group comprising tridentate, tetradentate, penta open-ended and do not exclude additional, non-recited dentate and hexadentate nitrogen donor ligands. members, elements or method steps. The terms "compris 0043. Whenever the term “substituted is used herein, it ing”, “comprises' and “comprised of also include the term is meant to indicate that one or more hydrogens on the atom “consisting of. indicated in the expression using “substituted” is replaced 0037. As used herein, the term “and/or,” when used in a with a selection from the indicated group, provided that the list of two or more items, means that any one of the listed indicated atoms normal valency is not exceeded, and that items can be employed by itself or any combination of two the Substitution results in a chemically stable compound, i.e. or more of the listed items can be employed. For example, a compound that is sufficiently robust to survive isolation if a list is described as comprising group A, B, and/or C, the from a reaction mixture. list can comprise A alone; B alone; C alone; A and B in 0044) Where groups can be substituted, such groups may combination; A and C in combination, B and C in combi be substituted with one or more, and preferably one, two or nation; or A, B, and C in combination. three substituents. Substituents may be selected from but not 0038 Reference throughout this specification to “one limited to, for example, the group comprising halogen; embodiment' or “an embodiment’ means that a particular Calkyl, haloCalkyl, haloCalkyloxy; hydroxyl, feature, structure or characteristic described in connection hydroxyC-alkyl, amino, aminoCalkyl, and carboxyl. with the embodiment is included in at least one embodiment 0045. The term “hydroxyl or “hydroxy” as used herein of the present invention. Thus, appearances of the phrases refers to the group —OH. “in one embodiment’ or “in an embodiment” in various 0046. The term “carboxy” or “carboxyl or “hydroxycar places throughout this specification are not necessarily all bonyl as used herein refers to the group —C(=O)CH. referring to the same embodiment, but may. Furthermore, 0047. The term “alkyl, as a group or part of a group, the particular features, structures or characteristics may be refers to a hydrocarbyl group of Formula —CH combined in any Suitable manner, as would be apparent to a wherein n is a number of at least 1. Alkyl groups may be person skilled in the art from this disclosure, in one or more linear, or branched and may be substituted as indicated embodiments. Furthermore, while some embodiments herein. Generally, the alkyl groups comprise from 1 to 24 described herein include some but not other features carbon atoms, preferably from 1 to 12 carbon atoms, pref included in other embodiments, combinations of features of erably from 1 to 10 carbon atoms, preferably from 1 to 6 different embodiments are meant to be within the scope of carbon atoms, more preferably 1, 2, 3, 4, 5, 6 carbon atoms. the invention, and form different embodiments, as would be When a subscript is used herein following a carbon atom, the understood by those in the art. subscript refers to the number of carbon atoms that the 0039. The term “about” as used herein when referring to named group may contain. For example, the term "C. a measurable value Such as a parameter, an amount, a 24alkyl, as a group or part of a group, refers to a hydro temporal duration, and the like, indicate that a value includes carbyl group of Formula —CH2 wherein n is a number the standard deviation of error for the device or method ranging from 1 to 24. Thus, for example, Calkyl groups being employed to determine the value. Preferably the term include all linear, or branched alkyl groups having 1 to 24 “about is meant to encompass variations of +/-10% or less, carbon atoms, and thus includes for example methyl, ethyl, preferably +/-5% or less, more preferably +/-1% or less, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers and still more preferably +/-0.1% or less of and from the (e.g. n-butyl, i-butyl and t-butyl); penty1 and its isomers, specified value, insofar Such variations are appropriate to hexyl and its isomers, heptyl and its isomers, octyl and its perform in the disclosed invention. It is to be understood that isomers, nonyl and its isomers, decyl and its isomers, US 2016/0304747 A1 Oct. 20, 2016 undecyl and its isomers, dodecyl and its isomers, tridecyl lamino, ethylmethylamino, methyl-n-propylamino, methyl and its isomers, tetradecyl and its isomers, pentadecyl and its i-propylamino, n-butylmethylamino, i-butylmethylamino, isomers, hexadecyl and its isomers, heptadecyl and its t-butylmethylamino, ethyl-n-propylamino, ethyl-i-propy isomers, octadecyl and its isomers, nonadecyl and its iso lamino, n-butylethylamino, i-butylethylamino, t-butylethyl mers, icosyl and its isomers, and the like. For example, amino, di-n-butylamino, di-i-butylamino, methylpenty Calkyl includes all linear, or branched alkyl groups lamino, methylhexylamino, ethylpentylamino, having 1 to 12 carbon atoms, and thus includes for example ethylhexylamino, propylpentylamino, propylhexylamino, methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and and the like. its isomers (e.g. n-butyl, i-butyl and t-butyl); penty1 and its 0053. The term "aminoCalkyl, as a group or part of a isomers, hexyl and its isomers, heptyl and its isomers, octyl group, refers to a group of formula—R NR'R' wherein R and its isomers, nonyl and its isomers, decyl and its isomers is Calkylene, R is hydrogen or C-alkyl as defined and the like. For example, Calkyl includes all linear, or herein, and R is hydrogen or C-alkyl as defined herein. branched alkyl groups having 1 to 6 carbon atoms, and thus 0054 The terms “CalkylaminoCalkyl or “mono- or includes for example methyl, ethyl, n-propyl, i-propyl. di-CalkylaminoCalkyl, as a group or part of a group, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl refers to a group of formula - R N(R')(R) wherein R' and t-butyl); penty1 and its isomers, hexyl and its isomers. and R are each independently selected from hydrogen, or 0048. When the suffix "ene' is used in conjunction with Calkyl, wherein at least one of R' or R is Calkyl and an alkyl group, i.e. 'alkylene', this is intended to mean the R’ is C-alkylene. alkyl group as defined herein having two single bonds as 0055. The term “cycloalkyl, as a group or part of a points of attachment to other groups. As used herein, the group, refers to a cyclic alkyl group, that is a monovalent, term "Calkylene', by itself or as part of another sub saturated, hydrocarbyl group having 1 or more cyclic struc stituent, refers to C-alkyl groups that are divalent, i.e., ture, and comprising from 3 to 12 carbon atoms, more with two single bonds for attachment to two other groups. preferably from 3 to 9 carbon atoms, more preferably from Alkylene groups may be linear or branched and may be 3 to 6 carbon atoms, still more preferably from 5 to 6 carbon Substituted as indicated herein. Non-limiting examples of atoms. Cycloalkyl includes all saturated hydrocarbon groups alkylene groups include methylene (-CH2—), ethylene containing 1 or more rings, including monocyclic or bicyclic (—CH2—CH2—), methylmethylene (-CH(CH)—), groups. The further rings of multi-ring cycloalkyls may be 1-methyl-ethylene (-CH(CH) CH ), n-propylene either fused, bridged and/or joined through one or more (—CH2—CH2—CH2—), 2-methylpropylene (-CH2—CH spiro atoms. When a subscript is used herein following a (CH)—CH ), 3-methylpropylene ( CH, CH, CH carbon atom, the subscript refers to the number of carbon (CH)—), n-butylene (-CH CH2—CH2—CH2—), atoms that the named group may contain. For example, the 2-methylbutylene (—CH2—CH(CH)—CH2—CH2—), term “Cecycloalkyl, a cyclic alkyl group comprising from 4-methylbutylene (—CH2—CH2—CH2—CH(CH)—), 3 to 6 carbon atoms, more preferably from 5 to 6 carbon pentylene and its chain isomers, hexylene and its chain atoms. Examples of Cecycloalkyl groups include but are isomers, heptylene and its chain isomers, octylene and its not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclo chain isomers, nonylene and its chain isomers, decylene and hexyl. Cycloalkyl groups may also be considered to be a its chain isomers, undecylene and its chain isomers, dode subset of homocyclic rings discussed hereinafter. When the cylene and its chain isomers. Suffix "ene' is used in conjunction with a cycloalkyl group, 0049. When the term “alkyl is used as a suffix following i.e. cycloalkylene, this is intended to mean the cycloalkyl another term, as in “hydroxyalkyl, this is intended to refer group as defined herein having two single bonds as points of to an alkyl group, as defined above, being Substituted with attachment to other groups. Non-limiting examples of “C. one or two (preferably one) substituent(s) selected from the 6cycloalkylene' include 12-cyclopropylene, 1,1-cyclopro other, specifically-named group, also as defined herein. The pylene, 1,1-cyclobutylene, 1.2-cyclobutylene, 1.3-cyclopen term “hydroxyCisalkyl therefore refers to a R* OH tylene, 1,1-cyclopentylene, and 1.4-cyclohexylene. group wherein R is Cisalkylene as defined herein. 0056. The term “C-cycloalkenyl', as a group or part of 0050. The term "Calkoxy' or “Calkyloxy’, as a a group, refers to a non-aromatic mono- or multicyclic group or part of a group, refers to a group having the hydrocarbyl substituent having the indicated number of Formula -OR wherein R is Calkyl as defined herein carbon atoms and containing at least one carbon-carbon above. Non-limiting examples of Suitable Calkoxy double bond. Non-limiting examples of cycloalkenyl include methoxy, ethoxy, propoxy, isopropoxy, butoxy, include cyclopentenyl, cyclopentadienyl, cyclohexenyl, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and hexyloxy. cyclohexadienyl, cycloheptenyl, cycloheptadienyl, cyclo 0051. The term “amino” refers to the group - NH. heptatrienyl, cyclooctenyl, cyclooctadienyl, cyclooctatrie 0052. The terms “Calkylamino” or “mono- or di-C. nyl, cyclooctatetraenyl, cyclononenyl, cyclononadienyl, 6alkylamino', as a group or part of a group, refers to a group cyclodecenyl, cyclodekadienyl and the like. of formula - N(R')(R) wherein R* and R are each inde 0057 The term "Caryl', as a group or part of a group, pendently selected from hydrogen, or Calkyl, wherein at refers to a polyunsaturated, aromatic hydrocarbyl group least one of R' or R is Calkyl. Thus, alkylamino include having a single ring (i.e. phenyl) or multiple aromatic rings mono-alkyl amino group (e.g. mono-Calkylamino group fused together (e.g. naphthalene), or linked covalently, typi Such as methylamino and ethylamino), and di-alkylamino cally containing 6 to 12 atoms; wherein at least one ring is group (e.g. di-Calkylamino group such as dimethylamino aromatic. The aromatic ring may optionally include one to and diethylamino). Non-limiting examples of Suitable alky two additional rings (either cycloalkyl, heterocyclyl or het lamino groups include n-propylamino, isopropylamino, eroaryl) fused thereto. Examples of suitable aryl include n-butylamino, i-butylamino, Sec-butylamino, t-butylamino, Coaryl, more preferably Cesaryl. Non-limiting examples pentylamino, n-hexylamino, di-n-propylamino, di-i-propy of Caryl comprise phenyl, biphenylyl, biphenylenyl, or US 2016/0304747 A1 Oct. 20, 2016

1- or 2-naphthanelyl; 5- or 6-tetralinyl, 1-, 2-, 3-, 4-, 5-, 6-, prising one or more carbon-carbon triple bonds and com 7- or 8-aZulenyl, 4-, 5-, 6 or 7-indenyl, 4- or 5-indanyl, 5-, prising from 2 to 24 carbon atoms. For example, Coalky 6-, 7- or 8-tetrahydronaphthyl, 1,2,3,4-tetrahydronaphthyl, nyl includes all linear, or branched alkynyl groups having 2 and 1,4-dihydronaphthyl. When the suffix "ene' is used in to 10 carbon atoms. For example, C-alkynyl includes all conjunction with an aryl group, this is intended to mean the linear, or branched alkynyl groups having 2 to 6 carbon aryl group as defined herein having two single bonds as atoms. Non limiting examples of Calkynyl groups include points of attachment to other groups. Suitable arylene ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 2-pentynyl and groups include 1.4-phenylene, 1.2-phenylene, 1,3-phe its chain isomers, 2-hexynyl and its chain isomers, and the nylene, biphenylylene, naphthylene, indenylene, and the like. Where alkynyl groups as defined herein are divalent like. Where a carbon atom in an aryl group is replaced with groups having single bonds for attachment to two other a heteroatom, the resultant ring is referred to herein as a groups, they are termed “alkynylene'. heteroaryl ring. 0064. As used herein, the term "heteroalkyl refers to an 0058. The term "CaryleneC-alkylene', as a group or alkyl group containing one or more S, N, O, P, or Si atoms, part of a group, refers to a group having the Formula meaning an alkyl as defined herein which comprises one or —R R' wherein R is Carylene as defined herein more heteroatoms in the hydrocarbon chain, whereas the and R is Calkylene as defined herein. heteroatoms may be positioned at the beginning of the 0059. The term "CarylC-alkyl, as a group or part hydrocarbon chain, in the hydrocarbon chain or at the end of of a group, means a C-alkyl as defined herein, wherein at the hydrocarbon chain. Examples of heteroalkyl include least one hydrogen atom is replaced by at least one Caryl alkoxy, alkoxyalkyl, alkylamino, alkylaminoalkyl, alkylthio. as defined herein. Non-limiting examples of CarylC. alkylthioalkyl, Such as methoxy, methylthio, ethoxy, 12alkyl group include benzyl, phenethyl, dibenzylmethyl, propoxy, CH-O-CH2—, CH, S -CH2—, CH methylphenylmethyl, 3-(2-naphthyl)-butyl, and the like. CH, O CH CH-NH (CH)N (CH)— 0060. The term “aralkyl as a group or part of a group CH-NHCH-CH , among many other examples. refers to an aryl-substituted alkyl radical, for example to a 0065. The term “halo' or “halogen as a group or part of CarylC-alkyl as described above. When a subscript is a group is generic for fluoro, chloro, bromo, and iodo, used herein following a carbon atom, the Subscript refers to preferably to F, Cl, Br, and I, more preferably to F, Cl, and the number of carbon atoms that the named group may Br. contain. 0066. The term “haloCalkyl” as a group or part of a 0061 The term "CalkylCaryl” as a group or part of group, refers to a C-alkyl group having the meaning as a group, refers to a Coaryl group as defined herein, defined above wherein one or more hydrogens are replaced wherein a hydrogen atom is replaced by a Calkyl as with one or more halogen as defined above. Non-limiting defined herein. The term "alkaryl' as a group or part of a examples of Such haloalkyl groups include chloromethyl, group refers to an alkyl-substituted aryl radical, for example 1-bromoethyl, fluoromethyl, difluoromethyl, trifluorom to a C-alkylCaryl as described above. When a subscript ethyl, 1,1,1-trifluoroethyl and the like. is used herein following a carbon atom, the Subscript refers 0067. The term “haloCalkoxy’, as a group or part of a to the number of carbon atoms that the named group may group, refers to a group of Formula—O R' wherein R is contain. haloCalkyl as defined herein. Non-limiting examples of 0062. The term “alkenyl as a group or part of a group, suitable haloCalkoxy include fluoromethoxy, difluo refers to an unsaturated hydrocarbyl group, which may be romethoxy, trifluoromethoxy, 2.2.2-trifluoroethoxy, 1.1.2.2- linear, or branched, comprising one or more carbon-carbon tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-dif double bonds. When a subscript is used herein following a luoroethoxy, 2.2.2-trichloroethoxy, trichloromethoxy, carbon atom, the subscript refers to the number of carbon 2-bromoethoxy, pentafluoroethyl, 3,3,3-trichloropropoxy, atoms that the named group may contain. For example, the 4,4,4-trichlorobutoxy. term "Calkenyl refers to an unsaturated hydrocarbyl 0068. The term “ether includes both mono and group, which may be linear, or branched comprising one or polyethers and refers to groups having a chain containing more carbon-carbon double bonds and comprising from 2 to carbon and oxygen and each of these units preferably 24 carbon atoms. For example, Coalkenyl includes all comprises 1 to 12 carbons for each oxygen atom. Examples linear, or branched alkenyl groups having 2 to 10 carbon are dimethyl, diethyl and dipropyl ethers, polyethyleneox atoms. For example, Calkenyl includes all linear, or ide, polyprolyleneoxide, polyethelene glycol, polybutelene branched alkenyl groups having 2 to 6 carbon atoms. oxide. Examples of alkenyl groups are ethenyl, 2-propenyl, 2-bute 0069. The term “C-alkyl ether as a group or part of a nyl, 3-butenyl, 2-pentenyl and its isomers, 2-hexenyl and its group, encompasses C-12alkoxyC-12alkyl, and refers to a isomers, 2.4-pentadienyl. and the like. Where alkenyl groups group having the Formula R'-O-R' wherein R' is as defined herein are divalent groups having single bonds for C-12alkyl as defined herein, and R' is C-12alkylene. The attachment to two other groups, they are termed 'alk term “C-alkyl ether refers to a group having the Formula enylene'. R O R” wherein R is Calkyl as defined herein, 0063. The term “alkynyl by itself or as part of another and R' is Calkylene. Substituent, refers to an unsaturated hydrocarbyl group, 0070 The term "Calkyl ether” as a group or part of a which may be linear, or branched, comprising one or more group, refers to a group having the Formula - R O R' carbon-carbon triple bonds. When a subscript is used herein wherein R is Calkenyl as defined herein, and R is following a carbon atom, the subscript refers to the number C-12alkylene; or wherein R is C-12alkyl as defined of carbon atoms that the named group may contain. For herein, and R is Calkenylene, or wherein R is example, the term "C-2-alkynyl refers to an unsaturated Calkenyl as defined herein, and R is C-12alkenylene. hydrocarbyl group, which may be linear, or branched com The term "Calkenyl ether as a group or part of a group US 2016/0304747 A1 Oct. 20, 2016 refers to a group having the Formula - R O R' indolyl, indolizinyl, isoindolyl, benzofuranyl, isobenzofura wherein R is Coalkenyl as defined herein, and R is nyl, benzothiophenyl, isobenzothiophenyl, indazolyl, benz Calkylene; or wherein R is Calkyl as defined herein, imidazolyl, 1,3-benzoxazolyl, 1.2-benzisoxazolyl, 2.1-ben and R is Calkenylene, or wherein R is Calkenyl as Zisoxazolyl, 1,3-benzothiazolyl, 1,2-benzoisothiazolyl, 2.1- defined herein, and R' is Calkenylene. benzoisothiazolyl, benzotriazolyl, 1,2,3-benzoxadiazolyl, 0071. The term "Calkylthio', as a group or part of a 2,1,3-benzoxadiazolyl, 1,2,3-benzothiadiazolyl, 2,1,3-ben group, refers to a group having the Formula – S R Zothiadiazolyl, thienopyridinyl, purinyl, imidazol-2-a wherein R is Calkyl as defined herein above. Non pyridinyl, 6-oxo-pyridazin-1 (6H)-yl, 2-oxopyridin-1 (2H)- limiting examples of Calkylthio groups include methyl y1, 6-oxo-pyridazin-1 (6H)-yl, 2-oxopyridin-1 (2H)-yl, 1,3- thio ( SCH), ethylthio ( SCHCH), n-propylthio, iso benzodioxolyl, quinolinyl, isoquinolinyl, cinnolinyl, propylthio, n-butylthio, isobutylthio, sec-butylthio, tert quinazolinyl, quinoxalinyl; preferably said heteroaryl group butylthio, and the like. is selected from the group consisting of pyridyl, pyrazinyl, 0072. The terms “heterocycloakyl” or "heterocyclyl” or pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl pyrimidi "heterocyclo', as a group or part of a group, refer to nyl, triazolyl and thiazolyl. non-aromatic, fully saturated or partially unsaturated cyclic (0075. The term “pyrrolyl” (also called azolyl) as used groups (for example, 3 to 7 member monocyclic, 7 to 11 herein includes pyrrol-1-yl, pyrrol-2-yl and pyrrol-3-yl. The member bicyclic, or containing a total of 3 to 10 ring atoms) term “furanyl' (also called “furyl') as used herein includes which have at least one heteroatom in at least one carbon furan-2-yl and furan-3-yl (also called furan-2-yl and furan atom-containing ring. Each ring of the heterocyclic group 3-yl). The term “thiophenyl' (also called “thienyl) as used containing a heteroatom may have 1, 2, 3 or 4 heteroatoms herein includes thiophen-2-yl and thiophen-3-yl (also called selected from N, O and/or S, where the N and Sheteroatoms thien-2-yl and thien-3-yl). The term "pyrazolyl (also called may optionally be oxidized and the N heteroatoms may 1H-pyrazolyl and 1,2-diazolyl) as used herein includes pyra optionally be quaternized. The heterocyclic group may be Zol-1-yl, pyrazol-3-yl pyrazol-4-yl and pyrazol-5-yl. The attached at any heteroatom or carbon atom of the ring or ring term “imidazolyl as used herein includes imidazol-1-yl, system, where valence allows. The rings of multi-ring het imidazol-2-yl, imidazol-4-yl and imidazol-5-yl. The term erocycles may be fused, bridged and/or joined through one “oxazolyl (also called 1.3-oxazolyl) as used herein includes or more spiro atoms. oxazol-2-yl: oxazol-4-yl and oxazol-5-yl. The term “isox 0073. Non limiting exemplary heterocyclic groups azolyl (also called 1.2-oxazolyl), as used herein includes include aziridinyl, oxiranyl, thiranyl, piperidinyl, azetidi isoxazol-3-yl, isoxazol-4-yl, and isoxazol-5-yl. The term nyl, 2-imidazolinyl, pyrazolidinyl imidazolidinyl, isoxazoli “thiazolyl (also called 1,3-thiazolyl), as used herein nyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazo includes thiazol-2-yl, thiazol-4-yl and thiazol-5-yl (also lidinyl, piperidinyl, succinimidyl, 3H-indolyl, indolinyl, called 2-thiazolyl, 4-thiazolyl and 5-thiazolyl). The term isoindolinyl, 2H-pyrrolyl, 1-pyrrolinyl, 2-pyrrolinyl, 3-pyr “isothiazolyl (also called 1,2-thiazolyl) as used herein rolinyl, pyrrolidinyl, 4H-quinolizinyl, 2-oxopiperazinyl, includes isothiazol-3-yl, isothiazol-4-yl, and isothiazol-5-yl. piperazinyl, homopiperazinyl, 2-pyrazolinyl, 3-pyrazolinyl, The term “triazolyl as used herein includes 1H-triazolyl tetrahydro-2H-pyranyl, 2H-pyranyl, 4H-pyranyl, 3,4-di and 4H-1,2,4-triazolyl, "1H-triazolyl includes 1H-1,2,3- hydro-2H-pyranyl, oxetanyl, thietanyl, 3-dioxolanyl, 1,4- triazol-1-yl, 1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, dioxanyl. 2,5-dioximidazolidinyl, 2-oxopiperidinyl, 2-ox 1H-1,2,4-triazol-1-yl, 1H-1,2,4-triazol-3-yl and 1H-1,2,4- opyrrolodinyl, indolinyl, tetrahydropyranyl. triazol-5-yl. “4H-1,2,4-triazolyl includes 4H-1,2,4-triazol tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydroquinoli 4-yl, and 4H-1,2,4-triazol-3-yl. The term “oxadiazolyl as nyl, tetrahydroisoquinolin-1-yl, tetrahydroisoquinolin-2-yl, used herein includes 1.2.3-oxadiazol-4-yl, 1.2.3-oxadiazol tetrahydroisoquinolin-3-yl, tetrahydroisoquinolin-4-yl, thio 5-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,5-ox morpholin-4-yl, thiomorpholin-4-ylsulfoxide, thiomorpho adiazol-3-yl and 1,3,4-oxadiazol-2-yl. The term “thiadiaz lin-4-ylsulfone, 1,3-dioxolanyl, 1,4-oxathianyl, 1,4-dithi olyl as used herein includes 1,2,3-thiadiazol-4-yl, 1,2,3- anyl, 1,3,5-trioxanyl, 1 H-pyrrolizinyl, tetrahydro-1,1- thiadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, dioxothiophenyl, N-formylpiperazinyl, and morpholin-4-yl. 1,2,5-thiadiazol-3-yl (also called furazan-3-yl) and 1,3,4- 0074 The term "heteroaryl as a group or part of a group, thiadiazol-2-yl. The term “tetrazolyl as used herein refers but is not limited to 5 to 12 carbon-atom aromatic includes 1H-tetrazol-1-yl, 1H-tetrazol-5-yl, 2H-tetrazol-2- rings or ring systems containing 1 to 2 rings which are fused y1, and 2H-tetrazol-5-yl. The term “oxatriazolyl as used together or linked covalently, typically containing 5 to 6 herein includes 1,2,3,4-oxatriazol-5-yl and 1,2,3,5-oxatri atoms; at least one of which is aromatic in which one or azol-4-yl. The term “thiatriazolyl as used herein includes more carbon atoms in one or more of these rings can be 1,2,3,4-thiatriazol-5-yl and 1,2,3,5-thiatriazol-4-yl. The replaced by N, O and/or S atoms where the N and S term "pyridinyl (also called “pyridyl') as used herein heteroatoms may optionally be oxidized and the N heteroa includes pyridin-2-yl, pyridin-3-yl and pyridin-4-yl (also toms may optionally be quaternized. Such rings may be called 2-pyridyl, 3-pyridyl and 4-pyridyl). The term "pyrim fused to an aryl, cycloalkyl, heteroaryl or heterocyclyl ring. idyl as used herein includes pyrimid-2-yl, pyrimid-4-yl, Non-limiting examples of such heteroaryl, include: pyrrolyl, pyrimid-5-yl and pyrimid-6-yl. The term "pyrazinyl as furanyl, thiophenyl, pyrazolyl, imidazolyl, oxazolyl, isox used herein includes pyrazin-2-yl and pyrazin-3-yl. The azolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadi term "pyridazinyl as used herein includes pyridazin-3-yl and azolyl, tetrazolyl, Oxatriazolyl, thiatriazolyl pyridinyl, pyridazin-4-yl. The term “oxazinyl (also called “1,4-oxazi pyrimidyl, pyrazinyl, pyridazinyl, oxazinyl, dioxinyl, thiazi nyl) as used herein includes 1,4-oxazin-4-yl and 1.4-OX nyl, triazinyl, imidazo[2,1-b1,3thiazolyl, thieno 3.2-b azin-5-yl. The term “dioxinyl (also called "1,4-dioxinyl) furanyl, thieno 3.2-bithiophenyl, thieno2.3-d1.3thiaz as used herein includes 1,4-dioxin-2-yl and 1,4-dioxin-3-yl. olyl, thieno2,3-dimidazolyl, tetrazolo 1.5-alpyridinyl, The term “thiazinyl (also called "14-thiazinyl) as used

US 2016/0304747 A1 Oct. 20, 2016

( N=N+=N ), formyl ( C(=O)—H), thioformyl ( C I0084) wherein R' is selected from the group consisting (=S)—H), amino ( NH), mono- and di-(Calkyl)- of Calkyl, Coaryl, heteroaryl, heteroarylC. Substituted amino, mono- and di-(Coaryl)-substituted 6alkyl, and CalkylaminoCalkyl, wherein het amino, Calkylamido (-NH-C(=O)-alkyl), Cary eroaryl is selected from the group consisting of pyridyl, lamido ( NH C(=O)-aryl), imino ( CR =NH wherein pyrazinyl, pyrazolyl pyrrolyl, imidazolyl, benzimida R is hydrogen, C2-alkyl, C-2 oaryl, C-2 alkaryl, zolyl pyrimidinyl, triazolyl and thiazolyl, preferably Coaralkyl, etc.), C-alkylimino (-CR'—N(Calkyl). pyriddin-2yl; wherein R' is optionally substituted with wherein R is hydrogen, C-2-alkyl, C-2aryl, C-2alkaryl, one or more Substituents, each independently selected etc.), Coarylimino (—CR'—N(Caryl), wherein R is from the group consisting of Calkyl, Coaryl, hydrogen, C2-alkyl, C-2aryl, C-2alkaryl, etc.), nitro Co-oarylCoalkyl: ( NO), nitroso ( NO), sulfo (—SO OH), sulfonato (—SO O—), C-alkylsulfanyl ( S-C alkyl; also I0085 R is selected from the group consisting of termed “Calkylthio'), arylsulfanyl (—S-aryl; also C-2-alkyl, Co-oaryl, heteroaryl, heteroarylCgalkyl, termed “arylthio'), C-alkylsulfinyl (—(SO)—C-alkyl). and CalkylaminoCalkyl, wherein heteroaryl is Coarylsulfinyl ( (SO)—Caryl), C-alkylsulfonyl Selected from the group consisting of pyridyl, pyrazi (—SO, C-alkyl). Carylsulfonyl (—SO C. nyl, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl, 2Oaryl), phosphono ( -P(O)(OH)), phosphonato ( P(O) pyrimidinyl, triazolyl and thiazolyl, preferably pyrid (O—)), phosphinato (-P(O)(O—)), phospho ( PO), and din-2yl; wherein R is optionally substituted with one phosphino ( PH), mono- and di-(Calkyl)-substituted or more Substituents, each independently selected from phosphino, and mono- and di-(Caryl)-substituted phos the group consisting of C-12alkyl, Co-oaryl, phino. Co-oarylCoalkyl: 0077. The terms described above and others used in the I0086) R is selected from the group consisting of H, specification are well understood to those in the art. Calkyl, C-alkyl-O-C-alkyl, C-alkyl-O- 0078 Preferred statements (features), and embodiments Co-oaryl, Co-oaryl, hydroxyC-12alkyl, and -(CH2) of the compounds and processes of this invention are now set forth. Each statement and embodiment of the invention C(O)OR; wherein R is selected from -H, so defined may be combined with any other statement and/or Calkyl, Co-oaryl, or CalkylCoaryl, and wherein embodiment unless clearly indicated to the contrary. In m is an integer selected from 0, 1, 2, 3, or 4, wherein particular, any feature indicated as being preferred or advan R is optionally substituted with one or more substitu tageous may be combined with any other feature or features ents, each independently selected from the group con indicated as being preferred or advantageous. Hereto, the sisting of Coalkyl, Co-oaryl, halogen, Calkoxy, present invention is in particular captured by any one or any haloCalkyl, and haloCalkoxy; combination of one or more of the below numbered aspects I0087 R is selected from the group consisting of H, and embodiments 1 to 27, with any other statement and/or Calkyl, C-alkyl-O-C-alkyl, C-alkyl-O- embodiments. Coaryl, Coaryl, hydroxyC-alkyl, and -(CH2) 0079 1. A drier composition for an autoxidizable alkyd C(O)OR; wherein R is selected from -H, based coating composition, comprising: Calkyl, Co-oaryl, or CalkylCoaryl, and wherein 0080 a) at least one Fe complex comprising Fe and at m is an integer selected from 0, 1, 2, 3, or 4, wherein least one nitrogen donor ligand, wherein said at least R" is optionally substituted with one or more substitu nitrogen donor ligand is selected from the group com ents, each independently selected from the group con prising tridentate, tetradentate, pentadentate and hexa sisting of C-galkyl, Co-oaryl, halogen, Calkoxy, dentate nitrogen donor ligands; haloCalkyl, and haloCalkoxy: I0081 b) at least one metal salt of a carboxylic acid, I0088 R is selected from the group consisting of H, wherein the metal is selected from the group compris halogen, —OH, Calkoxy, —NH-C(O)—H. ing: Mn, Ce, V, and Cu; and —NH C(O)—C-alkyl, - NH, -NH. C. 0082 c) at least one ligand comprising at least one 12alkyl, and C2alkyl; wherein R is optionally sub moiety selected from the group comprising 14.7-tri stituted with one or more Substituents, each indepen azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, dently selected from the group consisting of Calkyl, imidazolyl pyrazolyl, porphyrinyl, aliphatic, cycloali Co-oaryl, halogen, Cigalkoxy, haloC-alkyl, and phatic, and aromatic amines. haloCalkoxy; 0083. 2. A drier composition according to statement 1, I0089 R is selected from the group consisting of H, wherein the ligand in a) is a compound of formula (I); halogen, —OH, Calkoxy, —NH-C(O)—H. —NH CO) C-alkyl, - NH, -NH C. 12alkyl, and C2alkyl; wherein R is optionally sub (I) stituted with one or more Substituents, each indepen dently selected from the group consisting of Calkyl, Coaryl, halogen, Calkoxy, haloCalkyl, and haloCalkoxy; 0090 X is selected from –C(O) or -C(R) ; wherein n is an integer selected from 0, 1, 2 or 3, and each R is independently selected from the group con sisting of —H. —OH, Calkoxy and C-alkyl: wherein R is optionally substituted with one or more substituents, each independently selected from the group consisting of C1-alkyl, C-aryl, halogen, Calkoxy, haloCalkyl, and haloCalkoxy. US 2016/0304747 A1 Oct. 20, 2016

0091 3. A drier composition according to statement 1 or 0100 7. The drier composition according to any one of 2, wherein the ligand in a) is a compound of formula (I); statements 1 to 6, wherein the at least one ligand in c) is a compound of formula (V), wherein (I) (V)

0101 each R' is independently selected from the group consisting of Calkyl, C-scycloalkyl, hetero 0092 wherein R' and R are each independently cycloalkyl, heteroaryl, Coaryl and Coaryl-C- Selected from the group consisting of Calkyl, 6alkyl, each group being optionally Substituted with Coaryl, heteroaryl, heteroarylCalkyl, and one or more Substituents each independently selected CalkylaminoCalkyl, wherein heteroaryl is from the group consisting of —OH, Calkoxy, phe Selected from the group consisting of pyridyl, pyrazi noxy, carboxylate, carboxamide, carboxylic ester, Sul nyl, and pyrazolyl; fonate, amine, C-calkylamine and —N"(R'); 0093. Rand Rare each independently selected from the group consisting of —H, Cisalkyl, Csalkyl-O- 0102 each R is selected from H. Calkyl, Cisalkyl, Cisalkyl-O Coaryl, Co-oaryl, C2-alkenyl, Co-oaryl-C-6alkyl, Co-oaryl-C2-alk hydroxyCisalkyl, and —(CH),C(O)CR: R is enyl, Calkyloxy, Calkenyloxy, aminoCalkyl, selected from —H. Calkyl, Caryl, or aminoCalkenyl, C2-alkyl ether, Calkenyl ether, Calky1C-aryl, and m is an integer selected from 0. and –CX-R’; 1, 2, 3, or 4: (0103 each X* is independently selected from —H or (0094) each Rand R7 are independently selected from Calkyl and wherein each R’ is independently the group consisting of —H. —F. —Cl. —Br. —OH, selected from an optionally substituted heteroaryl Calkoxy, NH C(O) H, NH-C(O) C. group selected from the group consisting of pyridyl, 4alkyl, -NH2, —NH-Calkyl, and Calkyl, and, pyrazinyl, pyrazolyl pyrrolyl, imidazolyl, benzimida 0095 X is selected from C(O)– or -C(R) ; Zolyl, pyrimidinyl, triazolyl and thiazolyl; and, wherein n is an integer selected from 0, 1, 2 or 3, and each R is independently selected from the group con 0104 wherein at least one of R is C(X) R', sisting of —H, -OH, Calkoxy and Calkyl; preferably wherein the organic compound in c) is 0096 4. The drier composition according to any one of 1,4,7-trimethyl-1,4,7-tri-azacyclononane. statements 1 to 3, further comprising: 0105 8. The drier composition according to any one of (0097 d) a K salt of a carboxylic acid. statements 1 to 7, wherein components (b) and (c) of the 0098 5. The drier composition according to any one of drier composition are provided as the complex defined by statements 1 to 4, wherein the metal in b) is selected from Mn or Ce, preferably, wherein the metal in b) is Mn. CAS 13.81939-25-8. 0099. 6. The drier composition according to any one of 0106 9. The drier composition according to any one of statements 1 to 5, wherein the carboxylic acid is selected statements 1 to 8, comprising one or more carboxylate from branched-chain or straight-chain Saturated and salts of a compound of formula (VIII) unsaturated aliphatic, aromatic and alicyclic monocarbox ylic acids having 5 to 22 carbon atoms, cycloaliphatic monocarboxylic acids having 5 to 10 carbon atoms, or (VIII) mixtures of these acids, preferably the carboxylic acid is CH3 CH3 Selected from the group comprising 2-ethylbutanoic acid, V M 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, N N 2-ethyl-4-methylpentanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, neononanoic acid, ( '', /\ ? ) nonanoic acid, isodecanoic acid, neodecanoic acid, 2-eth chir MS2's N-CH yldecanoic acid, isotridecanoic acid, isotetradecanoic ( O '', ) acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, N N n-dodecanoic acid, cyclopentanoic acid, methylcyclopen A tanoic acid, cyclohexanoic acid, methylcyclohexanoic CH CH acid, 1,2-dimethylcyclohexanoic acid, cycloheptanoic acid, myristic acid, Stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, tall oil fatty acid, erucic 0107 10. The drier composition according to any one of acid, p-tert-butylbenzoic acid, monobutyl maleate, mono statements 1 to 9, wherein the ligand in a) is a ligand of decyl phthalate, naphthenic acid and mixtures thereof. formula (I) which belong to the bispidon class; wherein US 2016/0304747 A1 Oct. 20, 2016

each independently selected from the group consisting (I) of Coalkyl, Co-oaryl, halogen, Cigalkoxy, haloC 6alkyl, and haloCalkoxy; 0112 R is selected from the group consisting of H, halogen, —OH, Calkoxy, —NH-C(O)—H. —NH C(O)—C-alkyl, - NH, -NH. C. 12alkyl, and C2alkyl; wherein R is optionally sub stituted with one or more Substituents, each indepen dently selected from the group consisting of Calkyl, Co-oaryl, halogen, Cigalkoxy, haloC-alkyl, and haloCalkoxy; I0113 R’ is selected from the group consisting of H, halogen, —OH, Calkoxy, —NH-C(O)—H. I0108) R' is selected from the group consisting of —NH CO) C-alkyl, - NH, -NH C. C-2-alkyl, Co-oaryl, a group containing one or two 12alkyl, and C2alkyl; wherein R is optionally sub heteroatoms (e.g. N, O, or S) capable of coordinating to stituted with one or more Substituents, each indepen the Fe metal; wherein R' is optionally substituted with dently selected from the group consisting of Calkyl, one or more substituents, each independently selected Coaryl, halogen, Calkoxy, haloCalkyl, and from the group consisting of C-12alkyl, Co-oaryl, haloCalkoxy; Co-oarylC-alkyl, preferably said group containing I0114 X" is selected from C(O)—or —C(R).) ; one or two heteroatoms (e.g. N, O, or S) capable of wherein n is an integer selected from 0, 1, 2 or 3, and coordinating to the Fe metal, is selected from het each R is independently selected from the group con eroaryl, heteroarylCalkyl, CalkylaminoCalkyl sisting of —OH, -H, Calkoxy and C-alkyl: Such as —CH2—CH2—N(CH), wherein heteroaryl is wherein R is optionally substituted with one or more Selected from the group consisting of pyridyl, pyrazi substituents, each independently selected from the nyl, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl, group consisting of Coalkyl, Co-oaryl, halogen, pyrimidinyl, triazolyl and thiazolyl, preferably pyridin Calkoxy, haloCalkyl, and haloCalkoxy. 2yl; preferably R' is selected from the group consisting 0115 11. The drier composition according to any one of of C2-alkyl, Co-oaryl, heteroaryl, C-galkylaminoC statements 1 to 10, wherein the at least one nitrogen donor 6alkyl, and heteroarylCalkyl, wherein heteroaryl is ligand in a) is selected from the compounds of formula Selected from the group consisting of pyridyl, pyrazi- (II) or (III): nyl, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl, preferably pyridin 2yl; wherein R' is optionally substituted with one or (II) more substituents, each independently selected from N the group consisting of C-12alkyl, Co-oaryl, Co-oarylC-alkyl, 4. I0109 R is selected from the group consisting of C-2-alkyl, Co-oaryl, heteroaryl, C-galkylaminoC 6alkyl, and heteroarylCalkyl, wherein heteroaryl is Selected from the group consisting of pyridyl, pyrazi nyl, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl, preferably pyridin 2yl; wherein R is optionally substituted with one or more substituents, each independently selected from the group consisting of C-12alkyl, Co-oaryl, Co-oarylC-alkyl, I0110 R is selected from the group consisting of H, Calkyl, C-alkyl-O-C-alkyl, C-alkyl-O- (III) Coaryl, Coaryl, hydroxyC-alkyl, and -(CH2) C(O)OR; wherein R is selected from -H, Calkyl, Co-oaryl, or CalkylCo-oaryl, and wherein

m is an integer selected from 0, 1, 2, 3, or 4, wherein R is optionally substituted with one or more substitu ents, each independently selected from the group con sisting of C-galkyl, Co-oaryl, halogen, Calkoxy, haloCalkyl, and haloCalkoxy; I0111 R is selected from the group consisting of H, Calkyl, C-alkyl-O-C-alkyl, C-alkyl-O- Coaryl, Coaryl, hydroxyC-alkyl, and -(CH2) C(O)OR': wherein R is selected from -H, Ca alkyl, Co-oaryl, or CalkylCo-oaryl, and wherein m is an integer selected from 0, 1, 2, 3, or 4; wherein R' is optionally substituted with one or more substituents, US 2016/0304747 A1 Oct. 20, 2016

011 6 12. The drier composition according to any one of wherein each R are identical or different from each other, statements 1 to 11, wherein the iron complex in a) is a and independently selected from the group consisting of H, compound of formula (IV): Cis-alkyl, C-1s-alkenyl, C-1s-alkynyl, C-12-cycloalkyl, C-2-cycloalkenyl, C-2-heterocycloalkyl, C7-2-aralkyl, preferably wherein each R are identical or different from (IV) each other and independently selected from C-s-alkyl. I0121 17. The drier composition according to any one of statements 1 to 16, comprising one or more compounds of general structure (II*) or mixtures of different compounds of general structure (II*):

(CH2) CH H3C (CH2) N: sy, 1-ch, /... Mir-N-M in N (Chi-N\ / N /u-(CH2). N -N FeCl2 H2O CH HC

0117 13. The drier composition according to any one of wherein n is an integer in a range between 1 and 4. statements 1 to 12, wherein the iron complex in a) is the preferably between 2 and 4, for example 1, 2, 3, or 4, more compound with CAS nr. 478945-46-9. preferably wherein n is 2 or 3; and 0118 14. The drier composition according to any one of wherein X, Y, and Z are identical or different from each statements 1 to 12, wherein the iron complex in a) is iron other, and are selected from the group consisting of CH (1+).chlorodimethyl-9,9-dihydroxy-3-methyl-2,4-di-(2- COO and CH (CH), CH(CHCH) COO pyridyl-kN)-7-(2-pyridinyl-kN)methyl-3,7-diazabicy I0122 18. The drier composition according to any one of clo3.3.1 nonane-1,5-dicarboxylate-kN3.kN7-chloride statements 1 to 17, wherein the components (b) and (c) of the drier composition are provided as a complex, wherein (1-). said complex comprises manganese 2-ethylhexanoate and 0119) 15. The drier composition according to any one of 2,2'-bipyridyl. statements 1 to 14, wherein the ligand in c) is 1.4.7- I0123. 19. The drier composition according to any one of trimethyl-1,4,7-tri-azacyclononane statements 1 to 18, wherein the components (b) and (c) of 0120 16. The drier composition according to any one of the drier composition are provided as a complex, wherein statements 1 to 15, comprising one or more compounds of said complex comprises manganese 2-ethylhexanoate and general structure (I*) or mixtures of different compounds tolyldiethanolamine. of general structure (I*): 0.124 20. The drier composition according to any one of statements 1 to 19, wherein the components (b) and (c) of the drier composition are provided as a complex, wherein said complex comprises manganese octoate and a por (CH2) R1" R" (CH), phyrin ligand. 0.125 21. A coating composition, comprising: 0.126 a) at least one autoxidizable alkyd based binder; A). sy, \,L- s and 2- N, -1 2 0.127 b) at least one drier composition according to any one of statements 1 to 20. (CH3S \N / Z N N/u-(CH2). N / 0128 22. The coating composition according to state ment 21, further comprising an oxime, preferably a ketox ime, preferably methyl ethyl ketoxime. I0129 23. The coating composition according to state wherein each R'' are identical or different from each other, ment 21 or 22, comprising at most 0.01% by weight of and independently selected from the group consisting of anti-skinning agent other than an oxime, preferably at Cis-alkyl, Cis-alkenyl, Cis-alkynyl, and C-12-cycloalkyl, most 0.001% by weight, preferably at most 0.0001% by preferably wherein each R'' are identical or different from weight, based on the total weight of the coating compo each other and independently selected from the group con sition, preferably wherein the coating composition is sisting of C-1s-alkyl: more preferably wherein each R'' is essentially free of anti-skinning agents other than an methyl; oXime. wherein n is an integer in a range between 1 and 5. 0.130 24. The coating composition according to any one preferably between 2 and 5, for example 1, 2, 3, 4, or 5, more of statements 21 to 23, wherein the coating composition preferably wherein n is 2: comprises at least 0.0001% to at most 2% by weight of the wherein X, Y, and Z are identical or different from each metal in b), preferably at least 0.0002% to at most 0.1% other, and are RCOO-; and by weight of the metal in b), more preferably at least US 2016/0304747 A1 Oct. 20, 2016 12

0.0005% to at most 0.05% by weight of the metal in b), for example at least 0.001% to at most 0.02% by weight (I) of the metal in b), considering only the amount of metal

of said at least one metal salt of a carboxylic acid, with weight percent being based on the total weight of the alkyd binder. 0131 25. The coating composition according to any one of statements 21 to 24, wherein the coating composition is a solvent-borne coating composition. 0132 26. Use of the coating composition according to any one of statements 21 to 25 in a varnish, lacquer, paint, stain, enamel, printing ink or floor covering. 0.133 27. A substrate having applied thereon a coating I0142 R is selected from the group consisting of composition according to any one of Statements 21 to 25. C-2-alkyl, Co-oaryl, a group containing one or two het eroatoms (e.g. N, O, or S) capable of coordinating to the Fe 0134. In a first aspect, the present invention provides a metal; wherein R' is optionally substituted with one or more drier composition for an autoxidizable alkyd based coating Substituents, each independently selected from the group composition, comprising: consisting of Calkyl, Coaryl, CoarylCalkyl, pref erably said group containing one or two heteroatoms (e.g. N. I0135) a) at least one Fe complex comprising Fe and at O, or S) capable of coordinating to the Fe metal, is selected least one nitrogen donor ligand, wherein said at least from heteroaryl, heteroarylCalkyl, CalkylaminoC. nitrogen donor ligand is selected from the group com 6alkyl such as —CH2—CH2—N(CH), wherein heteroaryl prising tridentate, tetradentate, pentadentate and hexa is selected from the group consisting of pyridyl, pyrazinyl, dentate nitrogen donor ligands; pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl pyrimidi 0.136 b) at least one metal salt of a carboxylic acid, nyl, triazolyl and thiazolyl, preferably pyridin-2yl: wherein the metal is selected from the group compris I0143 preferably R' is selected from the group consisting ing: Mn, Ce, V, and Cu; and of C2-alkyl, Co-oaryl, heteroaryl, C-alkylaminoC 6alkyl, and heteroarylCalkyl, wherein heteroaryl is 0.137 c) at least one ligand comprising at least one selected from the group consisting of pyridyl, pyrazinyl, moiety selected from the group comprising 14.7-tri pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl pyrimidi azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, nyl, triazolyl and thiazolyl, preferably pyridin-2yl; wherein imidazolyl pyrazolyl, porphyrinyl, aliphatic, cycloali R" is optionally substituted with one or more substituents, phatic, and aromatic amines. each independently selected from the group consisting of 0.138. As used herein, the term “drier' (which is also C-12alkyl, Co-oaryl, Co-oarylC1-galkyl, referred to synonymously as “siccative' when in solution) 10144) R is selected from the group consisting of refers to organometallic compounds that are soluble in C-2-alkyl, Co-oaryl, heteroaryl, CigalkylaminoCo alkyl, organic solvents and binders. They are added to unsaturated and heteroarylCalkyl, wherein heteroaryl is selected from oils and binders in order to appreciably reduce their drying the group consisting of pyridyl, pyrazinyl, pyrazolyl pyr times, i.e. the transition of their liquid films to the solid rolyl, imidazolyl, benzimidazolyl pyrimidinyl, triazolyl and phase. Driers are available either as solids or in solution thiazolyl, preferably pyridin-2yl; wherein R is optionally (siccatives). Suitable solvents are organic solvents, fatty acid Substituted with one or more Substituents, each indepen esters and binders. The driers are present in amounts dently selected from the group consisting of Calkyl, expressed as weight percent of the metal based on the weight Co-oaryl, Co-oarylC1-alkyl, of binder solids (or resin) unless stated otherwise. (0145 R is selected from the group consisting of H, 0.139. As used herein, the term “drier composition” refers C-12alkyl, C-12alkyl-O-C-12alkyl, C-12alkyl-O-C- to the mixture of driers as presently claimed. The drier Ioaryl, Caryl, hydroxyC-alkyl, and —(CH),C(O) composition according to the invention comprises several OR; wherein R is selected from -H, Calkyl, Coaryl, drier compounds. The inventors have found that the present or CalkylCaryl, and wherein m is an integer selected selection of driers in an alkyd-based coating composition from 0, 1, 2, 3, or 4; wherein R is optionally substituted improves the drying speed of the coating composition while with one or more Substituents, each independently selected simultaneously reducing skin formation. from the group consisting of C1-alkyl, Co-oaryl, halogen, Calkoxy, haloCalkyl, and haloCalkoxy; 0140. According to an embodiment of the invention, the I0146) R' is selected from the group consisting of H, present drier composition comprises at least one Fe complex C-12alkyl, C-12alkyl-O-C-12alkyl, C-12alkyl-O-C- comprising Fe and at least one nitrogen donor ligand, 1oaryl, Coaryl, hydroxyC-alkyl, and —(CH),C(O) wherein said at least nitrogen donor ligand is selected from OR; wherein R is selected from -H, C alkyl, the group comprising tridentate, tetradentate, pentadentate Co-oaryl, or CalkylCo-oaryl, and wherein m is an integer and hexadentate nitrogen donor ligands; preferably selected selected from 0, 1, 2, 3, or 4: wherein R is optionally from the group comprising tetradentate, pentadentate, and Substituted with one or more Substituents, each indepen hexadentate nitrogen donor ligands. dently selected from the group consisting of Calkyl, 0141 Preferably, the ligandina) is a ligand of formula (I) Co-oaryl, halogen, Calkoxy, haloC1-alkyl, and haloC which belong to the bispidon class; wherein 6alkoxy; US 2016/0304747 A1 Oct. 20, 2016

I0147 R is selected from the group consisting of H, I0158 R is selected from the group consisting of halogen, —OH, Calkoxy, NH CO)—H. —NH C C-2alkyl, Co-oaryl, pyridyl, C-2alkylaminoC-2alkyl, (O)—C-alkyl, -NH2, —NH-C-alkyl, and wherein R is optionally substituted with one or more Calkyl; wherein R is optionally substituted with one or Substituents, each independently selected from the group more substituents, each independently selected from the consisting of Calkyl, phenyl, benzyl; group consisting of Calkyl, Coaryl, halogen, I0159 R is selected from the group consisting of Calkoxy, haloCalkyl, and haloCalkoxy; Coalkyl-O-C-alkyl, Cigalkyl-O-Co-oaryl, Co-oaryl, I0148 R is selected from the group consisting of H, hydroxyCoalkyl, and —(CH),C(O)OR; wherein R is halogen, —OH, Calkoxy, NH C(O)—H, -NH C selected from —H, C alkyl, Caryl, or CalkylC. (O)—C-alkyl, -NH2, —NH-C-alkyl, and 1oaryl, and wherein m is an integer selected from 0, 1, 2, or Calkyl; wherein R is optionally substituted with one or 3: more substituents, each independently selected from the (0160 R is selected from the group consisting of group consisting of Cigalkyl, Co-oaryl, halogen, Calkyl-O-C-alkyl, Calkyl-O-Coaryl, Coaryl, Calkoxy, haloCalkyl, and haloCalkoxy; hydroxyCoalkyl, and —(CH),C(O)CR'; wherein R is I0149 X is selected from C(O)— or —C(R).) ; selected from —H, Calkyl, Coaryl, or CalkylC. wherein n is an integer selected from 0, 1, 2 or 3, and each 1oaryl, and wherein m is an integer selected from 0, 1, 2, or R is independently selected from the group consisting of 3: —OH, -H, C-12alkoxy and C-12alkyl; wherein R is (0161 R is selected from the group consisting of H, optionally substituted with one or more substituents, each halogen, —OH, Calkoxy, NH CO)—H. —NH C independently selected from the group consisting of (O)—Calkyl, -NH2, —NH-C-alkyl, and Calkyl; Calkyl, Coaryl, halogen, Calkoxy, haloCalkyl, and (0162 R is selected from the group consisting of H, haloCalkoxy. halogen, —OH, Calkoxy, NH CO)—H. —NH C 0150. In some embodiments, R' is selected from the (O)—C alkyl, -NH. —NH-C-alkyl, and Calkyl: group consisting of C-2alkyl, Co-oaryl, heteroaryl, (0163 X is selected from C(O)— or —C(R).) ; CalkylaminoCalkyl, heteroarylCalkyl, wherein het wherein n is an integer selected from 0, 1, 2 or 3, and each eroaryl is selected from the group consisting of pyridyl, and (0164 R is independently selected from the group pyrazinyl, preferably pyridin-2yl; wherein R' is optionally consisting of —H. —OH, Calkoxy and Calkyl Substituted with one or more Substituents, each indepen 0.165 Preferably, the nitrogen donor ligand is a com dently selected from the group consisting of Calkyl, pound of formula (I); Co-oaryl, Co-oarylC-alkyl, (0166 wherein R' and Rare each independently selected 0151 R is selected from the group consisting of from the group consisting of C2-alkyl, Coaryl, het C-2alkyl, Co-oaryl, heteroaryl, CalkylaminoCalkyl, eroaryl, C-alkylaminoCalkyl, and heteroarylCalkyl; heteroarylCalkyl, wherein heteroaryl is selected from the wherein heteroaryl is selected from the group consisting of group consisting of pyridyl, and pyrazinyl, preferably pyri pyridyl, pyrazinyl, and pyrazolyl, din-2yl; wherein R is optionally substituted with one or (0167 Rand Rare each independently selected from the more substituents, each independently selected from the group consisting of —H, Cisalkyl, C-alkyl-O-C salkyl, group consisting of C1-alkyl, Co-oaryl, Co-oarylCalkyl, Cisalkyl-O Co-oaryl, Co-oaryl, hydroxyCisalkyl, and 0152 R is selected from the group consisting of H, —(CH),C(O)OR: R is selected from —H, Calkyl, Calkyl, Calkyl-O Cealkyl, Calkyl-O Coaryl, Co-oaryl, or CalkylCo-oaryl, and m is an integer selected Coaryl, hydroxyCoalkyl, and -(CH2),C(O)OR; from 0, 1, 2, 3, or 4: wherein R is selected from -H, C, alkyl, Co-oaryl, or (0168 each R and R7 are independently selected from CalkylCaryl, and wherein m is an integer selected the group consisting of —H. —F. —Cl. —Br. —OH, from 0, 1, 2, 3, or 4: Calkoxy, NH C(O) H, NH-C(O) C. I0153 R' is selected from the group consisting of H, 4alkyl, -NH2 —NH-Calkyl, and Calkyl, and, Calkyl, Calkyl-O-C alkyl, Calkyl-O-C-aryl, (0169. X" is selected from C(O)— or —C(R).) ; Coaryl, hydroxyCoalkyl, and -(CH2),C(O)CR': wherein n is an integer selected from 0, 1, 2 or 3, and each wherein R is selected from -H, C, alkyl, Coaryl, or R is independently selected from the group consisting of CalkylCaryl, and wherein m is an integer selected —H. —OH, Calkoxy and Calkyl. from 0, 1, 2, 3, or 4: (0170 wherein R' and Rare each independently selected 0154 R is selected from the group consisting of H, from the group comprising C-2-alkyl, C-12aryl, heteroaryl, halogen, —OH, Calkoxy, NH CO)—H. —NH C heteroarylCalkyl, and —CH2—CH2—N(CH), wherein (O)—Calkyl, -NH. —NH-C-alkyl, and Calkyl: heteroaryl is selected from the group comprising pyridyl, 0155 R7 is selected from the group consisting of H, pyrazinyl, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl, halogen, —OH, Calkoxy, NH CO)—H. —NH C pyrimidinyl, triazolyl and thiazolyl; (O)—Calkyl, -NH. —NH-C-alkyl, and Calkyl: (0171 RandR are each independently selected from the I0156 X" is selected from C(O)— or —C(R).) ; group comprising —H. C. salkyl, Csalkyl-O-C salky wherein n is an integer selected from 0, 1, 2 or 3, and each lene, Cisalkyl-O-C-12arylene, C-12aryl-O-C-salky R is independently selected from the group consisting of lene, Caryl, C-shydroxyalkyl, and -(CH),C(O)OR. —H, halogen, —OH, Calkoxy and Calkyl. wherein R is selected from-H or C-alkyl, m is an integer 0157. In some embodiments, R' is selected from the selected from 0 to 4: group consisting of C-2alkyl, Co-oaryl, pyridyl, C-2alky (0172 each Rand Rare independently selected from the laminoC-alkyl, wherein R' is optionally substituted with group comprising —H. —F. —Cl. —Br. —OH, Calkoxy, one or more Substituents, each independently selected from NH C(O) H, NH C(O)—Calkyl, -NH2, the group consisting of Calkyl, phenyl, benzyl; —NH-C-alkyl, and Calkyl; US 2016/0304747 A1 Oct. 20, 2016

(0173 X is selected from C(O) or -C(R)- formula (II) or (III). In a more preferred embodiment, the wherein n is an integer selected from 0 to 3, and each R is nitrogen donor ligand in a) is the compound of formula (II). independently selected from the group comprising —H. —OH, Calkoxy and Calkyl: (0174 Preferably R and R are each independently (II) selected from the group comprising —C(O)—O—CH, C(O) O CH, CH, —C(O)—O—CH2—CHs and CHOH. (0175 Preferably X is C—O. (0176 Preferred groups for R' and R are selected from the group comprising CH. —CHs —CH-7, benzyl, C4H9. —CH13. –CsH17, —C12H2s, and —C-sha7: —CH2-pyridyl, and pyridin-2-ylmethyl, and —CH2— CH, N(CH). (0177. In one embodiment, R' and Rare selected from a optionally Substituted heteroaryl, —CH, —CHs —CH7. —C4H9, CH3, CsP17, C12H2s. ClsH37, and —CH2— CH, N(CH4). More preferably, at least one of R' and R' is pyridin-2-yl, optionally substituted by —C-alkyl or (III) benzyl. Even more preferably, at least one of R' or R is pyridin-2-ylmethyl and the other is selected from —CH, C2H5. CH7. C4H9. CHs. CsH17, C12H2s.

(0178 X" is preferably selected from -C=O. (0179 Preferably, R and R are equal and are selected from —C(O)—O—CH –C(O)—O CHCH. —C(O)— O CHCHs and —CH2OH. 0180 Preferably, at least one of R' or R is pyridin-2- ylmethyl and the other is selected from —CH, —CHs. CH7, -CH3, —CHs. -Cs.H17, -CH3; R and R' are equal and are selected from —C(O)—O—CH, —C(O)—O CHCH. —C(O)—O CHCH and —CH-OH; and X is selected from -C=O, and Rand R' are H. 0181 Preferably, at least one of R' or R is pyridin-2- 0186 Preferably the ligand L is present in one or more of ylmethyl and the other is selected from —CH, —CHs. the forms (FeLC1), FeICICI, FeL(HO)(PF), FeIL CH, -CH, -CH, -Cs.H, -CHs; R and R' C1, FeLCIPF, and FeI (HO)(BF). Preferably the are equal and are selected from —C(O)—O—CH, ligand L is present in one or more of the form FeLC1. —C(O)—O CHCH, and —C(O)—O CHCHs; and X FeLCIIC1, FeIIC1, and FeL(HO)(BF). is -C=O, and R and R7 are H. 0187 Preferably, the iron complex in a) is a compound of 0182. A preferred class of bispidon is one in which at least one of R' or R is pyridin-2-ylmethyl or benzyl, formula (IV): preferably pyridin-2-ylmethyl. More preferably, R is pyri din-2-ylmethyl and R is methyl. (IV) 0183) A preferred ligand is 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 the iron complex thereof Fe(N2py3o-C1)Cl]Cl which can be pre pared as described in WO 02/48301. Another suitable ligand is 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-di carboxylate and the iron complex thereof. Other preferred bispidons are ones in which instead of having a methyl group at the 3 position have longer alkyl chains, namely isobutyl, (n-hexyl) C6, (n-octyl) C8, (n-dodecyl) C12, (n-tet radecyl) C14, (n-octadecyl) C18, which were prepared in an analogous manner. Preferred tetradentate bispidons are also described in WO00/60045 and preferred pentadentate bispi FeCl2 H2O dons are described in WOO2/48301 and WOO3/104379 the entirety of each of which are hereby incorporated by refer CCC. 0188 which may also be referred to as the active ingre 0184 Preferably the iron ion is selected from Fe(II) and dient of Borchi(R) Oxy Coat from OMG with CAS nr. Fe(III), preferably the iron ion is Fe(II). 478945-46-9. 0185. In a preferred embodiment, the at least one nitrogen 0189 In some embodiments, the iron complex is the donor ligand in a) is selected from the compounds of complex defined as CAS nr. 478945-46-9. US 2016/0304747 A1 Oct. 20, 2016

0190. In some embodiments, the iron complex is iron thereof. Optionally, monobasic acids are added. Such as a (1+).chlorodimethyl-9,9-dihydroxy-3-methyl-2,4-di-(2- saturated or unsaturated fatty acid after reaction with dienes, pyridyl-kN)-7-(2-pyridinyl-kN)methyl-3,7-diazabicyclo neodecanoic acid, naphthenic acid, isononanoic acid, Stearic 3.3.1 nonane-1,5-dicarboxylate-kN3, kN7-chloride(1-). acid, or any mixture thereof. Suitable polyols are glycerol, 0191 The drier composition according to the first aspect pentaerythritol, dipentaerythritol, synthetic polyols, or any of the invention also comprises: mixture thereof. The reactants are reacted in Such propor 0.192 b) at least one metal salt of a carboxylic acid, tions that there is preferably a small excess of basic con wherein the metal is selected from the group comprising: stituents, which results is a limited amount of free hydroxyl Mn, Ce, V, and Cu. functionality. This tends to insure a good solubility in the 0193 In a preferred embodiment, the metal in b) is binder formulation. Generally, but not exclusively, the man selected from Mn or Ce. In a preferred embodiment, the ganese compound is first reacted with an excess of the metal in b) is Mn. carboxylic acids, resulting in a lower molecular weight 0194 In a preferred embodiment, the carboxylic acid is manganese bearing compound with excess carboxylic func selected from branched-chain or straight-chain Saturated and tionality, which is then further reacted with one or more unsaturated aliphatic, aromatic and alicyclic monocarbox polyols to the final macro molecular structure. Preferred ylic acids having 5 to 22 carbon atoms, cycloaliphatic polymer compounds are described in WO2012000934 the monocarboxylic acids having 5 to 10 carbon atoms, or entirety of which is hereby incorporated by reference. mixtures of these acids. Preferably the carboxylic acid is 0196. The drier composition according to the first aspect selected from the group comprising 2-ethylbutanoic acid, of the invention also comprises as component (c) at least one 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 2-ethyl ligand comprising at least one moiety selected from the 4-methylpentanoic acid, 2-ethylhexanoic acid, isooctanoic group comprising 1,4,7-tri-azacyclononanyl. 2,2'-bipyridyl, acid, isononanoic acid, neononanoic acid, nonanoic acid, 1,10-phenantrolinyl, imidazolyl pyrazolyl, porphyrinyl, ali isodecanoic acid, neodecanoic acid, 2-ethyldecanoic acid, phatic, cycloaliphatic, and aromatic amino. isotridecanoic acid, isotetradecanoic acid, n-hexanoic acid, 0.197 In some embodiments, the at least one ligand n-octanoic acid, n-decanoic acid, n-dodecanoic acid, cyclo comprises an imidazole. As used herein, the term “imida pentanoic acid, methylcyclopentanoic acid, cyclohexanoic Zole” refers to a compound with the formula CHN. Imi acid, methylcyclohexanoic acid, 1,2-dimethylcyclohexanoic dazole refers to the parent compound whereas imidazoles acid, cycloheptanoic acid, myristic acid, Stearic acid, are a class of heterocycles that share the 1.3-CN ring but arachidic acid, behenic acid, oleic acid, linoleic acid, tall oil with varying substituents. Non-limiting examples of suitable fatty acid, erucic acid, p-tert-butylbenzoic acid, monobutyl imidazole ligands are selected from the group comprising: maleate, monodecyl phthalate, naphthenic acid and mixtures 1-octyl-1H-imidazole, 2-ethyl-4-methylimidazole, N. thereof. In a preferred embodiment, the carboxylic acid is N-bis-(2-ethyl-4-methylimidazol-5-ylmethyl) aminopro 2-ethylhexanoic acid, neodecanoic acid, or naphthenic acid. pane, 1,1'-(1,3-propanediyl)bis(1H-imidazole), 1,1'-(1,4-bu 0195 In an embodiment, the at least one Mn salt of a tatanediyl)bis(1H-imidazole), 1,1'-(1,5-pentanediyl)bis(1H carboxylic acid is a polymer compound comprising a man imidazole), 1,1'-(1,6-hexanediyl)bis(1H-imidazole), and ganese-bearing polymer, said polymer compound having a 1,1-1,4-phenylenebis(methylene)bis(1H-imidazole). manganese content of 0.5% to 12% by weight, a mean 0.198. In some embodiments, the at least one ligand molecular weight of more than 2000, comprising manganese comprises a pyrazole. As used herein, the term "pyrazole' carboxylate sequences, with an acid value of less than 40 mg refers to a compound with the formula CH-NH. Pyrazole KOHAg, preferably of less than 20 mg KOH/g. Fatty acids refers to the parent compound whereas pyrazoles are the are the preferred carboxylic acids, as Such alkyd type class of compounds that have the ring CN with adjacent polymers are more compatible with the alkyd binders used nitrogen centers. Non-limiting examples of Suitable imida in paints and inks. For the same reason, the polymer could Zole ligands are selected from the group comprising: 3-phe have an excess of hydroxyl groups. The mean molecular nyl-1H-pyrazole, 3-(4-methoxyphenyl)pyrazole, 3,3'-(1,3- weight can be estimated from the remaining free function phenylene)bis(1H-pyrazole), and 3,3'-(1,4-phenylene)bis alities of the polymer, or by any appropriate analytical (1H-pyrazole). technique. The polymer compound has preferably a manga 0199. In some embodiments, the at least one ligand nese content of between 1 and 6% by weight. Also, a mean comprises an amine. As used herein, the term "amine” refers molecular weight of more than 3000 is preferred. It may be to compounds that contain a basic nitrogen atom with a lone unsaturated. Polymer compounds having a mean molecular pair. The term "amine” comprises primaryl, secondaryl, and weight of less than 250000 are preferred. The manganese tertiary amines. Non-limiting examples of Suitable imida atoms can be an integral part of the backbone chain of the Zole ligands are selected from the group comprising: ethyl polymer. By this is meant that the manganese atoms form enediamine, N,N'-tetramethylethylenediamine, diethylen links in the backbone chain of polymers. The process for etriamine, 1,1,4,7,7-pentamethyldiethylenetriamine preparing Such polymer compound can comprise the steps of triethylenetetramine, 1,1,4,7,10,10-hexamethyltriethyl reacting a manganese salt or oxide, preferably manganese enetetramine, tetraethylenepentamine, pentaethylenehexam acetate, with an acid functional polymer, or with a mixture ine, and N,N'-tetramethylpropylenediamine. of polybasic and monobasic carboxylic acids, thereby 0200. As used herein, the term “ligand comprising at obtaining a first intermediate compound; and, of reacting least one 1,4,7-tri-azacyclononanyl moiety encompasses said first intermediate compound with a polyol, or a mixture ligands which comprise at least one optionally Substituted of polyols, until water evolution ceases. Suitable divalent 1.4.7-triazacyclononane structure which has one or more carboxylic acids are dimeric fatty acids, orthophtalic acid, nitrogen groups that complex with one metal salt of a isophtalic acid, terephtalic acid, maleic acid, adipic acid, carboxylic acid, to provide a tridentate, tetradentate, penta Succinic acid, sebacic acid, dodecanoic acid, or any mixture dentate or hexadentate ligand. US 2016/0304747 A1 Oct. 20, 2016 16

0201 In a preferred embodiment, the at least one ligand (0210 each X* is independently selected from H or in c) is a compound of formula (V), wherein Calkyl; and wherein each R’ is an independently selected organic group, preferably independently selected from an optionally Calkyl-substituted heteroaryl group selected (V) from the group consisting of pyridyl, pyrazinyl, pyrazolyl, R20 R20 pyrrolyl, imidazolyl, benzimidazolyl pyrimidinyl, triazolyl N N Y and thiazolyl; wherein at least one of R is C(X) R’. 0211. In a preferred embodiment, the at least one organic compound in (c) is a compound of formula (XI), wherein (--) (0212 each R" is independently selected from the group R20 consisting of Calkyl, C-cycloalkyl, heterocycloalkyl, heteroaryl, Co-oaryl and Co-oaryl-C-alkyl, optionally (0202 each R' is independently selected from the group substituted with a substituent selected from the group con consisting of Coalkyl, C-scycloalkyl, heterocycloalkyl, sisting of —OH, Calkoxy, phenoxy, carboxylate, carbox heteroaryl, Coaryl and Coaryl-Calkyl, Clalkyl-C- amide, carboxylic ester, Sulfonate, amine, Calkylamine Ioaryl, each group being optionally Substituted with one or and - N*(R'); more substituents each independently selected from the (0213) each R is selected from -H, C, alkyl, Calk group consisting of —OH, Calkoxy, phenoxy, carboxy enyl, Coaryl-Calkyl, Coaryl-Calkenyl, C. alky late, carboxamide, carboxylic ester, Sulfonate, amine, loxy, C2-alkenyloxy, aminoCalkyl, aminoC2-alkenyl, Calkylamino and N“(R'); Calkyl ether, Calkenyl ether, and —CX - Rif; (0203 each R is independently selected from -H, 10214) each X* is independently selected from H or Coalkyl, C2-loalkenyl, Co-oaryl-C-alkyl, Co-oaryl-C2 Calkyl; and wherein each R’ is independently selected 6alkenyl, C-alkyloxy, C2-galkenyloxy, aminoC-alkyl, from an optionally Calkyl-substituted heteroaryl group aminoCalkenyl, C-alkyl ether, Calkenyl ether, and selected from the group consisting of pyridyl, pyrazinyl, —CX R’; and, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl pyrimidi (0204 each X* is independently selected from H or nyl, triazolyl and thiazolyl; and, wherein at least one of R' Calkyl; and wherein each R’ is independently selected is –C(X). R’. Preferably R’ is selected from option from an optionally Calkyl-substituted heteroaryl group ally Substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1-yl, selected from the group consisting of pyridyl, pyrazinyl, quinolin-2-yl groups. Most preferably R’ is either a pyri pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl pyrimidi din-2-yl or a quinolin-2-yl. nyl, triazolyl and thiazolyl; preferably wherein at least one 0215. The ligand of formula (V) is also referred to as of R is C(X), R’. TACN-NX. (0205. In some embodiments, each R" is independently 0216 Preferably, the ligand in c) is 1,4,7-trimethyl-1,4, selected from the group consisting of Calkyl, C-scy 7-tri-azacyclononane. cloalkyl, heterocycloalkyl, heteroaryl, Coaryl and 0217 Preferably the ligand is a porphyrin ligand. A Coaryl-Calkyl, Calkyl-Coaryl, each group being porphyrin is a compound containing four nitrogen hetero optionally substituted with one or more substituents each cycles arranged in a cyclic structure. For example, in some independently selected from the group consisting of —OH, embodiments, the porphyrin ligands of interest have the Calkoxy, phenoxy, carboxylate, carboxamide, carboxylic structure of Formula (VI) ester, sulfonate, amine, C-alkylamine and —N"(R)s: 0206 each R is independently selected from —H. C-calkyl, C2-alkenyl, Co-oaryl-C-galkyl, Co-oaryl-C2 (VI) 6alkenyl, Calkyloxy, Calkenyloxy, aminoCalkyl, R72 R65 aminoCalkenyl, C2-alkyl ether, Calkenyl ether, and Z! —CX R’; and, s 0207 each X* is independently selected from —H or R71 N R66 Calkyl; and wherein each R’ is selected from an option N NH NS ally Calkyl-substituted heteroaryl group selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl pyrrolyl, R-Z Z-R62 imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thi azolyl; wherein at least one of R is C(X) R’. N HN (0208. In some embodiments, each R" is independently R70 \ I / R67 selected from the group consisting of Calkyl, C-scy Z3 cloalkyl, heterocycloalkyl, heteroaryl, Coaryl and R69 R68 Coaryl-Calkyl, Calkyl-Coaryl, each group being optionally substituted with one or more substituents each independently selected from the group consisting of —OH, 0218 Z, Z, Z, and Z are independently selected from Calkoxy, phenoxy, carboxylate, carboxamide, carboxylic C and N: ester, sulfonate, amine, Calkylamine and —N"(R)s: 0219 R'-R'' are each independently selected from 0209 each R is independently selected from -H, hydrogen, halo, Calkyl, Calkenyl, C-alkynyl, Calkyl, C2-alkenyl, Co-oaryl-C alkyl, Co-oaryl-C2 Co-20aryl, C-24alkaryl, C-24aralkyl, hydroxyl, C-2-alkoxy, 6alkenyl, Calkyloxy, C2-galkenyloxy, aminoCalkyl, C2-2-alkenyloxy, C2-alkynyloxy, C-2aryloxy, acyloxy, aminoCalkenyl, C-alkyl ether, Calkenyl ether, and acyl, C2-2-alkoxycarbonyl, Co-oaryloxycarbonyl, —CX R’; and, Calkylcarbonyl, Carylcarbonyl, halocarbonyl, US 2016/0304747 A1 Oct. 20, 2016 formyl, thioformyl, C-alkylcarbonato, Carylcarbon (0222 R'-R' may be selected from enols, ketones, ato, carboxy, carboxylato, carbamoyl, thiocarbamoyl, car esters, aldehydes, anhydrides, and acyl halides, ethers, epox bamato, carbamido, cyano, isocyano, cyanato, isocyanato, ies, phosphonics, phosphates, phospinites, phosphate esters, isothiocyanato, amino, Calkylamido, Coarylamido, imides, azides, azoles, nitrates, nitriles, carbimides, aziri imino, alkylimino, arylimino, nitro, nitroso, Sulfhydryl, dines, hydroxylamines, ketoximes, aldoximes, nitrate esters, Calkylsulfanyl, Carylsulfanyl, Sulfo, sulfino, Sulfo enamines, azoles, imidazols, pyrroles, indoles, purines, nyl, phosphino, phosphono, and O-phosphono, provided that pyrimidines, piperidines, pyridazines, pyridyl and deriva when Z, Z, Z, and Z' is N, then the corresponding R tives, linear, cyclic and aromatic, oxyhalides, sulfides, thio group (R', R. R. or R, respectively) is not present. ethers, thioesters, Sulfonates, Sulfinyls, thiocyanates, disul Any such groups may be unsubstituted or Substituted and fides, Sulfones, thioamides, Sulfoxides, isothyocyanates, may contain one or more heteroatoms as appropriate (i.e., as Sulfonamides, Sulfonyl halides, thioureates, and thiophos the chemical nature of the group allows for such substitution phate esters. or heteroatoms). Furthermore, any two adjacent groups 0223. In some embodiments, R. R. R. and R are selected from R'-R' may be taken together to form a cycle, the same. For example, in some embodiments, R. R. R. wherein Such cycle may be aliphatic, aromatic, heteroatom and R are the same and are selected from hydrogen, containing, and/or Substituted as appropriate. It will be Substituted or unsubstituted C-alkyl, substituted or unsub appreciated that the dashed lines and double bonds shown in stituted heteroatom-containing C-alkyl, Substituted or the formulae herein are drawn in certain orientations but are unsubstituted Caryl, and Substituted or unsubstituted not intended to imply a definite or fixed location of such heteroaryl. For example, R. R. R. and Rare the same bonds. In other words, resonance structures of the formulae and are selected from hydrogen, phenyl, and methoxyphe drawn herein are intended to be within the scope of the nyl. invention. 0224. In some embodiments, R. R. R7, R. R. 0220. For example, in some embodiments, Z, Z, Z. R", R', and R'' are the same. For example, in some and Z are N, and R. R. R. and Rare not present. In embodiments, R, R, R7, R. R. R79, R7, and R7?are some embodiments, Z, Z, Z, and Z are C, and R', R, the same and are hydrogen. R, and Rare present. In some embodiments, one or more 0225. In some embodiments, R. R. R. and Rare of Z, Z, Z, and Z are C, and one or more of Z, Z, Z, the same and are a first group, R. R. R. R. R. R', and Z are N. R', and R'' are the same and are a second group, and the 0221) For example, R-R'' are independently selected first and second groups are different groups. from: hydrogen; halo, including F, Cl, Br, and I; substituted 10226. In some embodiments, Z, Z, Z, and Z are the or unsubstituted C-2-alkyl, C2-alkenyl, C-2-alkynyl, same. In other embodiments, Z, Z, Z, and Z are not the Coaryl, C-alkaryl, Caralkyl; Substituted or unsub SaC. stituted heteroatom-containing C-2-alkyl, C2-alkenyl, 0227. In some embodiments, the ligands of interest have C2-24alkynyl, Co.20aryl, C-24alkaryl, C-24aralkyl: the structure of Formula (VII): hydroxyl; Substituted or unsubstituted Calkoxy, C2-2-alkenyloxy, C2-alkynyloxy, C-2aryloxy, acyloxy,

acyl, Calkoxycarbonyl, Coaryloxycarbonyl, (VII) Calkylcarbonyl, Carylcarbonyl, halocarbonyl, formyl, thioformyl; Calkylcarbonato, Carylcarbon ato; carboxy and carboxylato (including C-alkylcarboxy lato and Carylcarboxylato); carbamoyl (including mono (C-2-alkyl)-substituted carbamoyl, di-(C-2-alkyl)- Substituted carbamoyl, mono-Substituted arylcarbamoyl, and mixed alkyl/aryl substituted carbamoyl) and thiocar bamoyl; carbamato (including mono-(C-2-alkyl)-substi tuted carbamato, di-(Calkyl)-substituted carbamato, mono-Substituted arylcarbamato, and mixed alkyl/aryl Sub stituted carbamato); carbamido, cyano, isocyano, cyanato, isocyanato, and isothiocyanato; amino (including mono- and di-(Calkyl)-substituted amino, mono- and di-(Caryl)- 63 Substituted amino, and mixed alkyl/aryl Substituted amino); (R75). R alkylamido and Carylamido; imino, alkylimino, and arylimino; nitro; nitroso; sulfhydryl (including C-alkyl Sulfanyl, and Coarylsulfanyl); Sulfo (including C-alkyl 0228 wherein Z, Z, Z, and Z, R', R, R, and R' Sulfonato, and Carylsulfonato); Sulfino (including are as defined in formula (VI) above; p, q, r, and S are Calkylsulfinyl, and Carylsulfinyl); Sulfonyl (includ independently selected from the integers 0, 1, 2, 3, and 4: ing C-alkylsulfonyl, and Coarylsulfonyl); phosphino and each R', R, R', and R7 is independently selected (including mono-, di-, and tri-(Calkyl)-substituted phos from the groups defined above for R'-R' in formula (V). phinato, mono-, di-, and tri-(Caryl)-substituted phosphi 0229. For example, in Some embodiments, p, q, r, and S nato, mixed alkyl/aryl Substituted phosphinato, and phos are each 0. phine oxides); and phosphono (including mono- and di-(C- 0230. In some embodiments, pairs of substituents 24alkyl)-substituted phosphonato, mono- and di-(Caryl)- selected from R. R. R7, and R7 may be taken together substituted phosphonato, mixed alkyl/aryl substituted to form further cycles, wherein Such cycles are aliphatic, phosphonato, and O-phosphonato). aromatic, heteroatom-containing, and/or substituted. US 2016/0304747 A1 Oct. 20, 2016

0231. For example, in some embodiments, the ligand is chlorophyll. Additional specific ligands and methods for phthalocyanine, tetrabenzoporphyrin, tetraazaporphyrin, or their preparation can be found in the relevant literature, such porphyrin. as Kadish et al., Handbook of Porphyrin Science: With 0232 Ligands of interest include tetraarylporphyrins, Applications to Chemistry, Physics, and Materials (World diarylporphyrins, tetraalkylporphyrins, dialkylporphyrins, Scientific, 2010), the contents of which are incorporated by and mixed aryl/alkyl porphyrins, as well as porphyrins reference. containing alkenyl Substituents, alkynyl Substituents, het 0233 Preferably the components (b) and (c) of the drier eroatom-containing Substituents (e.g., heteroaryl, etc.), func composition can be provided as complexes. tionalized Substituents (e.g., alkyl Substituted with a car 0234. In a preferred embodiment, the drier composition boxyl group, etc.), and the like. Specific ligands of interest comprises one or more carboxylate salt of compound of include, but are not limited to: phthalocyanine; tetrabenzo formula (VIII), as a complex of (b) and (c). porphyrin, tetraazaporphyrin, tetratolylporphyrin, porphy 0235. In a preferred embodiment, the drier composition rin; porphyrazine; 5,10,15,20-tetrakisphenylporphyrin; comprises the 2-ethylhexanoate and acetate salt of a com 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin; 5-azapro pound of formula (VIII), as a complex of (b) and (c). toporphyrin dimethylester, bis-porphyrin, coproporphyrin III; coproporphyrin III tetramethylester; deuteroporphyrin; (VIII) deuteroporphyrin IX dimethylester; diformyldeuteroporphy CH3 CH3 rin IX dimethyl ester, dodecaphenylporphyrin, hematopor V M phyrin, hematoporphyrin IX; hematoporphyrin monomer; hematoporphyrin dimer; hematoporphyrin derivative; O f hematoporphyrin IX dimethylester; haematoporphyrin IX 1 f Y. dimethylester; mesoporphyrin dimethylester, mesoporphy CH3-N-- -360xi- -N-CH rin IX dimethylester; monoformyl-monovinyl-deuteropor ( f No1 ) phyrin IX dimethylester; monohydroxyethylvinyl deu N teroporphyrin, 5,10,15,20-tetra(o-hyd roxyphenyl) A porphyrin; 5,10,15,20-tetra(m-hydroxyphenyl)porphyrin; CH CH 5,10,15,20-tetrakis-(m-hydroxyphenyl)porphyrin; 5,10,15, 20-tetra(p-hydroxyphenyl)porphyrin; 5,10,15,20-tetrakis (3-methoxyphenyl)porphyrin; 5,10,15,20-tetrakis-(3,4-di 0236 which may also be referred to as the active ingre methoxyphenyl)porphyrin, 5,10,15,20-tetrakis(3,5- dient of Drycoat. dimethoxyphenyl)porphyrin, 5,10,15,20-tetrakis-(3,4,5- 0237 Preferably the components (b) and (c) of the drier trimethoxyphenyl)porphyrin; 2,3,7,8,12,13.17, 18-octaethyl composition can be provided as a complex, wherein said 5,10,15,20-tetraphenylporphyrin: Photofrin; porphyrin c; complex comprise the reaction mass of tri-L-(2-ethyl protoporphyrin, protoporphyrin IX; protoporphyrin dim hexanoato-O)-bis(N,N',N'-trimethyl-1,4,7-triazacy ethylester; protoporphyrin IX dimethylester; protoporphyrin clononane-N,N',N")di-manganese and u-(acetato-O)-di-u- propylaminoethylformamide iodide; protoporphyrin N.N- (2-ethylhexanoato-O)-bis(N,N',N'-trimethyl-1,4,7- dimethylaminopropylformamide; protoporphyrin propylam triazacyclononane-N,N',N")di-manganese (Cas 1381939 inopropylformamide iodide; protoporphyrin butylforina 25-8, EG-nr.: 937-913-7). mide; protoporphyrin N<-->-dimethylamino-formamide: 0238. In some preferred embodiments, the drier compo protoporphyrin formamide: Sapphyrin 13,12,13.22-tetra sition comprises a manganese compound as defined in WO ethyl-2.7, 18.23 tetramethyl sapphyrin-8,17-dipropanol; sap 2014/086556, hereby incorporated by reference in its phyrin 2 3,12,13.22-tetraethyl-2,7,18,23 tetramethyl sap entirety, preferably a manganese compound according to phyrin-8-monoglycoside; Sapphyrin 3; meso-tetra-(4-N- paragraphs 026-029 of WO 2014/086556, said para carboxyphenyl)-porphine; tetra-(3-methoxyphenyl)- graphs hereby incorporated by reference. porphine; tetra-(3-methoxy-2,4-difluorophenyl)-porphine; 0239. In some preferred embodiments, the drier compo 5,10,15,20-tetrakis(4-N-methylpyridyl)porphine; CSO sition comprises one or more compounds of general struc tetra-(4-N-methylpyridyl)porphine tetrachloride; meso-tetra ture (I*) or mixtures of different compounds of general (4-N-methylpyridyl)porphine; meso-tetra-(3-N-methyl structure (I*): pyridyl)-porphine; meso-tetra-(2-N-methylpyridyl) porphine; tetra(4-NNN-trimethylani finium)porphine; meso tetra-(4-NNN"-trimethylamino-phenyl)porphine tetrachloride; tetranaphthaloporphyrin; 5,10,15,20-tetraphe (CH2) RI R1" (CH2) nylporphyrin, tetraphenylporphyrin, meso-tetra-(4-N-sul RS-WN N NI Ya, \N 1N- RI2 . fonatophenyl)-porphine; tetraphenylporphine tetrasulfonate; meso-tetra-(4-sulfonatophenyl)porphine; tetra-(4-Sulfonato phenyl)porphine, tetraphenylporphyrin Sulfonate; meso tetra-(4-Sulfonatophenyl)porphine; tetrakis-(4-Sulfonato phenyl)porphyrin, meso-tetra(4-sulfonatophenyl)porphine; meso-(4-sulfonatophenyl)porphine; meso-tetra-(4-Sulfona tophenyl)porphine; tetrakis(4-Sulfonatophenyl)porphyrin, meso-tetra-(4-N-trimethylanilinium)-porphine; uroporphy (0240 wherein each R'' are identical or different from rin; uroporphyrin I; uroporphyrin IX; and uroporphyrin Ill. each other, and independently selected from the group In Some embodiments, naturally derived porphyrins are consisting of Cis-alkyl, C-s-alkenyl, Cis-alkynyl, and Suitable. Such as the porphyrin ligands found in heme or C-2-cycloalkyl; preferably wherein each R'' are identical US 2016/0304747 A1 Oct. 20, 2016

or different from each other and independently selected from preferred embodiment, components (b) and (c) of the drier the group consisting of Cis-alkyl; more preferably wherein composition are provided as the complex defined by Reach each R'' is methyl; Registration Number 01-21 19919049-35-0000. 0241 wherein n is an integer in a range between 1 and 5, 0254. In some preferred embodiments, the drier compo preferably between 2 and 5, for example 1, 2, 3, 4, or 5, more sition comprises a composition comprising <5% 2-ethyl preferably wherein n is 2: hexanol (CAS: 104-76-7, EG: 203-234-3), <10% Drycoat 0242 wherein X, Y, and Z are identical or different from Manganese complex (CAS: 1381939-25-8, EG: 937-913-7, each other, and are RCOO; and registration number: 01-21199.19049-35-0000), and 70-90% 0243 wherein each R" are identical or different from dearomatised kerosene (CAS: 64742-48-9, EG: 265-150-3, each other, and independently selected from the group registration number: 01-2119457273-39). consisting of H, Cis-alkyl, Cis-alkenyl, Cis-alkynyl, (0255 Preferably the components (b) and (c) of the drier Cs-12-cycloalkyl, C-12-cycloalkenyl, C-2-heterocy composition can be provided as a complex, wherein said cloalkyl, C., -aralkyl; preferably wherein each R" are complex comprises manganese 2-ethylhexanoate and 2,2'- identical or different from each other and independently bipyridyl. selected from C-s-alkyl. 0256 Preferably the components (b) and (c) of the drier 0244. In some preferred embodiments, the drier compo composition can be provided as a complex, wherein said sition comprises one or more compounds of general struc complex comprises manganese 2-ethylhexanoate and ture (I*) or mixtures of different compounds of general tolyldiethanolamine. structure (I*): 0257 Accordingly, in some embodiments the complexes 0245 wherein each R'' are identical or different from of interest are carboxylic salts of structures of Formula (IX) each other, and independently selected from the group or (X) consisting of C1-1s-alkyl, 0246 wherein n is an integer in a range between 1 and 5, preferably between 2 and 5, for example 1, 2, 3, 4, or 5, more (IX) preferably wherein n is 2: 0247 wherein X, Y, and Z are identical or different from each other, and are RCOO; 0248 wherein each R" are identical or different from each other and independently selected from the group con sisting of Cis-alkyl. 0249. In some preferred embodiments, the drier compo sition comprises one or more compounds of general struc ture (II*) or mixtures of different compounds of general structure (II*):

(X)

0250 wherein n is an integer in a range between 1 and 4, preferably between 2 and 4, for example 1, 2, 3, or 4, more preferably wherein n is 2 or 3: 0251 wherein X, Y, and Z are identical or different from each other, and are selected from the group consisting of CH COO and CH (CH) CH(CHCH) COO. 0252. In some preferred embodiments, the drier compo sition comprises the compound with CAS Number 0258 Wherein M is selected from Mn, Ce, V, and Cu; and 1381939-25-8. In some preferred embodiments, the drier p, q, r, s, Z-Z and R-R7 are as described above in composition comprises the compound with EG number Formula (VI) and Formula (VII). 937-913-7. In some preferred embodiments, the drier com (0259 Preferably the components (b) and (c) of the drier position comprises the compound with the Reach Registra composition can be provided as a complex, wherein said tion Number 01-21 1991 9049-35-0000. complex comprises manganese octoate and a porphyrin 0253) In some preferred embodiment, components (b) ligand. and (c) of the drier composition are provided as the complex 0260. In some embodiments, the drier composition com defined by CAS 13.81939-25-8. In some preferred embodi prises: ment, components (b) and (c) of the drier composition are 0261 a) at least one Fe complex comprising Fe and at provided as the complex defined by EG 937-913-7. In some least one nitrogen donor ligand, wherein said at least US 2016/0304747 A1 Oct. 20, 2016 20

nitrogen donor ligand is selected from the group com 0278 b-c) at least one Mn carboxylate complex of prising tetradentate, pentadentate and hexadentate formula (VIII). nitrogen donor ligands, preferably wherein the ligand is 0279. In some embodiments, the drier composition com a compound of formula (I); prises: 0262 b) at least one metal salt of a carboxylic acid, 0280 a) at least one Fe complex comprising Fe and at wherein the metal is Mn; and least one nitrogen donor ligand of formula (II) or (III), 0263 c) at least one ligand comprising at least one preferably (II); and moiety selected from the group comprising 14.7-tri 0281 b-c) at least one Mn carboxylate complex of azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, formula (I*). porphyrinyl; preferably at least one ligand comprising 0282. In some embodiments, the drier composition com at least one 1,4,7-tri-azacyclononanyl; preferably the prises: ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. 0283 a) at least one Fe complex comprising Fe and at 0264. In some embodiments, the drier composition com least one nitrogen donor ligand of formula (II) or (III), prises: preferably (II); and 0265 a) at least one Fe complex comprising Fe and at 0284 b-c) at least one Mn carboxylate complex of least one nitrogen donor ligand of formula (I); formula (II*). 10266 wherein R' and R are each independently 0285. In some embodiments, the drier composition com Selected from the group consisting of Calkyl, prises: Coaryl, heteroaryl, heteroarylCalkyl, and 0286 a) at least one Fe complex comprising Fe and at least one nitrogen donor ligand of formula (II) or (III), CalkylaminoCalkyl, wherein heteroaryl is preferably (II); and Selected from the group consisting of pyridyl, pyrazi 0287 b-c) at least one complex defined by CAS nyl, and pyrazolyl; 1381939-25-8. 0267 R and R are each independently selected from 0288. In some embodiments, the drier composition com the group consisting of —H. Calkyl, Csalkyl-O- prises: Cisalkyl, Cisalkyl-O Coaryl, Co-oaryl, 0289 a) at least one Fe complex of formula (IV); hydroxyCisalkyl, and —(CH),C(O)CR: R is 0290 b) at least one metal salt of a carboxylic acid, selected from —H. Calkyl, Caryl, or wherein the metal is Mn; and Calky1C-aryl, and m is an integer selected from 0. 0291 c) at least one ligand comprising at least one 1, 2, 3, or 4: moiety selected from the group comprising 14.7-tri 0268 each R and R7 are independently selected from azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, the group consisting of —H. —F. —Cl. —Br. —OH, porphyrinyl, preferably at least one ligand comprising Calkoxy, NH C(O) H, NH-C(O) C. at least one 1,4,7-tri-azacyclononanyl; preferably the 4alkyl, -NH2, —NH-Calkyl, and Calkyl, and, ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. 10269 X is selected from C(O)—or —C(R).) ; 0292. In some embodiments, the drier composition com wherein n is an integer selected from 0, 1, 2 or 3, and prises: each R is independently selected from the group con 0293 a) at least one Fe complex of formula (IV); and sisting of —H. —OH, Calkoxy and Calkyl; 0294 b-c) at least one Mn carboxylate complex of 0270 b) at least one metal salt of a carboxylic acid, formula (VIII). wherein the metal is Mn; and 0295. In some embodiments, the drier composition com 0271 c) at least one ligand comprising at least one prises: moiety selected from the group comprising 14.7-tri 0296 a) at least one Fe complex of formula (IV); and azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, 0297 b-c) at least one Mn carboxylate complex of porphyrinyl, preferably at least one ligand comprising formula (I*). at least one 1,4,7-tri-azacyclononanyl; preferably the 0298. In some embodiments, the drier composition com ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. prises: 0272. In some embodiments, the drier composition com 0299 a) at least one Fe complex of formula (IV); and prises: 0300 b-c) at least one Mn carboxylate complex of 0273 a) at least one Fe complex comprising Fe and at formula (II*). least one nitrogen donor ligands, having the structural 0301 In some embodiments, the drier composition com formula (II) or (III), preferably (II): prises: 0274 b) at least one metal salt of a carboxylic acid, 0302) a) at least one Fe complex of formula (IV); and wherein the metal is Mn; and 0303 b-c) at least one complex defined by CAS 0275 c) at least one ligand comprising at least one 1381939-25-8. moiety selected from the group comprising 14.7-tri 0304. According to an embodiment, the drier composi azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, tion also comprises at least one potassium (K) salt of a porphyrinyl, preferably at least one ligand comprising carboxylic acid. at least one 1,4,7-tri-azacyclononanyl; preferably the 0305 Preferably, the carboxylic acid of said at least one ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. K salt of a carboxylic acid is selected from branched-chain 0276. In some embodiments, the drier composition com or Straight-chain Saturated and unsaturated aliphatic, aro prises: matic and alicyclic monocarboxylic acids having 5 to 22 0277 a) at least one Fe complex comprising Fe and at carbon atoms, cycloaliphatic monocarboxylic acids having 5 least one nitrogen donor ligand of formula (II) or (III), to 10 carbonatoms, or mixtures of these acids, preferably the preferably (II); and carboxylic acid is selected from the group comprising 2-eth US 2016/0304747 A1 Oct. 20, 2016

ylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylpen and need not to be further described herein. The properties tanoic acid, 2-ethyl-4-methylpentanoic acid, 2-ethyl are primarily determined by the nature and the ratios of the hexanoic acid, isooctanoic acid, isononanoic acid, alcohols and acids used and by the degree of condensation. neononanoic acid, nonanoic acid, isodecanoic acid, neode Suitable alkyds include long oil, very long oil and medium canoic acid, 2-ethyldecanoic acid, isotridecanoic acid, iso oil alkyd resins e.g. derived from 45 to 85 wt % of fatty tetradecanoic acid, n-hexanoic acid, n-octanoic acid, n-de acids, preferably derived from 45 to 70 wt % of fatty acids. canoic acid, n-dodecanoic acid, cyclopentanoic acid, As used herein, the term “long oil alkyd refers to alkyd with methylcyclopentanoic acid, cyclohexanoic acid, methylcy an oil content of between 60 and 75 wt %, and a fatty acid clohexanoic acid, 1,2-dimethylcyclohexanoic acid, cyclo content of 57 to 70 wt %. As used herein, the term “medium heptanoic acid, myristic acid, Stearic acid, arachidic acid, oil alkyd refers to alkyd with an oil content of between 45 behenic acid, oleic acid, linoleic acid, tall oil fatty acid, wt % and 60 wt %, and a fatty acid content of 42 to 57 wt erucic acid, p-tert-butylbenzoic acid, monobutyl maleate, %. As used herein, the term “very long oil alkyd refers to monodecyl phthalate, naphthenic acid and mixtures thereof. alkyd with an oil content of between 75 and 85 wt %, and Particularly preferred acids include 2-ethylhexanoic acid, a fatty acid content of 70 to 80 wt %. In an embodiment, the isononanoic acid, isodecanoic acid, and mixtures thereof. alkyd is a medium oil alkyd. In another embodiment, the Preferably said K salt of a carboxylic acid is selected from alkyd is a long oil alkyd. In another embodiment, the alkyd the group comprising K-octoate, K-naphthenate and K-neo is a very long oil alkyd. To improve the performance of the decanoate. More preferably, said K salt of a carboxylic acid resins, the composition of the long oil and medium oil alkyd is K-Octoate. may be modified. For example, polyurethane modified 0306 Suitable potassium (K) driers are available from alkyds, silicone modified alkyds, styrene modified alkyds, the OM Group, Inc., and include Potassium Hex-CemR). acrylic modified alkyds (e.g. (meth)acrylic modified alkyds), 0307. In some embodiments, the drier composition also vinylated alkyds, polyamide modified alkyds, and epoxy comprises at least one Ca, Zr, Sr., Zn, Ba, Li, or Bi Salt of an modified alkyds or mixtures thereof are also suitable alkyd organic acid, preferably of a carboxylic acid. resins to be used in the present composition. 0308. In some embodiments, the drier composition also 0318 Preferably, said at least one autoxidizable alkyd comprises at least one Casalt of an organic acid. binder is selected from a medium or long oil unmodified 0309 Examples of suitable calcium (Ca) salts of an alkyd, a silicone modified alkyd, a polyurethane modified organic acid include, but are not limited to: calcium car alkyd, acrylic modified alkyd, polyamide modified alkyd, or boxylates such as calcium neodecanoates, calcium octoates, a combination thereof. Most preferably, said alkyd binder is calcium tallates, calcium linoleates, calcium propionate, a long oil (unmodified) alkyd, a silicone modified alkyd, a calcium decanate, calcium isononanoate, and calcium naph polyurethane modified alkyd, acrylic modified alkyd, poly thenates. Such calcium (Ca) driers are available from the amide modified alkyd, or a combination thereof. OM Group, Inc., and include calcium Ten-CemR), calcium 0319. The amount of alkyd binder in the present compo Cem-All(R), calcium Hex-CemR), and calcium Nap-All. sitions can typically range from about 10 to 98% by weight, 0310. In some embodiments, the drier composition also such as about 15 to about 90% by weight, preferably about comprises at least one Zr salt of an organic acid. 20 to 80% by weight, preferably about 25 to 70% by weight 0311 Examples of suitable zirconium (Zr) salts of an based on the total weight of the composition. organic acid include, but are not limited to: Zirconium 0320 In a preferred embodiment of the present invention, carboxylates Such as Zirconium propionate, Zirconium neo the alkyd binder has a solids content of at least 50%, decanoates, Zirconium octoates, and Zirconium naphthenates preferably at least 55%, more preferably at least 60% yet and mixtures thereof. Such zirconium (Zr) driers are avail more preferably at least 65%, yet more preferably at least able from the OM Group, Inc., and include zirconium 70%, whereby the solids content is defined as non-volatile Hex-Cem(R). Solids content or non-volatile matter or nVm. As used herein, 0312 Examples of suitable strontium (Sr) salts of an the term “solids content” refers to the proportion of non organic acid include, but are not limited to: strontium Volatile material contained in an adhesive, coating, ink, carboxylates Such as strontium octoate. Such strontium paint, or other suspension. It is the material left after the driers are available from the OM Group, Inc., and include volatile solvent (which serves as a carrier or vehicle for the strontium Hex-CemR). Solid content) has vaporized. 0313 According to a second aspect, the present invention 0321. The solids content may be determined by evapo also relates to a coating composition, comprising: rating to dryness a weighed sample of Solution and deter 0314 a) at least one autoxidizable alkyd based binder; mining the percent residue. More details on how the solids and content may be measured can be found in ISO3251. 0315 b) a drier composition according to the first aspect 0322. In certain embodiments, the coating composition of of the invention, and preferred embodiments thereof. the present invention further comprises anti-skinning agents 0316. According to the invention, the coating composi and anti-oxidants such as but not limited to methyl ethyl tion comprises at least one autoxidizable alkyd binder. ketoxime, n-butyl ketoxime, cyclohexanone oxime, methyl 0317. As used herein, the term “alkyd binder” or “alkyd isobutyl ketoxime, acetone oxime, 2-cyclohexylphenol, resin' are used interchangeably. Suitable autoxidizable 4-cyclohexylphenol, mono-tertiary butylhydroquinone, alkyd resin for use in the invention, are in general the diethyl hydroxylamine, 2-(1-methylpropyl)aminoethanol, reaction product of the esterification of polyhydric alcohols and 2.4-pentadione and the like. with polybasic acids (or their anhydrides) and unsaturated 0323. In a preferred embodiment, the coating composi fatty acids (or glycerol esters thereof), for example derived tion further comprises an oxime. from linseed oil, tung oil, tall oil as well as from other drying 0324. In a preferred embodiment, the coating composi or semi-drying oils. Alkyd resins are well-known in the art tion does not include any additional anti-skinning agents, or US 2016/0304747 A1 Oct. 20, 2016 22 includes only limited amounts of additional anti-skinning prising tetradentate, pentadentate and hexadentate agents. For example, the coating composition may comprise nitrogen donor ligands, preferably wherein the ligand is at most 0.01% by weight of anti-skinning agent other than a compound of formula (I); with at least 0.0001% to at an oxime, preferably at most 0.001% by weight, preferably most 1% by weight of the Fe in a), preferably at least at most 0.0001% by weight, based on the total weight of the 0.00010% to at most 0.1% by weight of the Fe in a), coating composition. Preferably the coating composition is more preferably at least 0.00015 to at most 0.01% by essentially free of anti-skinning agents other than an oxime. weight of the Fe ina), for example at least 0.0002% to Suitable oximes are such as but not limited to: formaldehyde at most 0.002% by weight of the Fe ina), considering oXime, acetaldehyde Oxime, propionaldehyde oXime, only the amount of Fe of said at least one Fe complex, acetone oxime, butyraldehyde oXime, isobutyraldehyde with weight percent being based on the total weight of oXime, methyl ethyl ketoxime, 2,3-butanedione monoxime, the alkyd binder; 4-methylpentan-2-one oxime, 3-methylbutyraldehyde 0331 b) at least one metal salt of a carboxylic acid, oXime, 2,4-dimethylpentan-3-one oxime, cyclopentanone wherein the metal is Mn, with at least 0.0001% to at oXime, hexan-2-one oxime, cyclohexanone oxime, 3-pyri most 2% by weight of the metal in b), preferably at least dinealdoxime, 4-pyridinealdoxime, heptanal oXime, 5-meth 0.0002% to at most 0.1% by weight of the metal in b), ylhexan-2-one oxime, benzaldehyde oxime, salicylaldox more preferably at least 0.0005% to at most 0.05% by ime, acetophenone oxime, and benzophenone oxime. In weight of the metal in b), for example at least 0.001% Some embodiments, the coating composition may comprise to at most 0.02% by weight of the metal in b), consid at most 0.01% by weight of anti-skinning agent other than ering only the amount of Mn of said at least one metal methyl ethyl ketoxime, preferably at most 0.001% by salt of a carboxylic acid, with weight percent being weight, preferably at most 0.0001% by weight, based on the based on the total weight of the alkyd binder; and total weight of the coating composition. Preferably the 0332 c) at least one ligand comprising at least one coating composition is essentially free of anti-skinning moiety selected from the group comprising 14.7-tri agents other than methyl ethyl ketoxime. azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, 0325 In an embodiment, the composition comprises at porphyrinyl; preferably at least one ligand comprising least 0.0001% to at most 1% by weight of the Fe in a), at least one 1,4,7-tri-azacyclononanyl; preferably the preferably at least 0.00010% to at most 0.1% by weight of ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. the Fe in a), more preferably at least 0.00015% to at most 0333. In some embodiments, the drier composition com 0.01% by weight of the Fe ina), for example at least 0.0002 prises: to at most 0.002% by weight of the Fe ina), considering only 0334 a) at least one Fe complex comprising Fe and at the amount of Fe of said at least one Fe complex, with least one nitrogen donor ligand of formula (I); with at weight percent being based on the total weight of the alkyd least 0.0001% to at most 1% by weight of the Fe ina), binder. preferably at least 0.00010% to at most 0.1% by weight 0326 In an embodiment, the composition comprises at of the Fe ina), more preferably at least 0.00015% to at least 0.0001% to at most 2% by weight of the metal in b). most 0.01% by weight of the Fe ina), for example at preferably at least 0.0002% to at most 0.1% by weight of the least 0.0002% to at most 0.002% by weight of the Fe metal in b), more preferably at least 0.0005% to at most ina), considering only the amount of Fe of said at least 0.05% by weight of the metal in b), for example at least one Fe complex, with weight percent being based on 0.001% to at most 0.02% by weight of the metal in b), the total weight of the alkyd binder; considering only the amount of metal of said at least one 0335 wherein R' and R are each independently metal salt of a carboxylic acid, with weight percent being Selected from the group consisting of C2-alkyl, based on the total weight of the alkyd binder. Coaryl, heteroaryl, heteroarylCalkyl, and 0327. In an embodiment, the coating composition com CalkylaminoCalkyl; wherein heteroaryl is prises at least 0.001% and at most 0.06% by weight of the Selected from the group consisting of pyridyl, pyrazi metal in b), based on the total weight of the alkyd binder. For nyl, and pyrazolyl; example, the coating composition may comprise at most 0336 RandR are each independently selected from 0.05% by weight of the metal in b), for example at most 0 the group consisting of —H. Calkyl, Csalkyl-O- 0.04% by weight of the metal in b), for example at most Cisalkyl, Cisalkyl-O Co-oaryl, Co-oaryl, 0.03% by weight of the metal in b), based on the total weight hydroxyCisalkyl, and —(CH),C(O)OR: R is of the alkyd binder. selected from —H. Calkyl, Caryl, or 0328. In an embodiment, the composition comprises CalkylCaryl, and m is an integer selected from 0. from 0.0001% to 2% by weight metal, preferably from 1, 2, 3, or 4: 0.0002% to 1.5% by weight metal, more preferably from 0337 each R and R7 are independently selected from 0.0005% to 1.0% by weight metal, with weight percent the group consisting of —H. —F. —Cl. —Br. —OH, being based on the total weight of the alkyd binder, wherein Calkoxy, NH C(O) H, NH-C(O) C. all metal of the composition is included, which comprises 4alkyl, -NH2 —NH-Calkyl, and Calkyl, and, the Fe of the Fe complex and the metal of the least one metal 0338 X is selected from –C(O) or -C(R) ; salt of a carboxylic acid as well as the metal of optional wherein n is an integer selected from 0, 1, 2 or 3, and additional driers. each R is independently selected from the group con 0329. In some embodiments, the drier composition com sisting of —H, -OH, Calkoxy and Calkyl; prises: 0339 b) at least one metal salt of a carboxylic acid, 0330 a) at least one Fe complex comprising Fe and at wherein the metal is Mn, with at least 0.0001% to at least one nitrogen donor ligand, wherein said at least most 2% by weight of the metal in b), preferably at least nitrogen donor ligand is selected from the group com 0.0002% to at most 0.1% by weight of the metal in b), US 2016/0304747 A1 Oct. 20, 2016

more preferably at least 0.0005% to at most 0.05% by 0348. In some embodiments, the drier composition com weight of the metal in b), for example at least 0.001% prises: to at most 0.02% by weight of the metal in b), consid 0349 a) at least one Fe complex of formula (IV); and ering only the amount of metal of said at least one metal at least 0.0001% to at most 1% by weight of the Fe in salt of a carboxylic acid, with weight percent being a), preferably at least 0.00010% to at most 0.1% by based on the total weight of the alkyd binder; and weight of the Fe in a), more preferably at least 0340 c) at least one ligand comprising at least one 0.00015% to at most 0.01% by weight of the Fe ina), moiety selected from the group comprising 14.7-tri for example at least 0.0002% to at most 0.002% by azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, weight of the Fe in a), considering only the amount of porphyrinyl, preferably at least one ligand comprising Fe of said at least one Fe complex, with weight percent at least one 1,4,7-tri-azacyclononanyl; preferably the being based on the total weight of the alkyd binder; ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. 0350 b) at least one metal salt of a carboxylic acid, 0341. In some embodiments, the drier composition com wherein the metal is Mn, with at least 0.0001% to at prises: most 2% by weight of the metal in b), preferably at least 0342 a) at least one Fe complex comprising Fe and at 0.0002% to at most 0.1% by weight of the metal in b), least one nitrogen donor ligands, having the structural more preferably at least 0.0005% to at most 0.05% by formula (II) or (III), preferably (II); with at least weight of the metal in b), for example at least 0.001% 0.0001% to at most 1% by weight of the Fe in a), to at most 0.02% by weight of the metal in b), consid preferably at least 0.00010% to at most 0.1% by weight ering only the amount of metal of said at least one metal of the Fe ina), more preferably at least 0.00015% to at salt of a carboxylic acid, with weight percent being most 0.01% by weight of the Fe ina), for example at based on the total weight of the alkyd binder; and least 0.0002% to at most 0.002% by weight of the Fe 0351 c) at least one ligand comprising at least one ina), considering only the amount of Fe of said at least moiety selected from the group comprising 14.7-tri one Fe complex, with weight percent being based on azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, the total weight of the alkyd binder; porphyrinyl, preferably at least one ligand comprising 0343 b) at least one metal salt of a carboxylic acid, at least one 1,4,7-tri-azacyclononanyl; preferably the wherein the metal is Mn, with at least 0.0001% to at ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. most 2% by weight of the metal in b), preferably at least 0352. In some embodiments, the drier composition com 0.0002% to at most 0.1% by weight of the metal in b). prises: more preferably at least 0.0005% to at most 0.05% by 0353 a) at least one Fe complex of formula (IV); and weight of the metal in b), for example at least 0.001% at least 0.0001% to at most 1% by weight of the Fe in to at most 0.02% by weight of the metal in b), consid a), preferably at least 0.00010% to at most 0.1% by ering only the amount of metal of said at least one metal weight of the Fe in a), more preferably at least salt of a carboxylic acid, with weight percent being 0.00015% to at most 0.01% by weight of the Fe ina), based on the total weight of the alkyd binder; and for example at least 0.0002% to at most 0.002% by 0344 c) at least one ligand comprising at least one weight of the Fe in a), considering only the amount of moiety selected from the group comprising 14.7-tri Fe of said at least one Fe complex, with weight percent azacyclononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, being based on the total weight of the alkyd binder; and porphyrinyl, preferably at least one ligand comprising 0354 b-c) at least one Mn carboxylate complex of at least one 1,4,7-tri-azacyclononanyl; preferably the formula (VIII); with at least 0.0001% to at most 2% by ligand is 1.4.7-trimethyl-1,4,7-tri-azacyclononane. weight of the metal in b), preferably at least 0.0002% 0345. In some embodiments, the drier composition com to at most 0.1% by weight of the metal in b), more prises: preferably at least 0.0005% to at most 0.05% by weight 0346) a) at least one Fe complex comprising Fe and at of the metal in b), for example at least 0.001% to at least one nitrogen donor ligand of formula (II) or (Ill), most 0.02% by weight of the metal in b), considering preferably (II); with at least 0.0001% to at most 1% by only the amount of metal of said at least one metal salt weight of the Fe ina), preferably at least 0.00010% to of a carboxylic acid, with weight percent being based at most 0.1% by weight of the Fe ina), more preferably on the total weight of the alkyd binder. at least 0.00015% to at most 0.01% by weight of the Fe 0355. In an embodiment, said composition can be for in a), for example at least 0.0002% to at most 0.002% mulated as an emulsion, preferably an alkyd emulsion. by weight of the Fe ina), considering only the amount Alkyd emulsions can be made in a variety of different of Fe of said at least one Fe complex, with weight methods. In an embodiment, said composition additionally percent being based on the total weight of the alkyd comprises water and an alkyd emulsion is obtained by phase binder; and inversion or homogenisation. Despite the choice of emulsion 0347 b-c) at least one Mn carboxylate complex of technology/process the outcome is dispersed alkyd droplets formula (VIII); with at least 0.0001% to at most 2% by in a water phase, wherein the water is the continuous media weight of the metal in b), preferably at least 0.0002% of the system. Emulsifiers can be used. A combination of two to at most 0.1% by weight of the metal in b), more or more different Surfactants may be used, Such as a com preferably at least 0.0005% to at most 0.05% by weight bination of one ionic (Small molecule that possesses high of the metal in b), for example at least 0.001% to at diffusion rate) for promoting the drops during the formation most 0.02% by weight of the metal in b), considering and one nonionic (large polymeric Surfactant) for stabilizing only the amount of metal of said at least one metal salt the droplets on a long term perspective. Alternatively stable of a carboxylic acid, with weight percent being based alkyd emulsions can be produced in the absence of an on the total weight of the alkyd binder. external emulsifier by neutralizing the free carboxyl groups US 2016/0304747 A1 Oct. 20, 2016 24 of the alkyd resin with an amine. After neutralization alkyd less than 25% by weight, such as less than 20% by weight, resins can be emulsified directly in water without use of low such as less than 15% by weight, such as less than 10% by molecular weight emulsifiers. The shearing device can be for weight, such as less than 5% by weight, or, in Some cases, instance a dissolver, specially designed stirrer, rotor-stator less than 2% by weight, or, in yet other cases, less than 1% homogenizator or high pressure homogenizator. A typical by weight, with the '% by weight being based on the total solid content of an alkyd emulsion is from 30-60%. weight of the coating composition. The amount of water 0356. Preferably, the coating composition is a solvent should remain lower than 25% by weight such that the alkyd borne coating composition. binder remains in the continuous phase. 0357. As used herein, the term “solvent-borne coating 0363. In a preferred embodiment, the coating composi composition” refers to a composition that utilizes one or tion further comprises at least one organic solvent in an more volatile organic materials as the primary dispersing amount of about 0.1% by weight to about 50% by weight, medium. According to certain embodiments, the coating preferably about 1.0% by weight to about 45% by weight, compositions of the present invention can be substantially preferably about 5% by weight to about 40% by weight, free of water, or, in Some cases, completely free of water. preferably about 10% by weight to about 35% by weight, 0358 As used herein, the term “volatile organic material' preferably about 15% by weight to about 30% by weight, refers to any organic compound having an initial boiling based on the total weight of the coating composition. point less than or equal to 250° C. measured at a standard 0364. In certain embodiments, the coating compositions pressure of 101.3 kPa. of the present invention comprise at least one colorant. The 0359. As used herein, the term “organic compound colorant component of the coating composition may com refers to any compound containing at least the element prise one or more inorganic or organic, transparent or carbon and one or more of hydrogen, oxygen, Sulfur, phos non-transparent pigments. Non-limiting examples of Such phorus, silicon, nitrogen, or a halogen, with the exception of pigments are titanium dioxide, iron oxides, mixed metal carbon oxides and inorganic carbonates and bicarbonates. oxides, bismuth Vanadate, chromium oxide green, ultrama 0360 Volatile organic materials are often included in rine blue, carbon black, lampblack, monoazo and disaZo coating compositions to reduce the viscosity of the compo pigments, anthraquinones, isoindolinones, isoindolines, qui sition sufficiently to enable forces available in simple coat nophthalones, phthalocyanine blues and greens, dioxazines, ing techniques, such as spraying, to spread the coating to quinacridones and diketo-pyrrolopyrroles; and extender pig controllable, desired and uniform thicknesses. Also, volatile ments including ground and crystalline silica, barium Sul organic materials may assist in Substrate wetting, resinous fate, magnesium silicate, calcium silicate, mica, micaceous component compatibility, package stability and film forma iron oxide, calcium carbonate, Zinc oxide, aluminum tion. Non-limiting examples of Suitable volatile organic hydroxide, aluminum silicate and aluminum silicate, gyp materials (also referred as solvent) for use in the present Sum, feldspar, talcum, kaolin, and the like. The amount of composition include aliphatic, cycloaliphatic, aromatic pigment that is used to form the coating composition is hydrocarbons and oxygenated solvents, such as hexane, understood to vary, depending on the particular composition heptane, octane, isooctane, cyclohexane, cycloheptane, tolu application, and can be Zero when a clear composition is ene and Xylene; isoparafins; ketones, such as methyl ethyl desired. ketone and methyl isobutyl ketone; alcohols, such as iso 0365 For example, a coating composition may comprise propyl alcohol, normal-butyl alcohol and normal-propyl up to about 300% by weight, for example about 0 to about alcohol; monoethers of glycols, such as the monoethers of 200% by weight of pigment based on the solids content of ethylene glycol and diethylene glycol, di-ethers of glycols the alkyd resin (pigment/binder), preferably up to 100% by Such as dipropylene glycol dimethyl ether; monoether glycol weight of pigment based on the Solids content of the alkyd acetates, such as 2-ethoxyethyl acetate; as well as compat resin. Depending on the particular end use, a preferred ible mixtures thereof. As examples of such solvents may be composition may comprise approximately 0 to 100% by mentioned hydrocarbon solvents available under the trade weight of pigment based on the Solids content of the alkyd marks Shellsol H, Shellsol K. Shellsol D40, Shellsol D60, CS1. Shellsol D70, and Shellsol AB, all from Shell Chemicals, the 0366. The coating compositions of the present invention Netherlands, the trademarked Solves.so 150 solvent from may include other additives, e.g. catalysts, other pigments Esso and also: EXXsol D40, EXXSol D60 and EXXSol D80, and pigment pastes, dyes, fillers, stabilizers, thixotropic and solvents such as ethyl diglycol, ethyl glycol acetate, agents, anti-Sagging agents, anti-oxidants, antifouling butyl glycol, butyl glycol acetate, butyl diglycol, butyl agents, anti-gelling agents, bactericides, fungicides, algae diglycol acetate, and methoxypropylene glycol acetate. Pref cides, insecticides, anti-settling agents, antifoaming agents, erably the solvent is an aliphatic hydrocarbon solvent, slip agents, flow and leveling agents, rheological modifiers, preferably a high-boiling aliphatic hydrocarbon Solvent, photo-initiators, UV-absorbers, synergists, HALS-radical such as Shellsol D40 and D60. (The boiling point range for Scavengers, corrosion inhibitors, matting agents, waxes, Shellsol D40 is 163-196° C. and for D60: 177-213° C.). mineral oils, flame retardants, anti-static agents, loss of dry 0361. As used herein, the term “substantially free” means inhibitors, optical brighteners, adhesion promoters, diluents, that the material being discussed is present in the composi elastomers, plasticizers, air release agents, desiccants, anti tion, if at all, as an incidental impurity. In other words, the crater additives, reinforcing agents, dispersing aids, Sub material does not affect the properties of the composition. As strate wetting agents, odorants, corrosion-inhibitive pig used herein, the term “completely free” means that the ments, additional hardeners and additional curable material being discussed is not present in the composition at compounds, depending on the application. Certain embodi all. ments of the coating compositions of the present invention 0362. In certain embodiments, the amount of water pres include Surface active agents, such as any of the well known ent in the coating compositions of the present invention is anionic, cationic or nonionic Surfactants or dispersing US 2016/0304747 A1 Oct. 20, 2016

agents. Examples of Suitable additives that may be added to to +50° C., in particular from 0° C. to 40° C., more in the coating composition may be found in Additives Guide, particular from 3 to 25° C. However, compositions of the Paint & Coatings Magazine, May 2006, hereby incorporated present invention may be cured by additional heating. by reference. If desired, other resinous materials can be 0377 The coating compositions of the present invention utilized in conjunction with the aforementioned alkyd resins. may be used as a single coating, a top coating, a base coating 0367 The metal drier combinations and optionally colo in a two-layered system, or one or more layers of a multi rants, pigments and extenders and optionally other additives layered system including a clear top coating composition, may be formulated into the coating compositions by mixing colorant layer and base coating composition, or as a primer and, if appropriate, dispersing and grinding with the liquid layer. A typical opaque system may comprise: 1 or 2 layers binder. primer and 1 or 2 layers of top coat (a total of 3 layers). 0368. In a preferred embodiment of the invention, the Alternative opaque systems may comprise: 1 primer layer, 1 coating composition is formulated as a one package coating layer of mid coat and 1 layer top coat. Examples of trans composition, also referred herein as one-component (1K) parent systems may comprise 1 layer of impregnant and 3 coating composition. layers of top coats or 3 layers of top coat for maintenance 0369. A “1K” or “one package” composition will be work. understood as referring to a composition wherein all of the 0378. The invention will be more readily understood by components are maintained in the same container after reference to the following examples, which are included manufacture, during storage, etc. A “two packages' or “2K merely for purpose of illustration of certain aspects and composition will be understood as referring to a composition embodiments of the present invention and are not intended wherein two components are maintained separately until just to limit the invention. prior to application. A "multi packages' or “multicompo nents' composition will be understood as referring to a Examples composition wherein various components are maintained 0379. Several examples and comparative examples are separately until just prior to application. described hereunder illustrating the effect of the composi 0370. The coating composition according to the inven tions according to embodiments of the present invention on tion can be used and/or formulated as varnish, lacquer, paint, the drying and skinning properties. stain, enamel, printing ink or floor covering and similar 0380 Unless otherwise indicated, all parts and all per compositions which contain autoxidizable alkyd binders. centages in the following examples, as well as throughout 0371. According to a third aspect, the present invention the specification, are parts by weight or percentages by also relates to the use of the coating composition according weight respectively. to the second aspect of the invention in a varnish, lacquer, 0381 Drying times were assessed in the following man paint, stain, enamel, printing ink or floor covering. 0372 According to a fourth aspect, the present invention 0382. The test composition was cast on a glass plate by also relates to a Substrate having applied thereon a coating using a draw bar with a gap size of 100 um. composition according to the second aspect of the invention. 0383 Dust-free: The coating is considered dust-free if 0373 The coating compositions of the present invention it does not pull fibers when a wad of cotton is blown can be applied to various Substrates including wood, paper, gently of a drying film in a horizontal direction. foam, and synthetic materials (such as plastics including 0384 Tack-free: The coating is considered tack free if elastomeric Substrates), leather, textiles, glass, ceramic, met it does not pull fibers when a wad of cotton is placed on als (such as iron, Steel and aluminum), concrete, cement, the drying film with a load of 1 kg/3 cm2 for 10 seconds brick, and the like. and afterwards blown gently away in a horizontal 0374. As a result, the present invention is also directed to direction. Substrates at least partially coated with at least one coating 0385) Drying times were obtained under ambient condi composition of the present invention. The Substrates may be tions of 23° C. and 50% RH and under adverse drying pretreated before application of the at least one coating conditions of 5° C. and 85% RH. composition. The Substrates may be post-treated after appli 0386 The storage stability tests were performed in closed cation of the at least one coating composition, with any other jars filled to 40% of the volume and having an air packed compositions. head space of 60%. The jars containing the paint products 0375 Any known method can be used to apply the were stored at 23° C. and examined at specified time coating compositions of the invention to a Substrate. Non intervals for signs of skin formation. A skin on the Surface limiting examples of such application methods are spreading of the composition was considered to have formed when it (e.g., with paint pad or doctor blade, or by brushing or had sufficient tensile strength to Support agentle indentation rolling), spraying (e.g., air-fed spray, airless spray, hot spray, by a spatula. Anti-skinning performance was defined as the and electrostatic spray), flow coating (e.g., dipping, curtain number of days at which skin formation was first observed. coating, roller coating, and reverse roller coating), and 0387 Discoloration is inversely proportional to the per electrodeposition. (See generally, R. Lambourne, Editor, centage of whiteness in the color of the dried coat and Paint and Surface Coating: Theory and Practice, Eilis Hor percentage whiteness can be conveniently measured by wood, 1987, page 39 et seq.). conventional spectrophotometric techniques. Therefore per 0376. The coating compositions of the present invention centage whiteness is a convenient inverse measure of dis can be applied and fully cured at ambient temperature coloration. To measure the initial whiteness and the yellow conditions in the range of from about -10° C. to 50° C. ing of the coating film, the test formulations were applied to Curing of said polymer composition according to the inven prepared color cards by using a draw bar with a gap size of tion typically can proceed very rapidly, and in general can 250 lum. The films were allowed to dry under controlled take place at a temperature within the range of from -10°C. conditions of constant temperature and humidity for 24 US 2016/0304747 A1 Oct. 20, 2016 26 hours. The relative whiteness of a paint film was measured 0399 Borchi(R) OXY-Coat 1101: contains 1 wt % Fe by conventional spectrophotometric techniques according to complex (bispidon ligand), equivalent to 0.09 wt % Fe. the Cie-lab algorithm. After 2 weeks of storing in daylight, dissolved in water, commercially available from OMG, these color cards were placed in an oven under conditions of comprising the complex of formula (IV) (CAS nr. 50° C. and the air fully saturated with water vapor for 24 478945-46-9, also known as iron (1+).chlorodimethyl hours and were measured again. 9,9-dihydroxy-3-methyl-2,4-di-(2-pyridyl-kN)-7-(2- 0388 A typical base paint without metal driers was pyridinyl-kN)methyl-3,7-diazabicyclo[3.3.1 nonane prepared by mixing together the constituents listed in Table 1,5-dicarboxylate-kN3.kN7-chloride(1-)). 1. 0400 Nuodex DryCoat: contains a manganese-amine TABLE 1. complex, equivalent to 1 wt % Mn, commercially available from Rockwood Pigments, UK (product num constituents parts by weight ber DCOAT). long oil alkyd 26.4 polyurethane modified alkyd 38.2 04.01. According to the manufacturer, Nuodex Drycoat acrylic modified alkyd 10.6 comprises <5% 2-ethyl-hexanol (CAS: 104-76-7, EG: 203 high boiling aliphatic hydrocarbon solvent 3.8 defoamer 0.7 234-3), <10% Drycoat-Manganese complex (CAS: calcium (5%) drier 2.2 1381939-25-8, EG: 937-913-7, registration number: zirconium (18%) drier 2.2 white alkyd colorant 9.9 01-21 19919049-35-0000), and 70-90% de-aromatised kero black alkyd colorant 6.0 sene (CAS: 64742-48-9, EG: 265-150-3, registration num total 1OO.O ber: 01-2119457273-39). 0402 Patcom 25 16: contains a mixture of manganese 0389. The solids content of the long oil alkyd was 90% 2-ethylhexanoate and 2,2'-bipyridyl, equivalent to 2.4 nvm, the solids content of the polyurethane modified alkyd to 4.8 wt % of Mn, commercially available from was 75% invm and the solids content of acrylic modified Patcham. Patcom 2516 contains 15-30% of Mn 2-eth alkyd was 85% (nvm). The total solids binder content of the ylhexanoate (EC 240-085-3, CAS 15956-58-8), 2.5- base paint in Table 1 was 68.4 wt % (including the alkyd 10% 2,2'-bipyridyl (EC 206-674-4, CAS 366-18-7), resins in the black and white colorant). and 50-80%. 2-butoxyethanol (EC 203-905-0, CAS 0390 zirconium (18%) drier: siccative based on Zirco 111-76-2). nium 2-ethylhexanoate and having a Zirconium content of 18% 0403. DriCAT 2700F: contains a complex comprising 0391 calcium (5%) drier: siccative based on calcium manganese octoate and a porphyrin ligand, equivalent isononanoate and having a calcium content of 5% to 0.8 wt % Mn, commercially available from Dura. 0392 An enamel was prepared by mixing together the DriCat 2700F comprises approximately 5 wt % of constituents listed in Table 1 with a drier composition manganese carboxylate (EINECS 240-085-3, CAS according to the invention or with a comparative drier 15956-58-8), approximately 60 wt % 1-hexanol, composition, as shown in Table 2. 2-ethyl-(EINECS 203-234-3, CAS 104-76-7), approxi 0393 Following compounds were used: mately 50 wt % distillates, petroleum, hydrotreated 0394 Methyl ethyl ketoxime, also abbreviated as light (EINECS 265-149-8, CAS 64742-47-8). MEKO. The MEKO commercially available from 0404 Worlee.Add VP 2500: contains a mixture of Rockwood under the tradename Exkin II and the manganese 2-ethylhexanoate and tolyldiethanolamine, methyl ethyl ketoxime content was >99%. equivalent to 0.6-1.1 wt % Mn, commercially available 0395 Exkin OXF: MEKO-free antiskinning agent, from Worlee. comprising diethylhydroxylamine, triphenyl phosphite and strontium carboxylate, commercially available 0405 Potassium Hex-Cem: contains potassium 2-eth from Rockwood. ylhexanoate, equivalent to 15 wt % K, commercially 0396 Ascinin R Anti Skin 0444: MEKO-free antiskin available from OMG ning agent, comprising an amino compound, commer 0406 Drying times (dust-free and tack-free) are shown in cially available from OMG. hours:minutes. The time for development of a skin is shown 0397) Cobalt (10%) drier: siccative based on cobalt neodecanoate and having a cobalt content of 10%, in days. commercially available from OMG-Borchers as Borch 0407 The data in table 2 demonstrate that the coating ers(R Deca Cobalt 10. composition and the drier composition according to embodi 0398 Borchi(R) OXY-Coat: contains 1 wt % Fe-com plex (bispidon ligand), equivalent to 0.09 wt % Fe. ments of this invention show reduced skinning while main dissolved in propylene glycol (99 wt %, EINECS taining excellent drying properties (even under adverse 200-33-8-0), commercially available from OMG, com drying conditions such as low temperature and high humid prising the complex of formula (IV) (CAS nr. 478945 ity). 46-9, also known as iron (1+).chlorodimethyl-9.9- dihydroxy-3-methyl-2,4-di-(2-pyridyl-kN)-7-(2- 0408. The metal concentrations of the examples in Table pyridinyl-kN)methyl-3,7-diazabicyclo[3.3.1 nonane 2 and 3 are 0.0038%-0.013% Mn (based on solids binder) 1,5-dicarboxylate-kN3.kN7-chloride(1-)). and 0.00023%-0.00116%. Fe (based on solids binder). US 2016/0304747 A1 Oct. 20, 2016

TABLE 2 comparative comparative comparative comparative comparative comparative comparative comparative example 1 example 2 example 3 example 4 example 5 example 6 example 7 example 8

base paint 1OO 100 1OO 100 100 1OO methyl ethyl 1.76 O.62 O.62 O.62 1.76 O.62 ketoxime Exkin OXF O.04 Ascinin (R Anti O.S3 Skin 0444 cobalt (10%) drier 0.44 Borchi (R) OXY O.88 O.88 O.88 O.88 Coat Borchi (R) OXY O.88 O.88 Coat 1101 Nuodex DryCoat O.88 Patcom 2516 DriCAT 27OOF Worlee Add VP 2SOO Potassium Hex Cem (15%) drying times (hours: minutes) dust-free O1:20 O2:00 O2:40 05:10 OS:10 O1:55 O2:15 O1:55 tack-free O1:35 03:25 05:15 07:05 07:05 O3:20 O3:20 O2:25 drying times (hours: minutes) at S. C. 85% RH dust-free O4:45 OS:10 O6:20 18:45 19:00 OS:OO 06:15 O4:00 tack-free OS:20 07:10 O8:10 20:00 20:30 O7:40 08:30 05:15 time required for >150 <1 4 7 18 <1 3 >150 development of skin (days) comparative example 9 example 1 example 2 example 3 example 4 example 5 example 6 example 7

base paint 100 100 100 1OO 100 1OO 100 methyl ethyl O.62 O.62 O.62 O.62 O.62 O.62 O.62 ketoxime Exkin OXF Ascinin (R Anti Skin 0444 cobalt (10%) drier Borchi (R) OXY O.18 0.44 O.88 O.88 O.88 O.88 Coat Borchi (R) OXY Coat 1101 Nuodex DryCoat O.88 O.88 O.26 Patcom 2516 O.88 O.26 DriCAT 27 OOF 2.65 Worlee Add VP 0.44 2SOO Potassium Hex O.35 Cem (15%) drying times (hours:minutes) at 23° C. SO% RH

dust-free O4:45 O1:25 O1:35 O1:25 O1:OS O2:30 O2:30 O1:40 tack-free 05:05 O1:55 O2:10 O1:55 O1:40 O2:SO O3:00 O2:30 drying times (hours:minutes) at S. C. 85% RH

dust-free 03:55 03:35 03:15 03:05 05:10 05:30 O4:30 tack-free 04:SO O4:30 04:05 O3:50 06:00 O6:40 05:30 time required for >150 >150 >150 >150 >150 >150 >150 development of skin (days) US 2016/0304747 A1 Oct. 20, 2016 28

04.09. A white formulation was prepared by mixing together the constituents listed in Table 3. 0410 Drying times (dust-free and tack-free) are shown in hours: minutes. The time for development of a skin is shown in days. TABLE 3 comparative comparative comparative example 10 example 11 example 12 example 8 Parts by weight long oil alkyd (80% invm) 28.5 28.4 28.4 28.4 polyurethane modified alkyd (75% invm) 28.7 28.6 28.6 28.6 acrylic modified alkyd (85% invm) 8.0 7.9 7.9 7.9 dispersant O.S O.S O.S O.S titanium dioxide 23.4 23.3 23.3 23.3 high boiling aliphatic hydrocarbon solvent 5.5 5.5 5.5 5.5 defoamer O6 O.6 O.6 O.6 calcium (5%) drier 2.1 2.1 2.1 2.1 zirconium (18%) drier 1.7 1.7 1.7 1.7 methyl ethyl ketoxime O.8 O.8 O.8 O.8 cobalt (10%) drier O.3 Nuodex DryCoat 0.7 O.9 O.2 Borchi OXY-Coat 0.7 drying times (hrs:min), colouristic performances (Cie-whiteness)

Dust-free (23° C.50% RH) 1:10 1:30 1:15 1:05 Tack-free (23° C./50% RH) 1:30 2:05 1:55 1:35 Dust-free (5° C./85% RH) 4:10 2:55 2:45 2:55 Tack-free (5° C./85% RH) 4:55 3:55 3:45 3:50 Whiteness (%) 68.5 66.2 62.1 74.5 Whiteness (%), after 24 h and 50° C. 64.1 52.5 SO.4 63.9

0411. The data in table 3 demonstrate that in a white 2. A drier composition according to claim 1, wherein the formulation (comparative examples 11 and 12), it is shown ligand in a) is a compound of formula (I); that high amounts of the Mn-based driers are required to obtain fast drying but these high Mn-concentrations com (I) promise unacceptably the esthetical properties (whiteness

and yellowing) of the film. It has been discovered that only low concentrations of Mn ions are needed for a successful performance of the composition 8 and that the level of discoloration of the dried coat of paint is at least tolerable and can even be lower than the levels obtained by conven tional cobalt systems.

1. A drier composition for an autoxidizable alkyd based coating composition, comprising: wherein R' is selected from the group consisting of a) at least one Fe complex comprising Fe and at least one C-2-alkyl, Co-oaryl, heteroaryl, heteroarylCgalkyl, nitrogen donor ligand, wherein said at least nitrogen and CalkylaminoCalkyl, wherein heteroaryl is donor ligand is selected from the group comprising Selected from the group consisting of pyridyl, pyrazi tridentate, tetradentate, pentadentate and hexadentate nyl, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl, nitrogen donor ligands; pyrimidinyl, triazolyl and thiazolyl, preferably pyrid b) at least one metal salt of a carboxylic acid, wherein the din-2yl; wherein R' is optionally substituted with one metal is selected from the group comprising: Mn, Ce, or more Substituents, each independently selected from V, and Cu; and the group consisting of C-12alkyl, Co-oaryl, c) at least one ligand comprising at least one moiety Co-oarylCoalkyl: Selected from the group comprising 1,4,7-tri-azacy R is selected from the group consisting of C-2 alkyl, clononanyl, 2,2'-bipyridyl, 1,10-phenantrolinyl, imida Coaryl, heteroaryl, heteroarylCalkyl, and Zolyl, pyrazolyl, porphyrinyl, aliphatic, cycloaliphatic, CalkylaminoCalkyl, wherein heteroaryl is and aromatic amines. Selected from the group consisting of pyridyl, pyrazi US 2016/0304747 A1 Oct. 20, 2016 29

nyl, pyrazolyl pyrrolyl, imidazolyl, benzimidazolyl, wherein R' and Rare each independently selected from pyrimidinyl, triazolyl and thiazolyl, preferably pyrid the group consisting of C-2-alkyl, Co-oaryl, het din-2yl; wherein R is optionally substituted with one eroaryl, heteroarylCalkyl, and CalkylaminoC. or more Substituents, each independently selected from 6alkyl; wherein heteroaryl is selected from the group the group consisting of C-12alkyl, Co-oaryl, consisting of pyridyl, pyrazinyl, and pyrazolyl; Co-oarylC1-galkyl, Rand Rare each independently selected from the group R is selected from the group consisting of -H, consisting of —H, Cisalkyl, Csalkyl-O-C salkyl, Calkyl, C-alkyl-O-C-alkyl, C-alkyl-O- Cisalkyl-O Co-oaryl, Co-oaryl, hydroxyCisalkyl, Co-oaryl, Co-oaryl, hydroxyC-12alkyl, and -(CH2) and —(CH),C(O)OR: R is selected from —H. C(O)OR; wherein R is selected from -H, Calkyl, Co-oaryl, or C-alkylCo-oaryl, and m is an Calkyl, Co-oaryl, or CalkylCo-oaryl, and wherein integer selected from 0, 1, 2, 3, or 4: m is an integer selected from 0, 1, 2, 3, or 4, wherein R is optionally substituted with one or more substitu each Rand Rare independently selected from the group ents, each independently selected from the group con consisting of —H. —F. —Cl. —Br. —OH, Calkoxy, sisting of C-galkyl, Co-oaryl, halogen, Calkoxy, NH C(O)—H, -NH C(O)—C alkyl, - NH, haloCalkyl, and haloCalkoxy; —NH-C-alkyl, and Calkyl; and, R" is selected from the group consisting of —H, X' is selected from C(O)—or —C(R) : wherein Calkyl, C-alkyl-O-C-alkyl, C-alkyl-O- n is an integer selected from 0, 1, 2 or 3, and each R Coaryl, Coaryl, hydroxyC-alkyl, and -(CH2) is independently selected from the group consisting of C(O)OR': wherein R is selected from -H, —H, -OH, Calkoxy and Calkyl; Calkyl, Co-oaryl, or CalkylCo-oaryl, and wherein 4. The drier composition according to any one of claims m is an integer selected from 0, 1, 2, 3, or 4, wherein 1 to 3, further comprising: R" is optionally substituted with one or more substitu d) a K salt of a carboxylic acid. ents, each independently selected from the group con 5. The drier composition according to any one of claims sisting of C-galkyl, Co-oaryl, halogen, Calkoxy, 1 to 4, wherein the metal in b) is selected from Mn or Ce, haloCalkyl, and haloCalkoxy; preferably, wherein the metal in b) is Mn. R is selected from the group consisting of -H, halogen, 6. The drier composition according to any one of claims —OH, Calkoxy, —NH COO)—H, NH C(O) 1 to 5, wherein the carboxylic acid is selected from Calkyl, -NH2, —NH-C-alkyl, and C-alkyl: branched-chain or straight-chain Saturated and unsaturated wherein R is optionally substituted with one or more aliphatic, aromatic and alicyclic monocarboxylic acids hav substituents, each independently selected from the ing 5 to 22 carbon atoms, cycloaliphatic monocarboxylic group consisting of Coalkyl, Co-oaryl, halogen, acids having 5 to 10 carbon atoms, or mixtures of these Calkoxy, haloCalkyl, and haloCalkoxy; acids, preferably the carboxylic acid is selected from the R’ is selected from the group consisting of -H, halogen, group comprising 2-ethylbutanoic acid, 2,2-dimethylpen —OH, Calkoxy, —NH COO)—H, NH C(O) tanoic acid, 2-ethylpentanoic acid, 2-ethyl-4-methylpen Calkyl, -NH2, —NH-C-alkyl, and C-alkyl: tanoic acid, 2-ethylhexanoic acid, isooctanoic acid, wherein R is optionally substituted with one or more isononanoic acid, neononanoic acid, nonanoic acid, isode substituents, each independently selected from the canoic acid, neodecanoic acid, 2-ethyldecanoic acid, isotri group consisting of Coalkyl, Co-oaryl, halogen, decanoic acid, isotetradecanoic acid, n-hexanoic acid, n-oc Calkoxy, haloCalkyl, and haloCalkoxy; tanoic acid, n-decanoic acid, n-dodecanoic acid, X' is selected from C(O)—or —C(R) : wherein cyclopentanoic acid, methylcyclopentanoic acid, cyclo n is an integer selected from 0, 1, 2 or 3, and each R hexanoic acid, methylcyclohexanoic acid, 1,2-dimethylcy is independently selected from the group consisting of clohexanoic acid, cycloheptanoic acid, myristic acid, Stearic —H, -OH, C-12alkoxy and C-12alkyl; wherein R is acid, arachidic acid, behenic acid, oleic acid, linoleic acid, optionally substituted with one or more substituents, tall oil fatty acid, erucic acid, p-tert-butylbenzoic acid, each independently selected from the group consisting monobutyl maleate, monodecyl phthalate, naphthenic acid of Coalkyl, Caryl, halogen, Cigalkoxy, haloC and mixtures thereof. 6alkyl, and haloCalkoxy. 7. The drier composition according to any one of claims 3. A drier composition according to claim 1 or 2, wherein 1 to 6, wherein the at least one ligand in c) is a compound the ligand in a) is a compound of formula (I); of formula (V), wherein

(I) (V) R20 N Y (--) R20 each R' is independently selected from the group con sisting of Calkyl, C-scycloalkyl, heterocycloalkyl, heteroaryl, Co-oaryl and Co-oaryl-Coalkyl, each group being optionally Substituted with one or more substituents each independently selected from the US 2016/0304747 A1 Oct. 20, 2016 30

group consisting of —OH, Calkoxy, phenoxy, car 11. The coating composition according to claim 9 or 10, boxylate, carboxamide, carboxylic ester, Sulfonate, comprising at most 0.01% by weight of anti-skinning agent amine, C-alkylamine and —N"(R)s: other than an oxime, preferably at most 0.001% by weight, each R is selected from -H, Calkyl, Calkenyl, preferably at most 0.0001% by weight, based on the total Co-oaryl-Coalkyl, Co-oaryl-C2-alkenyl, C-alky weight of the coating composition, preferably wherein the loxy, Calkenyloxy, aminoCalkyl, aminoCalk coating composition is essentially free of anti-skinning enyl, C2-alkyl ether, Coalkenyl ether, and —CX, - agents other than an oxime. R22. each X* is independently selected from —H or Calkyl 12. The coating composition according to any one of and wherein each R’ is independently selected from an claims 9 to 11, wherein the coating composition comprises optionally substituted heteroaryl group selected from at least 0.0001% to at most 2% by weight of the metal in b). the group consisting of pyridyl, pyrazinyl, pyrazolyl, preferably at least 0.0002% to at most 0.1% by weight of the pyrrolyl, imidazolyl, benzimidazolyl pyrimidinyl, tri metal in b), more preferably at least 0.0005% to at most azolyl and thiazolyl; and, 0.05% by weight of the metal in b), for example at least wherein at least one of R is C(X) R', preferably 0.001% to at most 0.02% by weight of the metal in b), wherein the organic compound in c) is 1.4.7-trimethyl considering only the amount of metal of said at least one 1.4.7-tri-azacyclononane. metal salt of a carboxylic acid, with weight percent being 8. The drier composition according to any one of claims based on the total weight of the alkyd binder. 1 to 7, wherein components (b) and (c) of the drier compo 13. The coating composition according to any one of sition are provided as the complex defined by CAS claims 9 to 12, wherein the coating composition is a solvent 1381939-25-8. borne coating composition. 9. A coating composition, comprising: 14. Use of the coating composition according to any one a) at least one autoxidizable alkyd based binder; and of claims 9 to 13 in a varnish, lacquer, paint, stain, enamel, b) a drier composition according to any one of claims 1 to printing ink or floor covering. 8. 10. The coating composition according to claim 9, further 15. A substrate having applied thereon a coating compo comprising an oxime, preferably a ketoxime, preferably sition according to any one of claims 9 to 13. methyl ethyl ketoxime. k k k k k