Liquid hardening

A curable liquid medium comprising:

• from 1 to 90 wt % of an alkyd-based resin;
• and
• from 0.0001 to 0.1 wt % of two or more siccatives 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
• (a) bispidon ligands of formula I,
• (b) N4py ligands of formula II,
• (c) TACN-Nx ligands of formula III,
• (d) cyclam ligands of formula IV,
• (e) cross-bridged ligands of formula V, and
• (e) trispicen ligands of formula VI;
• and further wherein the ligands are selected from the group consisting of formulae (I) to (VI):
• wherein:
• each R is independently selected from the group consisting of hydrogen, F, Cl, Br, hydroxyl, C1-4-alkylO', —NH—CO—H, —NH—CO—C1-4alkyl, —NH2, —NH—C1-4alkyl, and C1-4alkyl;
• R1 and R2 are independently selected from the group consisting of C1-24alkyl, C6-10aryl, and a group containing one or two heteroatoms (e.g. N, O or S) capable of coordinating to a transition metal;
• R3 and R4 are independently selected from the group consisting of hydrogen, C1-8alkyl, C1-8alkyl-O—C1-8alkyl, C1-8alkyl-O—C6-10aryl, C6-10aryl, C1-8hydroxyalkyl and —(CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen and C1-4alkyl,
• n is from 0 to 4
• X is selected from the group consisting of C═O, —[C(R6)2]y— wherein y is from 0 to 3;
• and
• each R6 is independently selected from the group consisting of hydrogen, hydroxyl, C1-4 alkoxy and C1-4 alkyl.
• wherein:
• each R1 and R2 independently represents —R4—R5;
• R3 represents hydrogen, C1-8-alkyl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-40 arylalkyl, or —R4—R5,
• each R4 independently represents a single bond or a linear or branched C1-8-alkyl-substituted-C2-6-alkylene, C2-6-alkenylene, C2-6-oxyalkylene, C2-6-aminoalkylene, C2-6-alkenyl ether, C2-6-carboxylic ester or C2-6-carboxylic amide, and
• each R5 independently represents an optionally N-alkyl-substituted aminoalkyl group or an optionally alkyl-substituted heteroaryl:
• selected from the group consisting of pyridinyl;
• pyrimidinyl;
• pyrazinyl;
• triazolyl;
• pyridazinyl;
• 1,3,5-triazinyl;
• quinolinyl;
• isoquinolinyl;
• quinoxalinyl;
• imidazolyl;
• pyrazolyl;
• benzimidazolyl;
• thiazolyl;
• oxazolidinyl;
• pyrrolyl;
• carbazolyl;
• indolyl;
• and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl.
• wherein:
• each R20 is independently selected from:
• C1-8-alkyl, C3-8-cycloalkyl, heterocycloalkyl selected from the group consisting of:
• pyrrolinyl;
• pyrrolidinyl;
• morpholinyl;
• piperidinyl;
• piperazinyl;
• hexamethylene imine;
• 1,4-piperazinyl;
• tetrahydrothiophenyl;
• tetrahydrofuranyl;
• 1,4,7-triazacyclononanyl;
• 1,4,8,11-tetraazacyclotetradecanyl;
• 1,4,7,10,13-pentaazacyclopentadecanyl;
• 1,4-diaza-7-thia-cyclononanyl;
• 1,4-diaza-7-oxa-cyclononanyl;
• 1,4,7,10-tetraazacyclododecanyl;
• 1,4-dioxanyl;
• 1,4,7-trithia-cyclononanyl;
• tetrahydropyranyl;
• and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl;
• heteroaryl selected from the group consisting of:
• pyridinyl;
• pyrimidinyl;
• pyrazinyl;
• triazolyl;
• pyridazinyl;
• 1,3,5-triazinyl;
• quinolinyl;
• isoquinolinyl;
• quinoxalinyl;
• imidazolyl;
• pyrazolyl;
• benzimidazolyl;
• thiazolyl;
• oxazolidinyl;
• pyrrolyl;
• carbazolyl;
• indolyl;
• and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-40-arylalkyl group optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R21)3,
• R21 is selected from hydrogen, C1-8-alkyl, C2-6-alkenyl, C7-40-arylalkyl, arylalkenyl, C1-8-oxyalkyl, C2-6-oxyalkenyl, C1-8-aminoalkyl, C2-6-aminoalkenyl, C1-8-alkyl ether, C2-6-alkenyl ether, and —CY2—R22,
• Y is independently selected from H, CH3, C2H5, C3H7 and
• R22 is independently selected from C1-8-alkyl-substituted heteroaryl:
• selected from the group consisting of:
• pyridinyl;
• pyrimidinyl;
• pyrazinyl;
• triazolyl;
• pyridazinyl;
• 1,3,5-triazinyl;
• quinolinyl;
• isoquinolinyl;
• quinoxalinyl;
• imidazolyl;
• pyrazolyl;
• benzimidazolyl;
• thiazolyl;
• oxazolidinyl;
• pyrrolyl;
• carbazolyl;
• indolyl;
• and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl;
• and
• wherein at least one of R20 is a —CY2—R22.
• wherein:
• Q is independently selected from
• p is 4;
• R is independently selected from:
• hydrogen, C1-6-alkyl, CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge;
• and
• R1, R2, R3, R4, R5 and R6 are independently selected from:
• H, C1-4-alkyl, and C1-4-alkylhydroxy.
• wherein:
• R1 is independently selected from H, C1-20 alkyl, C7-40-alkylaryl, C2-6-alkenyl or C2-6-alkynyl.
• R17R17N—X—NR17R17 (VI),
• wherein:
• X is selected from —CH2CH2—, —CH2CH2CH2—, —CH2C(OH)HCH2—;
• each R17 independently represents a group selected from:
• R17, C1-8-alkyl, C3-8-cycloalkyl, heterocycloalkyl selected from the group consisting of:
• pyrrolinyl;
• pyrrolidinyl;
• morpholinyl;
• piperidinyl;
• piperazinyl;
• hexamethylene imine;
• 1,4-piperazinyl;
• tetrahydrothiophenyl;
• tetrahydrofuranyl;
• 1,4,7-triazacyclononanyl;
• 1,4,8,11-tetraazacyclotetradecanyl;
• 1,4,7,10,13-pentaazacyclopentadecanyl;
• 1,4-diaza-7-thia-cyclononanyl;
• 1,4-diaza-7-oxa-cyclononanyl;
• 1,4,7,10-tetraazacyclododecanyl;
• 1,4-dioxanyl;
• 1,4,7-trithia-cyclononanyl;
• tetrahydropyranyl;
• and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl;
• heteroaryl:
• selected from the group consisting of:
• pyridinyl;
• pyrimidinyl;
• pyrazinyl;
• triazolyl;
• pyridazinyl;
• 1,3,5-triazinyl;
• quinolinyl;
• isoquinolinyl;
• quinoxalinyl;
• imidazolyl;
• pyrazolyl;
• benzimidazolyl;
• thiazolyl;
• oxazolidinyl;
• pyrrolyl;
• carbazolyl;
• indolyl;
• and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, and C7-40 arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R19)3, wherein
• R19 is selected from hydrogen, C1-8-alkyl, C2-6-alkenyl, C7-40-arylalkyl, C7-40-arylalkenyl, C1-8oxyalkyl, C2-6-oxyalkenyl, C1-8-aminoalkyl, C2-6-aminoalkenyl, C1-8-alkyl ether, C2-6-alkenyl ether, and —CY2—R18, in which each Y is independently selected from H, CH3, C2H5, C3H7 and R18 is independently selected from an optionally substituted heteroaryl:
• selected from the group consisting of:
• pyridinyl;
• pyrimidinyl;
• pyrazinyl;
• triazolyl;
• pyridazinyl;
• 1,3,5-triazinyl;
• quinolinyl;
• isoquinolinyl;
• quinoxalinyl;
• imidazolyl;
• pyrazolyl;
• benzimidazolyl;
• thiazolyl;
• oxazolidinyl;
• pyrrolyl;
• carbazolyl;
• indolyl;
• and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl;
• and at least two of R17 are —CY2—R18.