INH I US 20130102709A1 «) United States «2 Patent Application Publication (10) Pub. No: US 2013/0102709 Al Jansen et al. (43) Pub, Date: Apr. 25, 2013 (54) MANGANESE SALT COMPLEX AS DRIER ‘and b) polymer comprising unsaturated fay acid resides, FOR COATING COMPOSITIONS wherein the manganese salt complex has the following stmic- (716) tovenors: Johan FranzGradus Jansen, Geleen © E whetein the anon is selected from CT, NOS” or (NL); Franelseus Adrianus Cornelis a O07, in which ease n=2; o¢ the anion 10." in which Bergman, Zwolle (NL); Engelina case n-1; wherein X.Y. are independently selete from 0, Catharina Kleuskens, Fisioo (NL); OH, OH,, OC(R,)O, and R,BO. and wherein and b are Ronald Hage, Leiden (NL) independently an integer of valve 2,3 04 Ry =H, C1-C20 alkyl optionally substituted with heteroatoms, C6-C20 aryl optionally substituted with heteroatoms; R;=C1-C20 alkyl (2) PCTPiled: Feb. 11,2011 ‘optionally substituted with heteroatoms, C5-C20.ary opton= ally substituted with heteroatoms, ora polymeric residue:and (21) Appl.No: 13877976 (86) PCTNo: — PCTIER2011/052070 Re-C1-C20 aly optionally substituted with heteroatoms, $371 (01), C6-C20 ary optionally subsitted with heteroatoms, or @ 2), (4)Date: Dee. 28,2012 polymere reso. R*—C-C20 ally osonlly subsite. a ene iinet 0.20 pny ined wih Feb. 11,2010 (EP) 101533180 Publication Classification 0 (1) ect Coop 712 (2006.01), (2) US.CL. ae cee COP 71233 (2013.01) “te usc 52498; 42773855 oH) ABSTRACT Aa air drying uto-oxidisable resin compesiton comprising ‘components: drier comprising amanganese salt complex,US 2013/0102709 AI MANGANESE SALT COMPLEX AS DRIER FOR COATING COMPOSITIONS [0001] Theinventon is directed tothe use ofa specific Mn salt complex as a deer in anauto-oxidisable coating compo- sition, to an aut-xidisable coating composition comprising such drier, fo the use of sad composition and toa substrate coated with said composition, [002] "The use of fatty acid funetionalised resin in paint products has the advantage thatthe resins ae lazy deriv able from agricultural products, which are renewable sources, They are also easily biodegraded when buried in andl sites ‘which is advantageous. Furthermore upon drying the fatty acid derived polymers yield coatings with very good hyo [Mt stailty whichis very advantageous for outdoor uses [0003] - Coatings for professional and do-it-yourself use are subject to incressing technical and ecological tition, including thenature ofthe diet. driers forexamplea metal salt which acts as a catalyst forthe auto-oxidaton reaction \which s iatated on drying. Other known synonyms for deer in the art include siccaive, desiccator or desiceative, Examples of known drier salts inche polyvalent salts con- ‘aining cobalt, calcium, copper, zine, oa, zrcoaiuay, man ‘ganese, barium, zine, strontium, ithium and potassium as the cation; and halides, niteates, sulphates, carboxylates like acetates, ethylhexanoates, ecanoates and naphthentes oF acetoacetonates asthe ain, Nowadays driers use far auto ‘oxidisable coating composition are manly based on Co cata- Iysts as peimary deers [0004] However, for reasons of environmental protection, inthe last years there isa new aim to replace these cobalt- ‘sed catalysts with more eavironmentaly friendly alterna tives for use in coatings comprising an auto-oxiisabe resin, [0005] Simple Min based catalysts like Mn ethylhexanoate ‘combined with aceylacetonate ligands and bipyridine used asdrers has been described for example by E. Houwanan, R ‘van Gorkum, J.Coat. Technol. Res. 4,491-508 (2007). How- ever, experimental results have shown that such Ma systems 4o not allow sufiient drying in a coating composition com- prising an alkyl resin, especially in relation to tack fre time ‘Furhermore when employing such a drying system the coat ings suffers from severe dark yellowing Which renders then less usefl [006] Ober ligands with aliphatic and aromatic amines are also known, as for instance in the paper of R. van Gorkum, tal in J Catalysis 252 110-118 2007), Upon evaluation of these driers it was found that they are not as active asthe shove described Mavbipyridine/acetylacetone system, 0007] Inthe article of. 0. Oyman etal entitled “A prom- ‘sing environmentally friendly manganese based catalyst for alkyd emulsion coatings” Polymer, vol. 45,11 Sep. 2004, pg. 7431-7436 there is preseated a bimetallic Ma structure [Mn,(MeTACN), (1-0)3|PF)s sed for alkyd coatings, However, also alkyd coatings comprising such Mn based catalysts donot dy witha desired ellciency, as showa herein with comparative example A under Table I of teexperimen- tal section. [0008] "A geneeal problem with sltemative catalysts is that they ether do not work wel in deying as discussed above) or they may induce undesired yellowing ofthe coating espe- cially yellowing inthe dark, Moreover, often theres astorage lability problem related toa skin formation inside te pot ‘comprising the coating composition, for which addtional aniskinning compounds are needed in te coating composi tion, Therefore, there emains a strong need for ther driers Apr. 25, 2013 forstto-oxidissble coating compositions tobe ble to formu- [ate coatings without serous adverse effet on coating prop- cies, particularly allowing fast dying. 10009] It is the object of he invention to provide a drier ‘hich is environmentally friendly and ensues the desired properties of an auto-oxiisable coating composition com- rising such drier, as described above. Another abject of the ‘vention is to provide an auto-oxidisable coating composi- tion having after drying one or more of the following prop- erties advantageous for different types of aplication, such as low yellowing. no skin formation or low skin fomation, high solids content, short dust fee andor tack free time. {0010} Theinventors surprisingly found that one or monet these objects may be met by using a specific transition meta complex as a drier fr air drying suto-oxidisable resin com- positions This is especialy surprising since by changing the anion from (PF,")sof the manganese catalyst as known from the anicle of Oyman to other anions, resulted in changing from poorhmediere drying properties vo good deying prop cis for the air drying auto-oxiisable esin compositions according tothe invention, 0011] Accordingly, in a fist aspect the invention is directed to an air drying auto-oxiisable resin composition ‘comprising components [0012] s)adriercomprising manganese salt complex, and 0013] b)apolymercompising unsaturated fatty acid resi- us, ‘wherein the manganese salt complex has the following struc> ture 0 MuiczSMe "OPPO ‘whee the anion is selected fom CI, NO,” oF 8,COO™ ia ‘which ese n-2; rte anion s SO, in which ease n-1; ‘when X,¥7 aw independently selected from 0, OH, OH, ‘0C(R,)0, and BO, and wherein aand be independently anjnteger of value 2, 30rd: R.=H, C1-C20 ally optionally subsitted with heteroat- ons or C6-C20ryl optionally substuted with iterotoms; R,=C1-C20 alls opionaly substi wih heteroatoms, -€20 aryl opionaly substituted with hetrotoms, or & polymeric residue: nd R,=C1-C20 ally opionaly substi with heteroatoms, C6-C20 aryl optionally subsite with heteroatoms, or & polymeric residue R,=C1-C20 ally optionally substiutd with heteroatoms, .°€6-C20aryl optionally substnted with eeroatoms, pre erably Ry=CeHl oF its substituted analogues [0014] Inanoieraspecttheinveatoniswlatedtotheuseof atest a manganese salt complex of suture Ts a dir for tic drying auto-ondisable resin compositions comprising a polymer comprising usstursted fay sci residues. Ri] Cn Cv. sep]US 2013/0102709 AI [0015] Another aspect the invention is directed to an air dying auto-oxidisable resin composition comprising [0016] a) a drier comprising manganese sat complex with the structure according to formula I above; [0017] 5)» polymer comprising unsoturated faty acid resides, and [0018] c) a iquid medium, 0019] The present inventor: have found that favorable properties canbe achieved by using a manganese salt com= plexsocording to formula Las. die It was found that the air ‘tying ato-oxiisable resin composition ofthe invention has very good drying behaviour, especially concering the dust freeand the ack fre drying. Furthermore, edditional alvan- tages observed where a minimal yellowing and no ski for- ‘mation when the composition was stored ina pot for several ‘weeks (Le the auto-oxidisable resin composition stayed lig vid for relatively lng period when standard antiskinning ‘agents were used), [0020] Inthe air drying ato-oxidisable resin composition ‘according to the invention preferably the manganese salt ‘complex hs the anion selected from CI- or NO, in which «ase 0-2; or the anion is SO,?", in which ease [0021] Ine air drying auto-oxiisable resin composition according to the invention preferably the manganese salt complex bas Z=0. [0022] Inthe air drying ato-oxidisable resin composition according to the invention preferbly the manganese salt ‘complex bas X and YO, and integers and bd [0023] Inthe air drying auto-oxiisable resin composition ‘according to the invention preferably the manganese salt ‘complex as X and Y—=R,COO™, integers and anion selected from CT” a NO,”, in which case anion is SO, in which ease n-1 [0024] Ia te ie drying ato-oxidisable resin composition according to the invention preferably the manganese salt complexliasX and/or isR,BO, and the anion selected from CT, NO,” of R,COO", in Which ease n=2: or the anion is $0,*, in which case n-1. More preferably the anion is R,COO”, Preferably X andor Y is C,H,BO, (i. phenylbo- ronate(2), oF Ry=C.H)oF is substituted analogues. Most preferably X and Y are C,H,BO,, and integers aan b are 4 Reference is made to Angewandte Chemie International, vol 35, page 1552-1554 July 1996) foran example ofa phenyl. boron bridged Mn(IV) dimer with MoTACN. 0025] Inthe ar drying auto-oxiisable resin composition according to the invention preferably the manganese salt ‘complex as integer aor b=2 [0026] Inte resin composition sceonding tothe invention preferably the amount of the eation of the manganese salt comple, including where present aso the polymeric residue, {0.00001 wt%, more preferably 0.0001 wt % and most preferably 20.001 wt %, based on the total solids content oF the resin (polymer) comprising unsaturated fatty acid resi- dus, Preferably the amouat of the manganese salt complex is 55 1%, more preferably $2.5 wt%, even more preferably 1 w1% and most preferably 30.5 wt % based on the total solids content ofthe polymer comprising unsaturated Laty acid residues. These upper and lower wt % limits may be ‘combined in any mannet {0027} Theamount ofthe manganese carboxylate complex ‘may also be expressed in tems of maiol manganese metal per gof otal esin composition excluding volatile onganiccom- pound i.e. mmol Mav solid resin, Preferably the amount of the manganese iiaarange from 0.00004 to 200 mano! Mav, Apr. 25, 2013 sold resin more preferably inthe range from 0.004 10 150 ‘mol Ma/kg sold resin more preferably inthe range from (0.01 100 aol Marke sold resin, [0028] With otal solids coment ofthe polymer comprising stated fat acid resis is uperstod the resin witout diluents Polymer and eesin are herein interchangeable terms [0029] _R, andlor, inte ove formulas may be poly- ‘etic residue. This s the case when the Mn complex is ‘pared insta withthe polymer) Incase R, andlor isa polymeric residue the eesidve may orginat for exanple From an ocd foto polymer. na peer embodimeat inwhichR, andor, is polymeric res the manganese saltcomples is prepared init with an uastiatd fay acid ‘modifi polymer Inan especialy prefered embodiment the fatty acid meifed polymer comprises some remaining car boxe aid groups [0030] Preferably R,—=C1-C6 ais, more preferably, is rth [0031] Combinations of diferent types ofthe manganese saltcomplex drier aeondng to fom ar included forthe purpose o this iveaton. Also combinations of any mangn- essa complex die according formula andor driers ae inched forthe purpose o his iventon 10032] Another emibocimeat ofthe invention provides an aie drying autocxidisable resin compositions coapise a ‘manganese salt complex having stuctire I andr anyother othe profemed structures described above, withthe proviso tat the manganese salt complex is otor than a manganese caoxylate complex having the fellosng siete I: o C1-C20 alkyl optionally substituted with teat coms oF C6-C20 ay ptonllysubstned wititeratoms: and are independently selected from Oand OC(RS)O, in ‘which at when XO, anda-3 when X=OC(R)O, and in ‘which b= when Y=, and b-3 when YOC(R,}O, Re=C1-C20 aig opionaly subst with hetrotoms, C6-C20 any optionally substituted with heteroatoms oF & polymere resend R,=C1-C20 ail optonally substitute with heteroatoms, C6.C20 ary optionally subsited with heterostoms, or & polymere residue [0033] In accordance with the ae drying auo-oxidisble resin composition ofthe invention, any type of polymer b) comprising unsaturated fatty acid residves oF mixtues thereof may be used. The polymer inthe sie dying autonUS 2013/0102709 AI ‘xiisable resin composition may be for instance selected fromthe group consistingof alk, vnslpolymers polyure thane resin, hyperbranched resins and mixtures thereof. [0034] Polymer b) most comprise unsaturated fatty acid resides to ensure the air drying properies, however it may further comprise saturate fatty acid resides (.e. groups) and other fanetional soups Preferably the fatty acid residue isa carboxylic aid with aC12 10 C30 carbon atom chain [0038] _Soturted and unsaturated fatty acid groups may be obtained from natural andlor artificial sources. Natural sources include animal sources andor plant sources, Animal sources may comprise aninal fat, butter fat fs ol, la iver fats, sperm whale oi andor tallow il and waxes. Examples of wanesare beeswax, candelia andor motan, Pant sources may comprise waxesanilor oils suchas vegetable cils andlor ‘non-vegtabe oils. Examples of plant ols are: biter gourd borage calendala, canola, castor, china wood, coconut, coni- fer sed, com, cottonseed, dehydrated castor, faxseed, grape seed, Jacaranda mimosifoia ee, linseed olive, pa, palm erm, peanut, pomegranate sod, rapesoed saflower, snake gourd, soyafbean), sunflower, tung andor wheat gem. Ani= ficial sources inl syhetic waxes (such s miro costal line andlor paraffin wa), dstling tall il (a by-preoct of processing pine wood) andor synthesis (Kor example by chemical andor biochemical methods), Suitable fatty acids also include, (Z)-hexadan‘-emoic[paimitleic) acid (Cstl0,),(2)-oetadecan9-enoic oleic} acid (CH,0,), OZUE DB octadece9,11,13tienoie [atalpha)cleo- stearic also c-olenstearc] acl (CyHys0,) where ee stearic acid comprises 65% ofthe faty acids of tung oi), Tica eid, (97, 122)-otadecs-9.12-dienoe [linoleic] acid (Ciatlg0)), G282,11Z,142)-cicosa-5 8,11 14-tetranoic acd arechidoni acid] (C3s,0;), 1-hydroxy97)ccta- eca--140; for semi-rying ol he iodine ‘number is ranging betwoon 125 and 140, and for non-drying oilthe iodine numbers <125 Surface Coatings”, by Svar Paul, John Wiley and Soas: p. 83) [0038] Suitable unsaturated Lat seid for providing fatty ‘acid groups inthe polymer) include ity acids derived from, soybean oil, conjugated soybean oil, palm cil, linseed oil, ‘ung il, rapescedoil, sunflower cil, conjugated sunllower il, calenila ei, wood cil, tallow ol, (dehydrated) castor il, sailower oi, tua fish ol, coconut ol and deaydrated coco ‘ut ol, and combinations threo. Apr. 25, 2013 [0039] Polymer b) may comprise any amount of unsatr- ed fatty acid residues, whichamountwillalso depend onthe polymer type. Preferably the polymer b) comprises 20 wt 5, preferably 240 wt %, more preferably 250 wt % even more preferably 240 vt %, especially preferably 270 wt % and most preferably =80 wt Y% of unsaturated fty cid residues hased on the total olds content ofthe polymerb. [0040] Besides the unsaturated faty acid residues, other Fuetional groups may be attached to the auo-oxidisable resin by means of any well known reactions. Functional groups may be intriued into the ato-oxdisable resin sing two general methods: i) by uilisng in the polymerisation ‘process to form anauto-oxiisabe resin, monomers caning the functional group; or i) utilising monomers bearing selecied recive groups and which monomers sobsogunty reacted with a compound carrying the fonctional group and also a reactive group ofthe type which will react with the selected rectve groups on the monomer to provide attach ‘ment of the functional soup tothe autoxiisabe resin via covalent bonding. [0041] Other monomers bearing fanctional groups which ‘may be incorporated in or mixed with the auto-oxitisable resinare for instance monomers comprising(methaly,pro- arg, vinyl, (meth}ery, maleic, famari,taconic fnetion- lies, keto ester group, f-Keto amide groups and any combinations thereof {0042} Polymer b) may befor example any conventional alkyd resin, By ally resin herein is meant a resin prepared from the resetion ofa polyinydriealeool, a polybasie acid and an unsaturated ior ety acid to given unsaturated ty acid residue containing ester. The unsaturation inthe ester polyol imparts latent cos-lnkabilty pon autoxidation so tat when a coating composition thereo is died in th ai, n conjunction withthe dre, theeoating material undergoes cmss-linking (by suto-oxidaton) and thereby improving its properties, forexampleitschemical sistance, hardness and! ordurabily 10043} Another example ofa polymer b) may be @ vinyl pol)mer comprising unsaturated fatty acid groups. By viyl polymer herein is meant a polymer comprising ethylenically _nsaturated monomers, also known as (poly)aerylate In an embodiment according to the invention, unsaturated. fay acid groups canbe incorporate the vinyl polymer via ty acd finetional monomers (GMA fay aed add, such as describedin US. Pat. No. 6,599,972, US. Pat, N0.6,624,23, ‘W02007/042684 and US. Pat. No. 3,988,273) o via the reaction of epoxy groups (introduced inthe backbone) and te acid groups ofthe fatty acid (suchas described in US. Pat No. 7,235,608) {0048} Another example of polymer) suitable forthe ar drying auto-xidisable resin composition of the invention ray be polyurethanes functionalized with non-aetivated doublebondsin which, forexample, at acids incorporated iaa polyester polyol which contains fatty acid. [0045] In yet another embodiment the avto-oxidsable alkyd resin comprises a hyperbranched resin or © modified hyperbranched resin. Hyperbranched macromolecules are oflen refered to as dendritic species in the an. Hyper- branched macromolecules are three-timensional highly ‘branched molecles having a tree-like structure, Macromol cvules designated as dendrimers ae highly symmetric and belong to a particular class of hyperbranched molecules that hhaveapolydispersity index of approximately 1 whereasmac= romolecules designated as hyperbranched may toa certainUS 2013/0102709 AI degree be asymmetric and yet maintain a tresfike stator. WO 20071147589 desnbes water soluble unsaturated faty acd functional hyperbranched poland, [0046] Asa panieular concep, the polymer b) may havea bockbone of for instance a polyester, plyuretne or vinyl type and OH or other reactive fanetionaities incorporated such a the unsaturated fatty acid residues can attach othe reactive groups. {0047} The OH-functonal polymeric backbone is prefer abl polymere polyol usctonality more tha 2, but may beorincludea polymere dil. Such polyol in principle may be selected from any ofthe chemical classes of polymeric polyols used or proposed to be used ina urethaaised resin Synthesis. In particular the polymere polyol may be poly «ster polyol, a polyesteramide polyol, a polyether polyol, a polythioether polyol, a polyeatbonste pool, a plyacetal Polo. apolyviny! pol andra polsilaxane polyol. More preferably the polymeric polyol is selected rom a polyester poll, polyether pool andor a polysioxane polyol, and particulary preferably i selected from a polyether polyol andlor polyester poll [W048] Conventional aiedeying skys con be obi bya polycondensation reaction of ane or more poly lear hol, one of more polycarboxic acids orth comesponding mbydies andlong hain unsaturated fat acids ris: The ‘unsaturated groups in he auto-exdisable resin en be into duced by the saturated fat acs, tay ateratively oF axkltionaly, be nttodaced by one or more of the polyols, éaroxylic acids or anhydrides or oter building blocks sed, suc as fatty mono-aleohols [0049] Theester an compriseone or more polyol buiding ‘ek, such as diols or tos. Suitable monofunctional aleo- hols include for example eiosano and lu ae. Poly ols with to hydroxy groups per molecule include diols such as ethylene glycol, dithene glycol, dipropyleae alyca, | 2eethaneol, 13-propane dio, 1-butaneiol, 1 6-hexane diol, 1,2-dodecane diol, 3-methyl- S-pentane diol, 2.24- teimetiyl,6hexane diol, 2.2, in hich ease =I Examples 2-4 and Comparative Example F-H (Clear, Non-Pigmented Coatings [0126] _As poiymerb the aid resin Url 2423 (avail abe from DSM NeoResins BV as 60% ein in Exxsol D40) wav sed {0127} Forall experiment, the Exxcol Da was evaporated ‘under reduced pressure and next the resin was dissolved the ‘sed solsens via which esi solutions eatuining 65% solids ‘wor obtained. (0128] Theamount of ie was 2 mmo! Mn metal solid resin. 1 mmol Mia comple solids based only on Mo. [0129] The dsercomplees A was wes th concentrated ‘aterolution MaMeTACN* (PF), wasuselas 1%ésoh- tiominacetono. ier the ation of the dirt theres the resin Was sored overnight. Next the esa was applied as 100 ‘micron Wet fms ona gos plate using doctor Bale andthe dying aswell a the yellowing was monitored (0130) _Ascanbe clearly sen rom the able 2 below, only ‘withthe tanstion metal deers acconing othe vention a Fexer nd more eliient drying was obtained x compared to the known manganese complex having (PF. as anion Dew x ox Dwso x Drer 4 x x x MntetAcN (PF x x br mS as woo i Bis 57 2a as [131] Itcanbe een fom able 2, tht in all cases the drier according tothe invention surprisingly outperforms the prior at MaMeTACN* (PE,"), die. [0132] Similar compositions asin examples 24 could also ‘he prepared in which the anion ofthe Ma salt complex is CI- ‘or NO,” in which ease n=2; or S0,*, in which ease n=1 Example 5-6 [0133] Example’ was repeated except that besdescatalyst ‘A also ascorbic acid palmitate was added before storing the resin overnight in order to prepare abridged carboxylate of the manganese salt complex in situ (R,, R-=CH3, X=OC (R,)0 in which R, polymeric residue).Us 2013/0102709 AL 10 TABLES Eom Se ‘ be woot L ca tw he [0134] These examples demonstrate thatthe drying ean be Furter improved when abridged carboxylate of the manga- nese salt complex is used as drier. Further more these ‘examples demonstate that this bridge carboxylate can be a polymeric esdoe and that these bridge carboxylates can be repared insta [0135] Similar compositions asin examples 5-6 could also ‘be prepaved in which te anion ofthe Ma salt complex is” ‘of NO,” in which ease n-2: or $0, in which case a=1 Example 7 Preparation of Catalyst Complex B 0136] To 26.49 g (MnM&TACN** (OAc), (complex A, 3.5% solution in water, commercially obtained from Rab CCatayties) was added 0.264 g butyric acidand 0.279 gascor- bic acid. The mixture was sired and allowed to stand over- night ater which a wate solution of Ma salt complex B was blaine. (R, =CH,, Ry=CH,, X,¥=OC(CH,)0). [0137] _A similar complex asin example 7 could also be prepared having X and Y=C,H,BO,, anda and b-4 inthe ‘ridge instead ofthe butyrate Apr. 25, 2013 Proparation of a white paint [0138] 17.55 p Titanium dioxide (Kronos TR92), and 0.16 se Nuosperse FAGOL and 4.26 g Exxsol D40 were dispersed into 25.49 g Uralac S233 Q&S (a solvent based alkyd resin, available om DSM NeoResin BY, 85 wi solids) by using a dispeema, 10139] | Next 0:92 g ofthe above propared solution of com- plex B, 0.94 g Nuodex Ca 5% and O.2g Exkin Il were mixed {nalter which the mixture was allowed to stand overnight [0140] The amount of dryer was 2 mmol Mnvkg (based on {otal resin composition) [0141] The drying chaocteristes ofa 100 micron wet film ‘were DFT 25hrs, TET 3 hrs. [0142] The film showod no wakes also not when applied 8200 micron thick film, And the liguid formulation exhib ited no skin formation ater storage time of 21 days at room temperature [0143]. For comparision a formulation was made with the sume drying chareterities but based oa cobalt. Ia this ease (021 gNuodex Co10%6, 0194 g Nuodex Ca 5%, 08g Nuodex Ze 1Phand 0.2. Exkin I had to added. The amouat of dyer ‘was 7 mol CCofkg and 21 mmol Zrkg (based on total resin composition. [0144] This example indicates that manganese salt com- plex acording tothe invention actas very efective driers for air drying auto-oxidisable resin compositions comprising a polymer having unsaturated lay acid residues, [0145] _A similar white paint could also be prepared with complex according to example having X and Y=C,H,BO,, and a and bin the bridge instead ofthe butyrate. [0146] Otter Ma salt complex dries may also be prepared and used in air drying auio-oxiisable resin compositions in ‘aeordance to the above examples, such asthe driers fro, table 4, TABLES fea fab fe ud fue af xp xh Xx 000-00" RCO ROO RCO RCO ¥ 9 9 a Re00 RCo KOO OO zt 0 09 09 0 6 6 0 0 Pe ee ee Oe BR ROH ‘rion RCO SO NO SOC RKO RG, X —GHhNO, ClsBO, GO, GO, CIO, CSNO, EMRE, E,lBO, YY GaHO, C80, GLH, CAH, 0 OO rer Bea Ts Et ee y ° CHBO, CBO, CHRO, CBO, a 40) 4) 40) 40) 46) . 30) 3) aM 34) 8US 2013/0102709 AI ul 1. An aie dying auto-oxdisable resin composition com- rising components 4) drier comprising a manganese salt complex, and >) polymer comprising unsaturated faty acid resides, ‘wherein the manganese salt complex bas the following secure 0 (sion, ‘wherein the anion is selected from CT", NO." or R,COO™, in which ease n-2; or the anion is SO." in which case 1; ‘wherein XYZ. ar independently soleted from O, OH, Offs, OC(R,JO, and R,BO, and wherein a and b are indepeadently an integer of value 2,3 0 R,=H, C1-C20 alkyl optionally substituted with heteroa- toms, C6-C20 aryl optionally substtted with beteroa- toms R-=CI-C20 alkyl optionally substituted with hetemoat- ‘ms, C6-C20 aryl optionally substituted with heteoat- toms, ora polymeric residue: and Rs=CI-C20 alkyl optionally substituted with heteroat- ‘om, C6-C20 aryl optionally substituted with heteoat- toms, ora polymeric residue R/=CI-C20 alkyl optionally substituted with heteoat- ‘oms,oFC6-C20 ary] optionally substituted withbeteroa- toms Apr. 25, 2013 2. Anairdryingauto-xidisable resin composition accord {ng claim 1 wherein the anion s selected from CT of NO, in which case n-2: or the anion is SO, in which ease 3. Anair drying auto-oxdisable resin composition accor ing to claim 1 wherein 2—O, 4. Anair drying autocoidisable resin composition acco! {ng to claim 1 wherein X andlor is R,BO:. '. Anair drying autoxidisabe resin composition accord {ng to claim 4 wherein the anion is R,COO” 6. Anair drying auto-oxdisable resin composition acvor- ‘ng claima 1 wherein R,—C,H, orits substituted analognes, 7. Anair drying auto-xidisable resin composition accor ing to claim 6 wherein X andY are, H,BO,, anda and hare 4 8. Anair drying autooxidisable resin composition accor {ng to claim 2 wherein X and Y—O, and integers a and b-4 9, Anair drying auto-xidisable resin composition accord ingto claim 2 wherein X andY¥—R,COO™ and integers a and 10. An air drying. auto-oxiisable resin composition according to claim A wherein R, is CH, 11. outing composition comprising the auto-oxidisable resin composition according to claim 1 12.4 method of coating the aut-oxidisable resin compo- sition according to claim I or the coating composition on 3 substrate, comprising adding to the coating composition the ‘manganese salt complex as defined in claim 1, applying the ‘composition on a substrate, and drying the composition inthe presence of iro obiain a coating. 13. A substrate coated with @ composition according 10 claim 1. 14. Use of a manganese salt complex as defined in claim 1 asa drier forairdrying of anto-oxidisable resin compositions ‘according o eliza 1 18, Use ofa composition according to claim 1 in paints, adhesives, lacquers, inks and vanishes