Title of Invention | LIQUID HARDENING |
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Abstract | The present invention relates to a curing agents for air- drying alkyd-based resins, coatings, such as paint, varnish or wood stain, inks and linoleum floor coverings, based on an iron/manganese complex containing tetradentate, pentadentate or hexadentate nitrogen donor ligands. |
Full Text | FORM2 THE PATENTS ACT, 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) 1. Title of the invention. - "LIQUID HARDENING" 2. Applicant(s) (a) NAME : UNILEVER PLC (b) NATIONALITY : A British Company (c) ADDRESS : Unilever House, Blackfriars, London EC4P 4BQ,United Kingdom 3. PREAMBLE TO THE DESCRIPTION The following specification particularly describes the invention and the manner in which it is to be performed: WO 2008/003652 PCT/EP2007/056557 LIQUID HARDENING FIELD OF INVENTION 5 The present invention concerns the curing and hardening of liquids. In particular the present invention relates to the curing and hardening of inks and paints. BACKGROUND OF INVENTION 10 Recent reviews describe different alternatives, especially based on Mn and Fe compounds (Bieleman, J.H. in Additives in Plastics and Paints, Chimia, 56, 184 (2002); Bieleman, J.H., Marcomol. Symp., 187, 811 (2002); van Gorkum R, Bouwman E, 15 Coord. Chem. Rev., 249, 1709 (2005)). WO 03/093384 describes the use of transition-metal salts or complexes based on pyrazoles, aliphatic and aromatic amines, 2,2'-bipyridine, 1,10'-phenanthroline, 1,4,7-trimethyl- 20 1,4,7-triazacyclononane in combination with a reducing agent as drying agent. Especially Fe and Mn salts and complexes were preferred in combination with ascorbic acid or derivatives thereof. WO03/093384 demonstrates that iron compounds have a rather poor activity and hence high dosages 25 are needed to get satisfactory drying activity. A drawback of using iron compounds at high levels is that an unwanted yellowish/brownish colour is imparted to the mix. SUMMARY OF INVENTION 30 The present invention concerns settable liquid compositions that contain a siccative and an alkyd-based resin. The WO 2008/003652 PCT7EP2007/056557 siccative is the component of the liquid composition that facilitates drying, curing, setting, or hardening of the composition. 5 The liquid may be any settable liquid, for example, lacquer, inks and paints. The term paint includes lacquers. The term alkyd-based resin generally refers to polyesters modified with fatty acids. Alkyd-based resins are generally prepared via the condensation polymerisation reaction of three types 10 of monomers: polyalcohols, polybasic acids and fatty acids or triglyceride oils. We have found active iron and manganese compounds that are active as a siccative at relatively low concentrations. 15 In one aspect the present invention provides a curable liquid medium comprising: a) from 1 to 90 wt %, preferably from 20 to 70 wt%, of an alkyd-based resin; and, 20 b) from 0.0001 to 0.1 wt% of a siccative, wherein the siccative is an iron or manganese complex of a tetradentate, pentadentate or hexadentate nitrogen donor ligand; the tetradentate, pentadentate or hexadentate nitrogen donor ligands are described in detail below. 25 Preferably the iron or manganese complex is of a tetradentate or pentadentate nitrogen donor ligand. More preferably the iron compound contains a pentadentate nitrogen donor ligand and the manganese compound a 30 tetradentate nitrogen donor ligand. WO 2008/003652 PCT7EP2007/056557 In another aspect the present invention provides the composition of the present invention after curing. DETAILED DESCRIPTION OF INVENTION 5 The present invention relates to a siccative for alkyd-based resins, coatings, inks, and linoleum floor coverings, comprising an iron or manganese complex containing a tetradentate, pentadentate or hexadentate nitrogen donor 10 ligand. Whilst certain paints/inks contain unsaturated oils/acids as cross-linking agent, most of them contain alkyd-based resins that contain unsaturated groups. The alkyd-based air-drying coatings to which the siccative of the present invention can be added, comprise coatings, such 15 as paint, varnish or wood stain, and also includes inks and linoleum floor coverings and the like. The siccative is equally applicable to setting paints/inks/print which do not contain alkyd-based resins, but do contain at least 2% of double or triple unsaturated compound. 20 The coatings, inks, and linoleum floor coverings may also include compositions wherein besides the alkyd based binder also other binders are present, e.g. compositions comprising 1) an alkyd- based binder and 2) a polyacrylate and/or a 25 polyurethane binder. Conventional air~drying alkyds can be obtained by a polycondensation reaction of one or more polyhydric alcohols, one or more polycarboxylic acids or the corresponding anhydrides, and long chain unsaturated fatty acids or oils. WO 2008/003652 PCT/EP2007/056557 Due to its presence in naturally occurring oils, glycerol is a widely encountered polyol. Other examples of suitable polyhydric alcohols include: pentaerythritol, dipentaerythritol, ethylene glycol, diethylene glycol, 5 propylene glycol, neopentyl glycol, trimethylol propane, trimethylol ethane, di-trimethylol propane and 1,6-hexane diol. Polycarboxylic acids and the corresponding anhydrides, used to synthesise alkyds, comprise aromatic, aliphatic and cycloaliphatic components, which are generally derived from 10 petrochemical feedstocks. Typical examples of such polyacids include: phthalic acid and its regio-isomeric analogues, trimellitic acid, pyromellitic acid, pimelic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid and tetra-hydrophthalic acid. 15 Suitable drying fatty acids, semi-drying fatty acids or mixture thereof, useful herein, are ethylenically unsaturated conjugated or non-conjugated C2-C24 carboxylic acids, such as oleic, ricinoleic, linoleic, linolenic, 20 licanic acid and eleostearic acids or mixture thereof, typically used in the form of mixtures of fatty acids derived from natural or synthetic oils. By semi-drying and drying fatty acids is meant fatty acids that have the same fatty acid composition as the oils they are derived from. 25 The classfication of the oils is based on the iodine number; for drying oil the iodine number is >140; for semi-drying oil the iodine number is ranging between 125 and 140, and for non-drying oil the iodine number is 30 Suitable organic solvents to dilute the air- drying alkyds of the invention include aliphatic, cycloaliphatic and WO 2008/003652 PCT/EP2007/056557 aromatic hydrocarbons, alcohol ethers, alcohol esters and N-methylpyrrolidone. However it may also be an aqueous carrier containing the alkyd resin in the form of an emulsion and a suitable emulsifier as is well known in the art. 5 An ink of the present invention containing an alkyd varnish, modified with unsaturated fatty acids, as defined above, as a vehicle component of the ink is usable, but not limited to, as a metal plate ink, lithographic ink, relief printing 10 ink, screen ink or offset overprinting ink. The siccative will preferably be partly or completely dissolved in the alkyd resin, emulsion etc. The catalytic activity of the transition metal ion depends upon the ion 15 itself and on the type of ligands employed, as disclosed herein. The siccative may also be dosed to the composition just prior the use of the composition. The composition of the present invention can, if desired or 20 if necessary, also comprise other additives such as other siccatives. The invention is also an air-drying alkyd-based coating, resin, ink, or floor covering comprising a siccative 25 according to the invention, e.g. containing from 0.00001 to 0.1 wt% (based on the amount of binder; this will be generally 5 to 50 times higher than when metal-based, depending on the molecular weight of the compound defined herein) of the iron or manganese complex containing a 30 tetradentate, pentadentate or hexadentate nitrogen donor. The air-drying alkyd-based coating, resin, ink, or floor WO 2008/003652 PCT/EP2007/0S6557 covering may further comprise a polyacrylate and/or a polyurethane binder. The composition of the present invention may contain 5 colourants, pigment, anti-corrosive pigment, and/or extender pigment and/or a dye. It may further contain, if necessary, plasticizer, surface-controlling agents, anti-silking agent, a defoaming agent, a rheological controlling agent and/or an ultraviolet absorber. 10 The addition of the siccative itself is done with conventional techniques, known to the person skilled in the art. The siccative is either added during the production of the alkyd based resins, coatings, inks, and linoleum floor 15 coverings, or is added under stirring to them before use. The composition of the present invention is preferably stored under an inert atmosphere, for example nitrogen or carbon dioxide. 20 STABILITY AGENTS The composition of the present invention preferably comprises an antioxidant in the range 0.001% to 0.1%, most 25 preferably 0.002 and 0.05%. Suitable antioxidants are disclosed in US 6,586,383. Most preferably the antioxidant is selected from the group consisting of: di-tert-butyl hydroxy toluene, ethoxyquine, cx-tocopherol, and 6-hydroxy-2,5,7,8-tetra-methylchroman-2-carboxylic acid. WO 2008/003652 PCT/EP2007/056557 The composition of the present preferably comprises ethyleneglycol and/or glycerol in the range 0.1 and 50 wt%, preferably 0.3 and 5wt%. 5 SICCATIVE Preferably, the siccative is present in the a curable liquid medium from 0.0001 and 0.1% w/w, more preferably from 0.001 and 0.1% w/w and most preferably from 0.002 and 0.05% w/w. ]0 The tetradentate, pentadentate or hexadentate nitrogen donor ligand may be built up within any organic structure which will support coordinating nitrogen atoms. For example one can take a basic tridentate ligand such as 1,4,7- 15 triazacyclononane and have further nitrogen co-ordination groups, e.g., -CH2-CH2-NH2, -CH2-Py, covalently bound to one or more of the cyclic nitrogens or aliphatic groups. Preferably the iron ion is selected from Fe(II) and Fe(III) 20 and the manganese ion is selected from Mn(II), Mn(III), and Mn (IV) . Preferably the ligand is present in one or more of the forms [MnLCl2] ; [FeLCl2] ; [FeLCl]Cl; [FeL WO 2008/003652 PCT/EP2007/056557 If unspecified the length of any alkyl chain is preferably Cl to C8-alkyl chain and preferably linear. If unspecified the aryl group is a phenyl group. 5 BISPIDON The bispidon class are preferably in the form of an iron transition metal catalyst. 10 The bispidon ligand is preferably of the form: wherein each R is independently selected from: hydrogen, F, 15 Cl, Br, hydroxyl, Cl-C4-alkylO, -NH-CO-H, -NH-CO-C1-C4- alkyl, -NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl; Rl and R2 are independently selected from: Cl-C24-alkyl, C6-C10-aryl, and, 20 a group containing a heteroatom capable of coordinating to a transition metal; R3 and R4 are independently selected from hydrogen, C1-C8 alkyl, Cl-C8-alkyl-0-Cl-C8-alkyl, Cl-C8-alkyl-O-C6-C10-aryl, C6-Cl0-aryl, Cl-C8-hydroxyalkyl, and - (CH2) nC(0)OR5 25 wherein R5 is independently selected from: hydrogen, C1-C4- alkyl, n is from 0 to 4, and mixtures thereof; and, WO 2008/003652 PCT/EP20O7/0S6557 X is selected from C=0, -[C(R6)2Jy- wherein Y is from 0 to 3 each R6 is independently selected from hydrogen, hydroxyl, Cl-C4-alkoxy and Cl-C4-alkyl. 5 Preferably R3 = R4 and selected from -C(0)-0-CH3, -C(0)-0-CH2CH3, -C(0)-0-CH2C6H5 and CH20H. Preferably the heteroatom capable of coordinating to a transition metal is pyridin-2-ylmethyl optionally 10 substituted by -C0-C4-alkyl. Preferably X is OO or C(0H)2. Preferred groups for Rl and R2 are CH3, -C2H5, -C3H7, 15 benzyl, -C4H9, -C6H13, -C8H17, -C12H25, and -C18H37 and pyridin-2-yl. A preferred class of bispidon is one in which at least one of Rl or R2 is pyridin-2-ylmethyl or benzyl, preferably pyridin-2-ylmethyl. 20 A preferred bispidon is dimethyl 2, 4-di-(2-pyridyl) -3- methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-l,5-dicarboxylate (N2py3o-Cl) and the iron complex thereof FeN2py3o-Cl which was prepared as described in W002/48301. Other preferred bispidons are one in which 25 instead of having a methyl group (CI) at the 3 position have longer alkyl chains, namely isobutyl, (n-hexyl) C6, (n-octyl) C8, (n-dodecyl) C12, (n-tetradecyl) C14, (n-octadecyl) CI8, which were prepared in an analogous manner. WO 2008/003652 PCT/EP2007/056557 Preferred tetradentate bispidons are also illustrated in WO00/60045 and preferred pentadentate bispidons are illustrated in W002/48301 and WO03/104379. 5 N4py type The N4py are preferably in the form of an iron transition metal catalyst. The N4py type ligands are preferably of the form: Rl R2 10 wherein each R1 , R2 independently represents -R4-R5, R3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R4-R5, 15 each RA independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and 20 each R5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl. 25 Preferably R1 represents pyridin-2-yl or R2 represents pyridin-2-yl-methyl. Preferably R2 or R1 represents 2-amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-(N,N-di(m)ethyl)amino-ethyl. If substituted, R5 preferably represents 3-methyl WO 2008/003652 PCT/EP2007/056557 pyridin-2-yl. R3 preferably represents hydrogen, benzyl or methyl. The preferred ligands are N4Py (i.e. N, N-bis(pyridin-2-yl-5 methyl)-bis(pyridin-2-yl)methylamine) which is disclosed in W095/34628 and MeN4py (i.e. N,N-bis(pyridin-2-yl-methyl-l,1-bis(pyridin-2-yl)- 1- aminoethane, as disclosed in EP0909809. 10 TACN-Nx The TACN-Nx are preferably in the form of an iron transition metal catalyst. The ligands possess the basic 1,4,7-triazacyclononane 15 structure but have one or more pendent nitrogen groups that complex with the transition metal to provide a tetradentate, pentadentate or hexadentate ligand. Preferably, the basic 1,4,7-triazacyclononane structure has two pendent nitrogen groups that complex with the transition metal (TACN-N2). 20 The TACN-Nx is preferably of the form: R20^ i . R20 R20 (III) wherein each R20 is selected from: an alkyl, cycloalkyl, 25 heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+ (R21)3 WO 2008/003652 PCT/EP2007/0565S7 10 15 20 , wherein R21 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2-R22, in which Y is independently selected from H, CH3, C2H5, C3H7 and R22 is independently selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least one of R20 is a -CY2-R22. Preferably R22 is selected from optionally substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1-yl, quinolin-2-yl groups. Most preferably R22 is either a pyridin-2-yl or a quinolin-2-yl. CYCLAM AND CROSS BRIDGED LIGANDS The cyclam and cross bridged ligands are preferably in the form of a manganese transition metal catalyst. The cyclam ligand is preferably of the form: (Q)P (IV) wherein: Q is independently selected from: R WO 2008/003652 PCT/EP2007/056557 10 15 p is 4; R is independently selected from: hydrogen, Cl-C6-alkyl, CH2CH20H, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge; Rl, R2, R3, R4, R5 and R6 are independently selected from: H, Cl-C4-alkyl, and Cl-C4-alkylhydroxy. Preferred non-cross-bridged ligands are 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me4cyclam), 1,4, 7710-tetraazacyclododecane (cyclen), 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me4cyclen), and 1,4,7,10-tetrakis(pyridine-2ylmethyl)-1,4,7,10-tetraazacyclododecane (Py4cyclen). With Py4cyclen the iron complex is preferred. A preferred cross-bridged ligand is of the form: (V) 20 wherein "R1" is independently selected from H, and linear or branched, substituted or unsubstituted CI to C20 alkyl, alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the macropolycyclic rings are coordinated with the transition metal. WO 2008/003652 PCT/EP2007/056557 Preferably Rl = Me, which is the ligand 5,12-dimethyl- ■ 1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane of which the complex [Mn(Bcyclam)CI2] may be synthesised according to WO98/39098. 5 Other suitable crossed bridged ligands are also found in WO98/39098. TRISPlCEN-type 10 The trispicens are preferably in the form of an iron transition metal catalyst. The trispicen type ligands are preferably of the form: 15 R17R17N-X-NR17R17 (VI), wherein: X is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C (OH) HCH2-; and, 20 R17 independently represents a group selected from: R17 and alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, 25 amine, alkylamine and N+(R19)3 , wherein R19 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2-R18, in which Y is independently selected from H, CH3, C2H5, C3H7 and R18 is 30 independently selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl. WO 2008/003652 PCT/EP2007/056557 pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least two of R17 are -CY2-RI8. 5 The heteroatom donor group is preferably pyridinyl optionally substituted by -C0-C4-alkyl. Other preferred heteroatom donor groups are imidazol-2-yl, l-methyl-imidazol-2-yl, 4-methyl-imidazol-2-yl, imidazol-4-10 yl, 2-methyl-imidazol-4-yl, l-methyl-imidazol-4-yl, benzimidazol-2-yl and 1-methyl-benzimidazol-2-yl. Preferably three of R17 are CY2-R18. 15 The ligand Tpen (i.e. N, N, N', N'-tetra(pyridin-2-yl-methyl)ethylenediamine) is disclosed in W097/48787. The following are preferred trispicens: N-methyl-tris( pyridin-2-ylmethyl)ethylene-1/ 2-diamine; N-octyl- 20 tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N', N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-lr2-diamine; N-ethyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N',N'-tris(5- 25 methyl-pyridin-2-ylmethyl)ethyl ene-1,2-diamine;N-ethyl-N,N',N'-tris(5-methy1-pyridin-2-ylmethyl)ethylene-1, 2-diamine; N-benzyl- N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethyl ene-1,2-diamine; WO 2008/003652 PCT/EP2007/056557 N-butyl-N,N!,N'-tris(pyridin-2-ylmethyl)ethyl ene-1,2-diamine; N-octyl-N,N',N'-tris(pyridin-2-ylmethyl)ethyl ene-1,2-diamine; N-dodecyl-N,N', N'-tris(pyridin-2-ylmethyl)ethyl ene-1,2-diamine; N-octadecyl-N,N',N1-tris(pyridin-2-5 ylmethyl)ethyl ene-1,2-diamine; N-Methyl-N,N',N'- Tris(imidazol-2ylmethyl)- ethylenediamine; N-ethyl-N,N', N' -Tris(imidazol-2ylmethyl)-ethylenediamine; N,N'-dimethyl-N,N'-bis(imidazol-2-ylmethyl)-ethylenediamine; N-(1-propan-2-ol)-N, N',N'-Tris(imidazol-2ylmethyl)-ethylenediamine; N- 10 (l-propan-2-ol)-N,N',N'-Tris(l-methyl-imidazol-2ylmethyl)-ethylenediamine; N,N-diethyl-N',N",N"-Tris(5-methyl-imidazol-4ylmethyl)-diethylenetriamine; N-(3-propan-l-ol)-N,N',N'-Tris(l-methyl-imidazol-2-ylmethyl)-ethylenediamine; N-hexyl-N,N',N'-Tris(imidazol-2ylmethyl)-ethylenediamine; N- 15 methyl-N,N',N'-tris(benzimidazol-2ylmethyl)-ethylenediamine; and, N- (3-propan-l-ol)methyl-N,N',N'-tris(benzimidazol-2ylmethyl)-ethylenediamine. Other suitable trispicens are found in WO02/077145. 20 Of the non-bispidon type siccatives the following are most preferred: 5,12-dimethyl-l,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 5,12-dibenzyl-l,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 25 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7,10-tetraazacyclododecane, 1,4,7,10-tetramethyl-l,4,7,10-tetraazacyclododecane, and 1,4,7,10-tetrakis(pyridine-2ylmethyl)-1,4,7,10-tetraazacyclododecane, N,N-bis(pyridin- 30 2-yl-methyl)-bis(pyridin-2-yl)methylamine, N,N-bis(pyridin-2-yl-methyl-l,1-bis(pyridin-2-yl)- 1- aminoethane. WO 2008/003652 PCT/EP2007/056557 N,N,N',N'-tetra(pyridin-2-yl-methyl)ethylenediamine, N-methyl-tris ( pyridin-2-ylmethyl) ethylene-1, 2-diamine; N-butyl-N/N1, N'-tris(pyridin-2-ylmethyl)ethylene-1, 2-diamine; N-octyl-N,Nf,N'-tris(pyridin-2-ylmethyl)ethylene-1,2-5 diamine; N-dodecyl-N, N', N'-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-N,N', N'-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N',Nr-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2- 10 diamine; N-methyl-N,N',N'-tris(5-methyl-pyridin-2- ylmethyl)ethylene-1,2-diamine;N-ethyl-N,N' ,N'-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl- N,N',N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylene- 15 1,2-diamine; N-methyl-N,N',N'-tris(imidazol-2ylmethyl)- ethylenediamine; N-ethyl-N,N',N'-tris(imidazol-2ylmethyl)-ethylenediamine; N,N'-dimethyl-N,N'-bis(imidazol-2-ylmethyl)-ethylenediamine; N-(l-propan-2-ol)-N,N', N' -tris(imidazol-2ylmethyl)-ethylenediamine; N-(l-propan-2-ol)- 20 N,N',N'-tris(l-methyl-imidazol-2ylmethyl)-ethylenediamine; N,N-diethyl-N',N",N"-tris(5-methyl-imidazol-4ylmethyl)-diethylenetriamine; N-(3-propan-l-ol)-N,N', N'-tris(1-methyl-imidazol-2-ylrnethyl)-ethylenediamine; N-hexyl-N,N',N'-tris(imidazol-2ylmethyl)-ethylenediamine; N-methyl-N,N',N'- 25 tris(benzimidazol-2ylmethyl)-ethylenediamine; and, N- (3-propan-1-ol)methyl-N,N', N'-tris(benzimidazol-2ylmethyl)-ethylenediamine; 1,4-bis(quinolin-2-ylmethyl)-7-octyl-l,4,7-triazacyclononane; 1,4-bis(quinolin-2-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(quinolin-2-ylmethyl)-7- 30 methyl-1,4,7-triazacyclononane, ; 1,4-bis(pyridyl-2-methyl)-7-octyl-l,4,7-triazacyclononane ; 1,4-bis(pyridyl-2-methyl)- WO 2008/003652 PCT/EP2007/056557 7-ethyl-l,4,7-triazacyclononane; 1,4-bis(pyridyl-2-methyl)-7-methyl-l,4,7-triazacyclononane; 1,4-bis(pyrazol-l-ylmethyl) -7-octyl-l,4,7-triazacyclononane; 1,4-bis(pyrazol-l-ylmethyl) -7-ethyl-l,4,7-triazacyclononane; 1,4-5 bis(pyrazol-l-ylmethyl)-7-methyl-l,4, 7-triazacyclononane, 3,5-dimethylpyrazol-l-ylmethyl)-7-octyl-l,4,7-triazacyclononane; 3,5-dimethylpyrazol-l-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 3,5-dimethylpyrazol-l-ylmethyl)-7-methyl-1,4,7-triazacyclononane; 1,4-bis(1-methylimidazo1-2- 10 ylmethyl)-7-octyl-l,4,7-triazacyclononane; 1,4-bis (1- methylimidazol-2-ylmethyl)-7-ethyl-l,4,7-triazacyclononane; 1,4-bis(l-methylimidazol-2-ylmethyl)-7-methyl-l,4,7-triazacyclononane; and, 1,4,7-tris(quinolin-2-ylmethyl)-1,4,7-triazacyclononane; 1,4,7-tris(pyridin-2-ylmethyl)- 15 1,4,7-triazacyclononane. EXAMPLES Cobalt(II) 2-ethylhexanoate (65 wt. % solution in mineral 20 spirits) was obtained from Aldrich. Dimethyl 2, 4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-l,5-dicarboxylate (N2py3o-Cl) and the iron(II) complex thereof [Fe(N2py3o-25 C1)C1]C1 was prepared as described in WO0248301. Dimethyl 2,4-di-(2-pyridyl)-3-octyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-l,5-dicarboxylate (N2py3o-C8) and Dimethyl 2,4-di-(2-pyridyl)-3-octadecyl-7-30 (pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2py3o-C18) and the corresponding iron WO 2008/003652 PCT/EP2007/056557 complexes, [Fe(N2py3o-C8)CI]CI and [Fe(N2py3o-C18)Cl]Cl, were prepared as described in WO 2005042532. N,N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine, 5 hereafter referred to as N4Py, and the corresponding iron(II) complex, [Fe(N4py)Cl]Cl, were prepared as described in EP0765381. N,N-bis(pyridin-2-yl-methyl-l,1-bis(pyridin-2-yl)- 1-10 aminoethane , hereafter referred to as MeN4Py, and the corresponding iron (II) complex, [Fe(MeN4py)Cl]Cl, were prepared as described in EP0909809. 4,11-dimethyl-l,4,8,11-tetraazabicyclo[6.6.2]hexadecane , \5 hereafter referred to as Bcyclam, and the corresponding manganese (II) complex, [Mn(Bcyclam)CI2] , were prepared as described in WO98/39098 and J.Am. Chem.Soc, 122, 2512 (2000)). 20 N-methyl-trispicen (Metrispicen), N-octyl-trispicen (C8-trispicen), N-octadecyl-trispicen (C18-trispicen) were synthesised according to literature procedures (Bernal, J.; et al. J. Chem. Soc, Dalton Trans. 1995, 3667) and GB2386615. The corresponding iron (II) complexes, 25 [Fe(Metrispicen)Cl]Cl, [Fe(C8-trispicen)Cl]Cl, and [Fe(C18-trispicen)Cl]Cl, were prepared similarly to the procedure described in EP0909809 for the MeN4py analog. 1,4-bis(quinolin-2-ylmethyl)-7-ethyl-l,4,7-triazacyclononane 30 (Quin2TACN) and the corresponding [Fe (Quin2TACN) Cl] C104 compound were prepared as disclosed in EP1259522. WO 2008/003652 PCT/EP2007/056557 Mn2(H-0)3(l, 4, 7-trimethyl-l, 4, 7-triazacyclononane)2] PF6) 2 was prepared as published elsewhere (J. Chem. Soc, Dalton Trans, 353 (1996)). 5 Experiment 1 Homogeneous bleaching of p-carotene in hexane with methyllinoleate This experiment was done to show that the (3-carotene can be 10 degraded by interaction of the various iron and manganese catalysts with methyllinoleate, as an indicator for radical reactions (which in turn should lead to increased rate of paint/ink drying). 15 UV/VIS experiments were performed on a Hewlett Packard 8453 apparatus. All the experiments were performed at 35 CC and measurements were conducted over a period of 1 hour in the UV/VIS kinetic mode. The assays were done in a quartz cuvette and were shaken thoroughly before starting the 20 measurements. The stopper was removed from the cuvettes during measurements. The hexane solutions contained 85.6 ^lM (3-carotene, 6.0 mM methyllinoleate, approximately 5 p.M of the catalyst and 3.1% 25 (v/v) ethanol. The initial absorbance at 452 nm was about 0.45 A.U. The difference between the initial absorbance and absorbance after 600 seconds in each case is given in table 1. A higher value indicates a higher p-carotene bleaching activity. WO 2008/003652 PCT/EP2007/0S6557 Table 1: Homogeneous bleaching experiments using (5-carotene and methyl-linoleate in combination with 5 \iM of each catalyst. AA452 nm (600 s) Blank (no catalyst added) 0.01 [Fe(N2py3o-Cl)Cl]Cl 0.08 [Fe(N2py3o-C8)Cl]Cl 0.11 [Fe(N2py3o-C18)Cl]Cl 0.10 [Fe(MeN4py)Cl]Cl 0.06 [Mn(Bcyclam)Cl2] , 0.07 [Fe(Metrispicen)CljCl 0.03 [Fe(C8-trispicen)Cl]Cl 0.06 [Fe(C18-trispicen)Cl]Cl 0.08 [Fe (Quin2TACN) CI]C104 0.06 Cobalt(II)-(2-ethylhexanoate)2 0.01 5 The results presented in table 1 clearly indicate that the iron and manganese compounds disclosed in this invention furnish a significant enhancement of p-carotene bleaching with methyllinoleate. 10 Experiment 2 Drying time of linseed oil paint A solvent borne model (linseed oil in n-heptane) is used for 15 alkyd based systems. All experiments were performed at room temperature and films were made on a petridish. The starting catalyst concentrations that were used were between 0.016 mM and 0.32 mM as exemplified in Table 2. Co(II)-2-ethylhexanoate (1.63 mM) and a blank (linseed oil/heptane 20 50/50 v/v) were also incorporated for comparison. WO 2008/003652 PCT/EP2007/056557 The film on the petridish consisted of 100 |il (50/50 v/v linseed/n-heptane) and 25 |il catalyst solution in ethanol (vide supra for final concentrations in linseed oil/heptane solutions). 5 The results of the tested iron and manganese complexes are shown in table. In all cases, the time needed to establish tack-free drying is given in the table. Films were classified as tack-free when they gave a straight line when a pin was 10 run through the film, but a fingerprint was still visible on the film. Through-dry indicates that the coating was hard and no print was visible anymore. A lower value indicates a faster drying time. Different concentrations of drying catalysts were taken, to establish the lowest level that 15 still can attain an equal or better drying than the cobalt salt. Table 2: Drying times to need tack free or completely dry linseed paint with different compounds and levels. Starting Concentration Tack free drying Concen- in film time (h) tration (jag/100 jal linseed) Blank - = >120 Cobalt (II)-(2- 1.63 mM 22 28 ethylhexanoate)2 [Fe(N2py3o-Cl)Cl]Cl 0.064 mM 1.0 20 [Fe(N2py3o-Cl)Cl]Cl 0.016 mM 0.26 28 [Fe(N2py3o-C8)Cl]Cl 0.064 mM 1.2 • 20 [Fe(N2py3o-C8)Cl]Cl 0.032 mM 0.61 28 WO 2008/003652 PCT/EP2007/056S57 [Fe(N2py3o-C18)Cl]Cl 0.064 mM 1.4 20 [Fe(N2py3o-C18)Cl]Cl 0.032 mM 0.7 28 [Fe(N4py)Cl]Cl 0.32 mM 4 22 (through dry) [Fe(MeN4py)Cl]Cl 0.064 mM 0.8 20 [Fe(MeN4py)Cl]Cl 0.016 mM 0.2 27 [Mn(Bcyclam)Cl2] 0.32 mM 3.1 20 (through dry) The results presented in the table clearly show that these iron and manganese compounds are much more active on molar basis than the reference, i.e. Cobalt(II)- (2-5 ethylhexanoate)2. Especially [Fe(N2py3o-Cl)CI]CI and [Fe(MeN4py)Cl]CI show an improvement of a factor of 100 on molar basis compared to the Co-ethylhexanoate drier. Table 3: Drying times to need tack free or completely dry 0 linseed paint with [Mn (Bcyclam) Cl2] and Mn2 ((X—0) 3 (1, 4, 7- trimethyl-1,4,7-triazacyclononane)2] PFe) 2 (abbr. as Mn-Me3TACN) Starting Tack free drying Concen- time (h) tration "Blank = >120 Cobalt(II)-(2- 1.63 mM 28 ethylhexanoate)2 [Mn (Bcyclam)Cl2] 2.5 mM 6 (tack free) [Mn(Bcyclam)Cl2] 0.5 mM 10 (tack free) Mn-Me3TACN 0.5 mM 20 (tack free) [Mn(Bcyclam) Cl2] 0.2 mM 20 (tack free) Mn-Me3TACN 0.2 mM 23 (tack free) WO 2008/003652 PCT/EP2007/056557 The data shown in table 3 show that [Mn(Bcyclam)CI2] exhibits a significantly higher activity than Mn-Me3tacn, exemplifying that the manganese complex with a tetradentate nitrogen donor ligand shows a faster paint drying activity 5 than a manganese complex containing the tridentate triazacyclononane ligand. Experiment 3 Storage stability of catalysts in linseed oil paint in the 10 presence of ( + ) -cc-tocopherol (Vitamin E) , purchased from Sigma. The drying activity of the [Fe(MeN4py)CI]Cl and [Fe(N2py3o-C18)C1]C1 were monitored in the presence of (+)-a-tocopherol 15 (Vitamin E) An oil-paint sample based on linseed was prepared containing 4 ml linseed, 3820 \il n-heptane, 80 jil (10 mM ( + )-a-tocopherol in heptane) and 100 (il catalyst solution in 20 ethanol. As a reference an oil-paint sample without ( + )-cc-tocopherol is included containing 4 ml linseed, 3.9 ml n-heptane and 100 JJ.1 catalyst solution in ethanol. The oil-paint samples were stored in closed glass vials under ambient conditions. Films were painted, each with a separate 25 brush, on a wooden board after certain storage periods. The drying time was monitored and the results are summarised in table 4 and 5. Table^ 4 30 Drying activity of 0.004% wt. [Fe(MeN4py)Cl]Cl (0.0004% based on Fe metal) in the absence and presence of 0.009% wt. a- WO 2008/003652 PCT/EP2007/056557 tocopherol in the formulation after different times of storage at room temperature. The amount catalyst dosed is based on the amount in the linseed oil (and not on the linseed oil/heptane mixture). Storage time (days) Without a-tocopherol drying time With CC-tocopherol drying time 0 3 5 25 h n.d. 6 n.d. 10 > 30 h; 11 n.d. > 24 h; Table 5 10 Drying activity of 0.006% [Fe(N2py3o-Cl8)CI]CI (0.0004% based on Fe metal) in the absence and presence of 0.009% a-tocopherol in the formulation after storage at room temperature. The amount catalyst dosed is based on the amount in the linseed oil (and not on the linseed 15 oil/heptane mixture). WO 2008/003652 PCT/EP2007/056557 Storage time (days) Without a-tocopherol Tack free drying time With a-tocopherol Drying time 0 22 h 22 h 3 24 h n.d. 5 25 h n.d. 6 n.d. 22 h 10 30 h n.d. 11 n.d. 22 h The results shown in tables 3 and 4 indicate that the presence of a-tocopherol retards the decreased linseed oil drying activity of the catalysts. 5 Experiment 4 Storage stability of catalysts in linseed oil paint under nitrogen vs atmospheric conditions 10 Oil-paint samples based on raw linseed oil and n-heptane were prepared in glass vials (50/50 v/v) and stored under nitrogen. [Fe(MeN4py)CI]Cl was present in 0.004 weight % (0.0004% based on Fe metal) - added as a solution in ethanol and a-tocopherol was present in 0.009 weight % (added as a 15 solution in n-heptane). The level dosed of [Fe(MeN4py)Cl]Cl is based on the weight of the compound. Similarly, experiments were conducted using 0.005% [Fe(N2py3o-Cl)Cl]Cl (0.0004% based on Fe metal)- added as a solution in ethanol. The amount catalyst dosed is based on the amount in the 20 linseed oil (and not on the linseed oil/heptane mixture). The oil-paint samples were purged with nitrogen every time the glass vials were opened. After certain storage periods the samples were painted on a wooden board and the drying WO 2008/003652 PCT/EP2007/056557 time was monitored. The drying times are summarised in table 6 and 7 for [Fe(MeN4py)Cl]Cl and [Fe(N2py3o-Cl)Cl]Cl respectively. 5 Table 6 Drying activity of 0.004% [Fe(MeN4py)Cl]Cl (0.0004% based on Fe metal) stored under ambient atmospheric conditions and under nitrogen. The amount catalyst dosed is based on the amount in the linseed oil (and not on the linseed 10 oil/heptane mixture). Entries 2 and 4 show the times needed to achieve drying in the presence of 0.009% oc-tocopherol in the formulation. Storage time (days) Stored under ambient atmospheric conditions Drying time Stored under nitrogen drying time 0 (without tocopherol 0 (with tocopherol) 30 (without tocopherol More than 32 h, but less than 47 29 h 30 (with tocopherol) More than 30 h, but less than 46 h 29 h 15 20 Table 7 Storage stability of 0.005% [Fe(N2py3o-Cl)Cl]Cl (0.0004% based on Fe metal) stored under ambient atmospheric conditions and under nitrogen. The amount catalyst dosed is based on the amount in the linseed oil (and not on the linseed oil/heptane mixture). WO 2008/003652 PCT/EP2007/056557 Entries 2 and 4 show the times neede^ to achieve drying in the presence of 0.009% a-tocopherol j_n the formulation. WO 2008/003652 PCT/EP2007/056557 Storage time (days) Stored under ambient atmospheric conditions Drying time Stored under nitrogen Drying time 0 (without tocopherol 0 (with tocopherol) 30 (without tocopherol 32 h 24 h 30 (with tocopherol) 28 h 26 h The results in table 5 and 6 illustrate that nitrogen also retards the decreased linseed oil drying activity of the 5 catalysts. Experiment 5 Storage stability of catalysts in linseed oil paint in the presence of ethylene glycol. 10 Oil-paint samples based on linseed and n-heptane (700 1; 50/50 v/v) were prepared containing 0.005% [Fe(MeN4py)CI]CI (0.0005% based on Fe metal) added as a solution in ethylene glycol (100 [il) . The tack free drying time of this sample is 15 compared with the tack free drying time of a sample to which 0.005% [Fe(MeN4py)Cl]Cl (0.0005% based on Fe metal) is added as a solution in ethanol (table 7). The amount catalyst dosed is based on the amount in the linseed oil (and not on the linseed oil/heptane mixture). 20 After certain storage periods the samples were painted on a wooden board and the drying time was monitored (table 8). WO 2008/003652 PCTYEP2007/056557 Table 8 Storage stability of 0.005% [Fe(MeN4py)Cl]Cl (0.0005% based on Fe metal) in dissolved in ethanol (left) and ethylene glycol (right) and added to the linseed oil after different 5 times of storage at room temperature. Storage time (days) Catalyst dissolved in ethanol Tack free drying time Catalyst dissolved in ethylene glycol Tack free drying time 0 31 29 h The data shown in table 7 clearly show that the presence of ethylene glycol over ethanol largely retards the decreased 10 linseed oil drying activity. WO 2008/003652 PCT/EP2007/056557 We claim: 10 A curable liquid medium comprising: a) from 1 to 90 wt % of an alkyd-based resin; and, b) from 0.0001 to 0.1 wt% of a siccative, wherein the siccative is an iron or manganese complex of a tetradentate, pentadentate or hexadentate nitrogen donor ligand, wherein the ligand is selected from the group consisting of: Rl I 15 20 wherein each R is independently selected from: hydrogen, F, CI, Br, hydroxyl, Cl-C4-alkylO-, -NH-CO-H, -NH-CO-Cl-C4-alkyl, -NH2, -NH-Cl-C4-alkyl, and C1-C4-alkyl; Rl and R2 are independently selected from: Cl-C24-alkyl, C6-C10-aryl, and, a group containing a heteroatom capable of coordinating to a transition metal; R3 and R4 are independently selected from hydrogen, Cl-C8 alkyl, Cl-C8-alkyl-0-Cl-C8-alkyl, Cl-C8-alkyl-0-C6-ClO-aryl, C6-C10-aryl, Cl-C8-hydroxyalkyl, and -(CH2)nC(0)OR5 WO 2008/003652 PCTYEP2007/056557 wherein R5 is independently selected from: hydrogen, Cl-C4-alkyl, n is from 0 to 4, and mixtures thereof; and, X is selected from C=0, -[C(R6)2]y- wherein Y is from 0 to 3 each R6 is independently selected from hydrogen, hydroxyl, Cl-C4-alkoxy and Cl-C4-alkyl; wherein 10 each R1 , R2 independently represents -R^-R5, R3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R4-R5, each R4 independently represents a single bond or optionally substituted alkylene, alkenylene, 15 oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, 20 pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; WO 2008/003652 PCT/EP2007/056557 wherein each R20 is selected from: an alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, 5 carboxylic ester, sulphonate, amine, alkylamine and N+(R21)3 , wherein R21 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY~2-R22, in which Y is independently 10 selected from H, CH3, C2H5, C3H7 and R22 is independently selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at 15 least one of R20 is a -CY2-R22; (Q)P (IV) 20 p is 4; R is independently selected from; hydrogen, Cl-C6-alkyl, CH2CH20H, pyridin-2-ylmethyl, and CH2COOH; Rl, R2, R3, R4, R5 and R6 are independently selected from H, Cl-C4-alkyl, and Cl-C4-alkylhydroxy; WO 2008/003652 PCT/EP2007/056557 wherein "R1" is independently selected from H, and linear or branched, substituted or unsubstituted Cl to C20 alkyl, 5 alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the macropolycyclic rings are coordinated with the transition metal; R17R17N-X-NR17R17 (VI), 10 wherein: X is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C(OH)HCH2-; and, R17 independently represents a group selected from: R17 and alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, 15 aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R19)3 , wherein R19 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, 20 arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2-R18, in which Y is independently selected from H, CH3, C2H5, C3H7 and R18 is independently selected from an optionally substituted heteroaryl group selected from WO 2008/003652 PCT/EP2007/056557 pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and wherein at least two of R17 are -CY2-RI8. 5 2. A curable liquid medium according to claim 1, wherein in formula (I) the heteroatom capable of coordinating to a transition metal is pyridin-2-yl optionally substituted by -C0-C4-alkyl. 10 3. A curable liquid medium according to claim 2, wherein the heteroatom donor group is unsubstituted pyridinyl. 4. A curable liquid medium according to claim 1 to 4, wherein in formula (I) X is C=0 or C(OH)2. 15 5. A curable liquid medium according to any one of claims 1 to 5, wherein in formula (I): R3 = R4 and selected from -C(0)-0-CH3, -C(0)-0-CH2CH3, -C(0)-0-CH2C6H5 and CH20H. 20 6, A curable liquid medium according to any preceding claim, wherein in formula (I) at least one of Rl or R2 is pyridin-2-ylmethyl and the other is selected from - CH3, -C2H5, -C3H7, -C4H9, C6H13, C8H17, C12H25, and 25 C18H37. 7. A curable liquid medium according to claim 1, wherein the ligand is selected from the group consisting of: 5,12-dimethyl-l,5,8,12-tetraaza- 30 bicyclo[6.6.2]hexadecane, 5,12-dibenzyl-l,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 1,4,8,11- WO 2008/003652 PCT/EP2007/056557 tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7,10-tetraazacyclododecane, 1,4,7,10-tetramethyl-l,4,7,10-tetraazacyclododecane, and 1,4,7,10-tetrakis(pyridine-5 2ylmethyl)-1,4,7,10-tetraazacyclododecane, N,N- bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine, N,N-bis(pyridin-2-yl-methyl-2,1-bis(pyridin-2-yl)- 1-aminoethane, N,N,N',N'-tetra(pyridin-2-yl¬methyl) ethylenediamine, N-methyl-tris( pyridin-2- 10 ylmethyl)ethylene-1,2-diamine; N-butyl-N,N', N1- tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-dodecyl-N,N', N'-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine; N-octadecyl-N,N',N'-tris(pyridin-2- 15 ylmethyl)ethylene-1,2-diamine; N~methyl-N,INJ',N!-tris (3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-tris(3-methyl-pyridin-2- ylmethyl)ethylene-1,2-diamine; N-methyl-N,N',N'-tris (5-methyl-pyridin-2-ylinethyl) ethylene-1, 2-diamine;N-ethyl- 20 N,N',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl- N,N',N1-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl-N,N', N'-tris (5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-N,N',N'-tris(imidazol-2ylmethyl)- 25 ethylenediamine; N-ethyl-N,N',N'-tris(imidazol-2ylmethyl)-ethylenediamine; N,N'-dimethyl-N,N'-bis(imidazol-2-ylmethyl)-ethylenediamine; N-(1-propan-2-ol)-N,N',N'-tris(imidazol-2ylmethyl)-ethylenediamine; N- (l-propan-2-ol)-N,N', N'-tris(1-methyl-imidazol- 30 2ylmethyl)-ethylenediamine; N,N-diethyl-N',N",N"- tris(5-methyl-imidazol-4ylmethyl)-diethylenetriamine; WO 2008/003652 PCT/EP2007/056557 N-(3-propan-l-ol)-N,N',N' -tris(l-methyl-imidazol-2-ylmethyl)-ethylenediamine; N-hexyl-N,N', N' -tris(imidazol-2ylmethyl)-ethylenediamine; N-methyl-N,N',N'-tris(benzimidazol-2ylmethyl)-ethylenediamine; 5 and, N-(3-propan-l-ol)methyl-N,N',N'-tris(benzimidazol-2ylmethyl)-ethylenediamine; 1,4-bis(quinolin-2-ylmethyl)-7-octyl-l,4,7-triazacyclononane; 1,4-bis(quinolin-2-ylmethyl)-7-ethyl-l,4,7-triazacyclononane; 1,4-bis(quinolin-2-ylmethyl)-7- 10 methyl-1,4,7-triazacyclononane, ; 1,4-bis(pyridyl-2-methyl)-7-octyl-l,4,7-triazacyclononane ; 1,4-bis(pyridyl-2-methyl)-1-ethyl-1,4,7-triazacyclononane; 1,4-bis(pyridyl-2-methyl)-7-methyl-l,4,7-triazacyclononane; 1,4-bis(pyrazol-1-ylmethyl)-7-octyl- 15 1,4,7-triazacyclononane; 1,4-bis(pyrazol-1-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(pyrazol-1-ylmethyl)-7-methyl-l,4, 7-triazacyclononane, 3,5-dimethylpyrazol-1-ylmethyl)-7-octyl-l,4, 7-triazacyclononane; 3,5-dimethylpyrazol-l-ylmethyl)-7- 20 ethyl-1,4,7-triazacyclononane; 3,5-dimethylpyrazol-l-ylmethyl) -7-methyl-l,4,7-triazacyclononane; 1,4-bis(1-methylimidazol-2-ylmethyl)-7-octyl-l, 4, 7-triazacyclononane; 1,4-bis(l-methylimidazol-2-ylmethyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis (1- 25 methylimidazol-2-ylmethyl)-7-methyl-l, 4, 7- triazacyclononane, 1,4,7-tris(quinolin-2-ylmethyl)-1,4,7-triazacyclononane; and, 1,4,7-tris(pyridin-2-ylmethyl)-1,4,7-triazacyclononane. 30 8. A curable liquid medium according to any preceding claim, wherein the iron ion is selected from Fe(II) and WO 2008/003652 PCTYEP2007/056557 Fe(III) and the manganese ion selected from Mn(II), Mn(III) , and Mn(IV) . 9. A curable liquid medium according to any of the 5 preceding claims wherein the content of the siccative is between 0.0001 and 0.5% w/w. 10. A curable liquid medium according to any of the preceding claims further comprising 0.001% and 0.1% of 10 the following antioxidants: di-tert-butyl hydroxy toluene, Ethoxyquine, a-tocopherol, and 6-hydroxy-2,5/7,8-tetra-methylchroman-2-carboxylic acid. 11. A curable liquid medium according to claim 10, wherein 15 the composition comprises between 0.002 and 0.05% of antioxidant. 12. A curable liquid medium according to claim 10 or 11, wherein the antioxidant is selected from a-tocopherol. 20 13. A curable liquid medium to any of the preceding claims that is stored under nitrogen or argon gas. 14. A curable liquid medium according to any of the 25 preceding claims, containing between 0.001 and 90% of ethylene glycol, diethylene glycol, dipropylene glycol, glycerol, pentaerythritol, dipenta erythritol, neopentyl glycol, trimethylol propane, trimethylol ethane, di-trimethylol propane and 1,6-hexane diol. 30 WO 2008/003652 PCT/EP2007/056557 15. A curable liquid medium according to claim 14, containing 0.1 and 50% of ethyleneglycol or glycerol. 16. A curable liquid medium according to claims 15, 5 containing 0.3 and 5% of ethyleneglycol or glycerol. 17. A curable liquid medium according to any of the preceding claims, containing between 0.001 and 2.5% of lead, zirconium, bismuth, barium, vanadium, cerium, 10 calcium, lithium, strontium, and zinc. 18. A curable liquid medium according to any one of the preceding claims when cured. |
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2732-MUMNP-2008-ANNEXURE TO FORM 3(25-7-2011).pdf
2732-MUMNP-2008-CANCELLED PAGES(8-9-2011).pdf
2732-MUMNP-2008-CLAIMS(AMENDED)-(8-9-2011).pdf
2732-MUMNP-2008-CLAIMS(GRANTED)-(24-4-2012).pdf
2732-MUMNP-2008-CORRESPONDENCE(1-1-2009).pdf
2732-MUMNP-2008-CORRESPONDENCE(11-5-2009).pdf
2732-MUMNP-2008-CORRESPONDENCE(13-11-2009).pdf
2732-MUMNP-2008-CORRESPONDENCE(21-6-2010).pdf
2732-mumnp-2008-correspondence(23-12-2008).pdf
2732-MUMNP-2008-CORRESPONDENCE(27-3-2012).pdf
2732-mumnp-2008-correspondence.pdf
2732-mumnp-2008-description(complete).doc
2732-mumnp-2008-description(complete).pdf
2732-MUMNP-2008-DESCRIPTION(GRANTED)-(24-4-2012).pdf
2732-mumnp-2008-form 13(1-1-2009).pdf
2732-mumnp-2008-form 13(8-9-2011).pdf
2732-MUMNP-2008-FORM 18(11-5-2009).pdf
2732-MUMNP-2008-FORM 2(GRANTED)-(24-4-2012).pdf
2732-MUMNP-2008-FORM 2(TITLE PAGE)-(GRANTED)-(24-4-2012).pdf
2732-mumnp-2008-form 2(title page).pdf
2732-mumnp-2008-form 3(23-12-2008).pdf
2732-MUMNP-2008-FORM 3(24-2-2010).pdf
2732-MUMNP-2008-FORM 3(3-8-2010).pdf
2732-mumnp-2008-general power of attorney.pdf
2732-MUMNP-2008-MARKED COPY(8-9-2011).pdf
2732-mumnp-2008-pct-isa-210.pdf
2732-mumnp-2008-pct-isa-237.pdf
2732-MUMNP-2008-REPLY TO EXAMINATION REPORT(25-7-2011).pdf
2732-MUMNP-2008-REPLY TO EXAMINATION REPORT(8-9-2011).pdf
2732-MUMNP-2008-SPECIFICATION(AMENDED)-(8-9-2011).pdf
2732-MUMNP-2008-US DOCUMENT(25-7-2011).pdf
2732-mumnp-2008-wo-international publication report a1.pdf
Patent Number | 252076 | |||||||||
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Indian Patent Application Number | 2732/MUMNP/2008 | |||||||||
PG Journal Number | 17/2012 | |||||||||
Publication Date | 27-Apr-2012 | |||||||||
Grant Date | 24-Apr-2012 | |||||||||
Date of Filing | 23-Dec-2008 | |||||||||
Name of Patentee | UNILEVER PLC | |||||||||
Applicant Address | UNILEVER HOUSE, 100 VICTORIA EMBANKMENT, LONDON EC4Y 0DY, GB, FORMERLY OF UNILEVER HOUSE, BLACKFRIARS, LONDON EC4P 4BQ, LONDON | |||||||||
Inventors:
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PCT International Classification Number | C09F9/00 | |||||||||
PCT International Application Number | PCT/EP2007/056557 | |||||||||
PCT International Filing date | 2007-06-29 | |||||||||
PCT Conventions:
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