EP4662282A1 - Système d'agent siccatif et anti-peau pour une composition de revêtement - Google Patents

Système d'agent siccatif et anti-peau pour une composition de revêtement

Info

Publication number
EP4662282A1
EP4662282A1 EP24704007.4A EP24704007A EP4662282A1 EP 4662282 A1 EP4662282 A1 EP 4662282A1 EP 24704007 A EP24704007 A EP 24704007A EP 4662282 A1 EP4662282 A1 EP 4662282A1
Authority
EP
European Patent Office
Prior art keywords
drier
formula
skinning agent
weight
coating composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24704007.4A
Other languages
German (de)
English (en)
Inventor
Tjian Hong ANG
Johannes Gerardus Jozef WEIJNEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Europe BV
Original Assignee
PPG Europe BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PPG Europe BV filed Critical PPG Europe BV
Publication of EP4662282A1 publication Critical patent/EP4662282A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/46—Anti-skinning agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F9/00—Compounds to be used as driers, i.e. siccatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

  • the present invention relates to a drier and anti-skinning agent system for a coating composition.
  • the present invention relates to a drier and anti-skinning agent system for oxidatively drying binder-based coatings.
  • the present invention also extends to a coating composition comprising the drier and anti-skinning agent system, and to a substrate coated with a coating derivable from the coating composition.
  • Autoxidisable alkyd resins are long-established binder polymers for film-forming coating compositions acknowledged for their aesthetic properties, low surface tension (which enables the wetting of and adhesion on a wide variety of substrates and facilitates pigment wetting), applicability by various techniques, and cost-effectiveness. Because of these properties, alkyd resins are the most widely used air drying binders in coating compositions. Autoxidisable alkyd resins comprise drying or semi-drying unsaturated fatty acids or oils, which are chemically grafted to the polyester backbone composed of polyols and polycarboxylic acids.
  • the drying process starts by solvent evaporation and the unsaturated fatty acid side chains of the binder undergo autoxidation and subsequently form cross-links between the polymer chains resulting in a solid and coherently dried film.
  • the drying process of autoxidisable alkyd resins takes place in the presence of oxygen under ambient or forced drying conditions, whereby the presence of oxygen is essential.
  • the time for such compositions to dry depends on the concentration and type of unsaturated oil or fatty acids used to prepare the resin. Autoxidation and crosslinking of the unsaturated oil/fatty acid side chains can proceed unaided, but the time for drying is generally found to be unacceptably long for many practical applications.
  • the curing is significantly accelerated by the addition of a metal-based drying catalyst, commonly referred to as a "drier" or "siccative".
  • catalytic oil drying agents are commonly divided into three main classes according to their catalytic activity: primary driers, which all possess significant catalytic activity, coordination driers, which promote the film-forming process by bridging two or multiple polymer chains, and secondary driers, which have little to no catalytic effect when used on their own but assist the drying process by activating the metal in the primary drier.
  • Examples of known primary drier salts include carboxylates of transition metals such as cobalt, copper, iron, manganese, and vanadium, which have at least two accessible valence states.
  • transition metals such as cobalt, copper, iron, manganese, and vanadium
  • the decomposition of the fatty acid peroxides catalyzed by metal ions generate fatty acid oxide radicals and fatty acid peroxide radicals.
  • the metal catalyst is recurrently converted from the lower to the higher oxidation state and back again.
  • a liquid coating composition containing resins based on unsaturated fatty acids and metal driers when exposed to air, will rapidly convert into a drying polymeric matrix.
  • oxygen is required for the formation of surface skin on air-drying coatings by oxidative polymerization processes.
  • the concentration of driers found in the skin is disproportionate and removal will lead to a prolongation of drying time of the remaining coating material.
  • anti-skinning agents are included in coating formulations.
  • Oximes, and in particular methyl ethyl ketoxime (MEKO) are known to reduce skin formation considerably, particularly in alkyd formulations containing cobalt-based driers.
  • MEKO methyl ethyl ketoxime
  • the mechanism associated with the antiskinning performance of oximes is still not accepted unanimously, the prevailing hypothesis concerns the association of the oxime to the free coordination sites of the metal carboxylate thereby suppressing the activity of the catalyst.
  • the weak metal - oxime complex will stay intact. However, after the can is opened for paint application, the complex will dissociate and the relatively volatile oxime will be released into the surrounding atmosphere.
  • a drier and anti-skinning agent system for an oxidatively drying binder-based coating composition comprising: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising i. an alkanolamine of formula (I) wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl, or an arylalkyl; wherein each R 3 and R 4 independently represent hydrogen, or an alkyl; wherein m represents 0 or 1 ; wherein n represents an integer from 1 to 10; and ii.
  • a drying agent comprising an iron ligand complex and/or a manganese ligand complex
  • an anti-skinning agent comprising i. an alkanolamine of formula (I) wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl, or an arylalkyl; wherein each R 3
  • R 5 represents an alkyl or an arylalkyl
  • X represents a methylene or a carbonyl group
  • Y represents methylene group or oxygen
  • (B) is a diketone of formula (III) or a
  • a drier and anti-skinning agent system for an oxidatively drying binderbased coating composition comprising: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising a mercaptan of formula (II) wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; and wherein Y represents methylene group or oxygen.
  • a coating composition comprising an oxidatively drying binder and the drier and anti-skinning agent systems disclosed herein.
  • a substrate having a coating on at least a portion thereof, the coating being derived from a coating composition disclosed herein.
  • a method of preventing or mitigating skin formation in an oxidatively drying binder-based coating composition comprising using a drier and anti-skinning agent system comprising: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising i. an alkanolamine of formula (I) wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl, or an arylalkyl; wherein each R 3 and R 4 independently represent hydrogen, or an alkyl; wherein m represents 0 or 1 ; wherein n represents an integer from 1 to 10; and ii.
  • a drying agent comprising an iron ligand complex and/or a manganese ligand complex
  • an anti-skinning agent comprising i. an alkanolamine of formula (I) wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl
  • R 5 represents an alkyl or an arylalkyl
  • X represents a methylene or a carbonyl group
  • Y represents methylene group or oxygen
  • (B) is a diketone of formula (III) where p represents 0, 1 or 2
  • a method of preventing or mitigating skin formation in an oxidatively drying binder-based coating composition comprising using a drier and anti-skinning agent system comprising: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising a mercaptan of formula (II) wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; and wherein Y represents methylene group or oxygen.
  • a drying agent comprising an iron ligand complex and/or a manganese ligand complex
  • an anti-skinning agent comprising a mercaptan of formula (II) wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; and wherein Y represents methylene group or oxygen.
  • a drier and anti-skinning agent system comprising: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising i. an alkanolamine of formula (I) wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl, or an arylalkyl; wherein each R 3 and R 4 independently represent hydrogen, or an alkyl; wherein m represents 0 or 1 ; and wherein n represents an integer from 1 to 10; and ii.
  • R 5 represents an alkyl or an arylalkyl
  • X represents a methylene or a carbonyl group
  • Y represents methylene group or oxygen
  • (B) is a dike
  • a drier and anti-skinning agent system comprising: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising a mercaptan of formula (II) wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; and wherein Y represents methylene group or oxygen, to prevent or mitigate skin formation in an oxidatively drying binder-based coating composition.
  • a drying agent comprising an iron ligand complex and/or a manganese ligand complex
  • an anti-skinning agent comprising a mercaptan of formula (II) wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; and wherein Y represents methylene group or oxygen, to prevent or mitigate skin formation in an oxidatively drying binder-based coating composition.
  • the drier and anti-skinning agent of the present invention is suitable for use in a one-component (1 K) coating composition.
  • a coating composition comprising: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising a mercaptan of formula (II) wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; and wherein Y represents methylene group or oxygen, wherein the coating composition is a one-component (1 K) coating composition.
  • a coating composition comprising: aa. an oxidatively drying binder a. drying agent comprising an iron ligand complex and/or a manganese ligand complex; b. an anti-skinning agent comprising i. an alkanolamine of formula (I) wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl, or an arylalkyl; wherein each R 3 and R 4 independently represent hydrogen, or an alkyl; wherein m represents 0 or 1 ; and wherein n represents an integer from 1 to 10; and ii.
  • R 5 represents an alkyl or an arylalkyl
  • X represents a methylene or a carbonyl group
  • Y represents methylene group or oxygen
  • (B) is a diketone of formula (III) where p represents 0, 1 or 2
  • a coating composition comprising: aa. an oxidatively drying binder b. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; c. an anti-skinning agent comprising a mercaptan of formula (II) wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; wherein Y represents methylene group or oxygen.
  • a drying agent means one drying agent or more than one drying agent.
  • an anti-skinning agent means one anti-skinning agent or more than one anti-skinning agent.
  • the term "and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a list is described as comprising group A, B, and/or C, the list can comprise A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.
  • substituted when used herein, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using “substituted” is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e. a compound that is sufficiently robust to survive isolation from a reaction mixture.
  • optionally substituted when used herein at the start of a list of chemical species it is meant to indicate that all of the species in the list which can be substituted may be optionally substituted; that is it is not meant that only the first species mentioned in the list may be optionally substituted.
  • optionally substituted when used herein means unsubstituted or substituted with a suitable group.
  • substituents may be selected from but not limited to, for example, the group comprising halogen, alkyl, haloalkyl, haloalkyloxy, hydroxyl, hydroxyalkyl, amino, aminoalkyl, carboxyl, a nitro group, a nitrile group, an imine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group.
  • an aliphatic group is a hydrocarbon moiety that may be straight chain or branched and may be completely saturated, or contain one or more units of unsaturation, but which is not aromatic.
  • the term “unsaturated” means a moiety that has one or more double and/or triple bonds.
  • the term “aliphatic” is therefore intended to encompass alkyl, alkenyl or alkynyl groups, and combinations thereof.
  • hydroxyl or "hydroxy” as used herein refers to the group -OH.
  • alk or “alkyl”, as used herein unless otherwise defined, relates to saturated hydrocarbon radicals being straight, branched, cyclic or polycyclic moieties or combinations thereof and contain 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 8 carbon atoms, such as 1 to 6 carbon atoms, or even 1 to 4 carbon atoms.
  • radicals may be optionally substituted with a chloro, bromo, iodo, cyano, nitro, OR 19 , OC(O)R 20 , C(O)R 21 , C(O)OR 22 , NR 23 R 24 , C(O)NR 25 R 26 , SR 27 , C(O)SR 27 , C(S)NR 25 R 26 , aryl or Het, wherein R 19 to R 27 each independently represent hydrogen, aryl or alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or dialkylsiloxane groups.
  • radicals may be independently selected from methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, pentyl, iso-amyl, hexyl, cyclohexyl, 3-methylpentyl, octyl and the like.
  • alkylene as used herein, relates to a bivalent radical alkyl group as defined above. For example, an alkyl group such as methyl which would be represented as -CH3, becomes methylene, -CH2-, when represented as an alkylene. Other alkylene groups should be understood accordingly.
  • alkenyl relates to hydrocarbon radicals having, such as up to 4, double bonds, being straight, branched, cyclic or polycyclic moieties or combinations thereof and containing from 2 to 18 carbon atoms, such as 2 to 10 carbon atoms, such as from 2 to 8 carbon atoms, such as 2 to 6 carbon atoms, or even 2 to 4 carbon atoms.
  • radicals may be optionally substituted with a hydroxyl, chloro, bromo, iodo, cyano, nitro, OR 19 , OC(O)R 20 , C(O)R 21 , C(O)OR 22 , NR 23 R 24 , C(O)NR 25 R 26 , SR 27 , C(O)SR 27 , C(S)NR 25 R 26 , or aryl, wherein R 19 to R 27 each independently represent hydrogen, aryl or alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or dialkylsiloxane groups.
  • radicals may be independently selected from alkenyl groups include vinyl, allyl, isopropenyl, pentenyl, hexenyl, heptenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, 1 -propenyl, 2-butenyl, 2-methyl-2-butenyl, isoprenyl, farnesyl, geranyl, geranylgeranyl and the like.
  • alkynyl relates to hydrocarbon radicals having, such as up to 4, triple bonds, being straight, branched, cyclic or polycyclic moieties or combinations thereof and having from 2 to 18 carbon atoms, such as 2 to 10 carbon atoms, such as from 2 to 8 carbon atoms, such as from 2 to 6 carbon atoms, or even from 2 to 4 carbon atoms.
  • radicals may be optionally substituted with a hydroxy, chloro, bromo, iodo, cyano, nitro, OR 19 , OC(O)R 20 , C(O)R 21 , C(O)OR 22 , NR 23 R 24 , C(O)NR 25 R 26 , SR 27 , C(O)SR 27 , C(S)NR 25 R 26 , or aryl, wherein R 19 to R 27 each independently represent hydrogen, aryl or lower alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or dialkylsiloxane groups.
  • alkynyl radicals examples include ethynyl, propynyl, propargyl, butynyl, pentynyl, hexynyl and the like.
  • alkynylene as used herein, relates to a bivalent radical alkynyl group as defined above.
  • an alkynyl group such as ethynyl which would be represented as -CECH
  • ethynylene, -CEC- when represented as an alkynylene.
  • Other alkynylene groups should be understood accordingly.
  • aryl as used herein, relates to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic.
  • radicals may be optionally substituted with a hydroxy, chloro, bromo, iodo, cyano, nitro, OR 19 , OC(O)R 20 , C(O)R 21 , C(O)OR 22 , NR 23 R 24 , C(O)NR 25 R 26 , SR 27 , C(O)SR 27 , C(S)NR 25 R 26 , or aryl, wherein R 19 to R 27 each independently represent hydrogen, aryl or lower alkyl, and/or be interrupted by oxygen or sulphur atoms, or by silano or d ial kylsilcon groups.
  • radicals may be independently selected from phenyl, p-tolyl, 4-methoxyphenyl, 4-(tert-butoxy)phenyl, 3-methyl-4-methoxyphenyl, 4- fluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 3-aminophenyl, 3-acetamidophenyl, 4-acetamidophenyl, 2- methyl-3-acetamidophenyl, 2-methyl-3-aminophenyl, 3-methyl-4-aminophenyl, 2-amino-3- methylphenyl, 2,4-dimethyl-3-aminophenyl, 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 1 -naphthyl, 2- naphthyl, 3-amino-1 -naphthyl, 2-methyl-3-amino-1 -naphthyl, 6-amino-2-naphthyl, 4,6-dimethoxy-2-
  • arylene relates to a bivalent radical aryl group as defined above.
  • an aryl group such as phenyl which would be represented as -Ph, becomes phenylene, -Ph-, when represented as an arylene.
  • Other arylene groups should be understood accordingly.
  • alkyl is used as a suffix following another term, as in “hydroxyalkyl,” this is intended to refer to an alkyl group, as defined above, being substituted with one or two substituent(s) selected from the other, specifically-named group, also as defined herein.
  • hydroxyalkyl therefore refers to a -R 13 -OH group wherein R 13 is alkylene as defined herein.
  • alkoxy or “alkyloxy”, as a group or part of a group, refers to a group having the Formula -OR 14 wherein R 14 is alkyl as defined herein above.
  • alkyl, alkenyl, alkynyl, aryl or aralkyl in composite groups herein should be interpreted accordingly, for example the reference to alkyl in aminoalkyl or alk in alkoxyl should be interpreted as alk or alkyl above etc.
  • Ci-i2alkylene by itself or as part of another substituent, refers to Ci-i2alkyl groups that are divalent, i.e., with two points of attachment to two other groups.
  • Alkylene groups may be linear or branched and may be substituted as indicated herein.
  • Non-limiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methyl-ethylene (- CH(CH 3 )-CH 2 -), n-propylene (-CH2-CH2-), 2-methylpropylene (-CH 2 -CH(CH 3 )-CH 2 -), 3- methylpropylene (-CH2-CH2-CH(CH 3 )-), n-butylene (-CH2-CH2-CH2-), 2-methylbutylene (-CH2- CH(CH 3 )-CH2-CH2-), 4-methylbutylene (-CH2-CH2-CH2-CH(CH 3 )-), pentylene and its chain isomers, hexylene and its chain isomers, heptylene and its chain isomers, octylene and its chain isomers, nonylene and its chain isomers, decylene and its chain isomers, undecylene and its chain isomers, do
  • heteroalkyl As set out above in relation to the terms “heteroalkyl”, “heteroalkenyl” and “heteroalkynyl”, the terms “heteroalkylene”, “heteroalkenylene” and “heteroalkynylene” refer mutatis mutandis to an alkylene, alkenylene or alkynylene group containing one or more S, N, O, P, or Si atoms.
  • amino refers to the group -NH2.
  • ether includes both mono and polyethers and refers to groups having a chain containing carbon and oxygen and each of these units suitably comprises 1 to 12 carbons for each oxygen atom. Examples are dimethyl, diethyl and dipropyl ethers, polyethyleneoxide, polypropyleneoxide, polyethylene glycol, polybutyleneoxide.
  • halo or "halogen” as a group or part of a group is generic for fluoro, chloro, bromo, and iodo, suitably to F, Cl, Br, and I, more suitably to F, Cl, and Br.
  • haloalkyl as a group or part of a group, refers to an alkyl group having the meaning as defined above wherein one or more hydrogens are replaced with one or more halogen as defined above.
  • cycloalkyl refers to a cyclic alkyl group, that is a monovalent, saturated, hydrocarbyl group having 1 or more cyclic structure, and comprising from 3 to 12 carbon atoms, suitably from 3 to 9 carbon atoms, suitably from 3 to 6 carbon atoms, suitably from 5 to 6 carbon atoms.
  • Cycloalkyl includes all saturated hydrocarbon groups containing 1 or more rings, including monocyclic or bicyclic groups. The further rings of multi- ring cycloalkyls may be either fused, bridged and/or joined through one or more spiro atoms.
  • Cs-ecycloalkyl a cyclic alkyl group comprising from 3 to 6 carbon atoms, suitably from 5 to 6 carbon atoms.
  • Examples of cycloalkyl groups include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
  • ene is used in conjunction with a cycloalkyl group, i.e. cycloalkylene, this is intended to mean the cycloalkyl group as defined herein having two single bonds as points of attachment to other groups.
  • iron ligand complex or “manganese ligand complex” refers to an iron complex or a manganese ligand complex comprising a ligand that acts as a donor of an electron lone pair to form a coordination complex thereby increasing the stability of the manganese or iron ion-containing material in the composition.
  • the term “drier and anti-skinning agent system” refers to a composition comprising a drying agent and an anti-skinning agent.
  • the present inventors have found that the drier and anti-skinning agent systems of the invention in autoxidizable binder based compositions improves the drying times of the composition, while simultaneously providing prolonged skin-free periods.
  • the term “drier” refers to organometallic compounds that are soluble in organic solvents and binders. They are added to unsaturated oils and binders in order to appreciably reduce their curing times, i.e. the transition of their liquid films to the solid phase. Driers are available either as solids or in solution (siccatives). Suitable solvents are organic solvents, fatty acid esters and oxygenated solvents as glycol ethers. The driers are present in amounts expressed as weight percent of the metal atom based on the weight of binder solids (or resin) unless stated otherwise.
  • the term “substantially free” means that the material being discussed is present in the composition, if at all, as an incidental impurity. In other words, the material does not affect the properties of the composition. As used herein, the term “completely free” means that the material being discussed is not present in the composition at all.
  • the drying agent comprises an iron ligand complex and/or a manganese ligand complex.
  • the iron ligand complex and/or a manganese ligand complex may be substantially free of cobalt.
  • the drying agent comprising an iron ligand complex and/or a manganese ligand complex may comprise a primary drying agent.
  • the primary drying agent may be substantially free of cobalt.
  • the drier and anti-skinning agent system may comprise less than 0.001 wt% of cobalt, such as less than 0.0001 wt% of cobalt, such as less than 0.00001 , 0.000001 or 0.0000001 wt% of cobalt based on the total solid weight of the oxidatively drying binder.
  • the drying agent comprising a primary drying agent or an iron ligand complex and/or a manganese ligand complex may be completely free of cobalt.
  • the drier and anti-skinning agent system may comprise a further drier comprising an organic salt of one or more of manganese, cerium, zirconium and calcium.
  • the drier and anti-skinning agent system of the invention may comprise a further drier comprising an organic salt of manganese and/or cerium.
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex and/or a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I) ii. a mercaptan of formula (II).
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex and/or a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a mercaptan of formula (V): wherein R 5 represents an alkyl or an arylalkyl
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex and/or a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a diketone of formula (III) or a diketone of formula (IV).
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex and/or a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a mercaptan of formula (II) or formula (V); and
  • the drier and anti-skinning agent system may comprise: a. a drying agent comprising an iron ligand complex and/or a manganese ligand complex; and b. an anti-skinning agent comprising a mercaptan of formula (II) or formula (V)
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex or a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a mercaptan of formula (II) or a mercaptan of formula (V).
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex or a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a diketone of formula (III) or a diketone of formula (IV).
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex or a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a mercaptan of formula (II) or formula (V); and
  • the drier and anti-skinning agent system of the invention may comprise: a) a drying agent comprising an iron ligand complex or a manganese ligand complex; b) an anti-skinning agent comprising a mercaptan of formula (II) or formula (V)
  • the drier and anti-skinning agent system of the invention may comprise: a) a drying agent comprising an iron ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I) ii. a mercaptan of formula (II) or a mercaptan of formula (V).
  • the drier and anti-skinning agent system of the invention may comprise: a) a drying agent comprising an iron ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a diketone of formula (III) or a diketone of formula (IV).
  • the drier and anti-skinning agent system of the invention may comprise: a) A drying agent comprising an iron ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a mercaptan of formula (II) or formula (V); and
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising an iron ligand complex; b) an anti-skinning agent comprising a mercaptan of formula (II) or formula (V)
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I) ii. a mercaptan of formula (II) or a mercaptan of formula (V).
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a diketone of formula (III) or a diketone of formula (IV).
  • the drier and anti-skinning agent system may comprise: a) A drying agent comprising a manganese ligand complex; and b) an anti-skinning agent comprising i. an alkanolamine of formula (I); and ii. a mercaptan of formula (II) or formula (V); and
  • the drier and anti-skinning agent system may comprise: a) a drying agent comprising a manganese ligand complex; b) an anti-skinning agent comprising a mercaptan of formula (II) or formula (V).
  • the iron and/or manganese ligand complexes may be primary drying agents.
  • the above defined primary drying agents may promote the curing (or oxidative polymerisation) of an autoxidizable resin.
  • the above defined primary drying agents may reduce the drying or curing time of the alkyd resin.
  • the iron and/or manganese may have at least two accessible valence states.
  • the primary drying agent may be selected from a manganese ligand complex, and/or an iron ligand complex.
  • Such manganese and/or iron ligand complexes may comprise a salt of an organic or an inorganic anion (and mixtures thereof).
  • suitable organic anions for forming the salts include carboxylates (for example octoates, napthenates, neodecanoates, linoleates and tallates) and p-diketonates (for example acetylacetonates, benzoylacetones and dibenzoylmethanes).
  • the primary drying agent may comprise a complex of an organic or inorganic salt of a manganese ion and/or iron ion and a bidentate, tridentate, tetradentate, pentadentate or hexadentate nitrogen ligand.
  • Suitable inorganic anions for forming the salts include phosphates and halides (for example chlorides or bromides).
  • Suitable iron and/or manganese ligand complexes can be prepared according to known procedures or can be obtained commercially.
  • suitable commercially available primary drying agents that comprise a manganese ligand complex include Nuodex® Drycoat (Venator).
  • suitable commercially available primary drying agents that comprise an iron ligand complex include Borchi® OXY-Coat (Borchers).
  • the percentage of manganese, and/or iron in the coating composition may be dependent on the type of oxidatively drying binder used in the coating composition.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00007 to 0.07 % by weight or greater of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00007 to 0.07 % by weight, such as from 0.000075 to 0.065 % by weight, such as from 0.00008 to 0.06 % by weight, such as from 0.000085 to 0.055 % by weight, such as from 0.00009 to 0.05 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise at least 0.00007 % by weight, such as at least 0.000075 % by weight, such as at least 0.00008 % by weight, such as at least 0.000085 % by weight, such as at least 0.00009 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise up to 0.07 % by weight, such as up to 0.065 % by weight, such as up to 0.06 % by weight, such as up to 0.055 % by weight, such as up to 0.05 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00007 to 0.07 % by weight, such as from 0.00007 to 0.065 % by weight, such as from 0.00007 to 0.06 % by weight, such as from 0.00007 to 0.055 % by weight, such as from 0.00007 to 0.05 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.000075 to 0.07 % by weight, such as from 0.000075 to 0.065 % by weight, such as from 0.000075 to 0.06 % by weight, such as from 0.000075 to 0.055 % by weight, such as from 0.000075 to 0.05 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00008 to 0.07 % by weight, such as from 0.00008 to 0.065 % by weight, such as from 0.00008 to 0.06 % by weight, such as from 0.00008 to 0.055 % by weight, such as from 0.00008 to 0.05 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.000085 to 0.07 % by weight, such as from 0.000085 to 0.065 % by weight, such as from 0.000085 to 0.06 % by weight, such as from 0.000085 to 0.055 % by weight, such as from 0.000085 to 0.05 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and antiskinning agent system may comprise from 0.00009 to 0.07 % by weight, such as from 0.00009 to 0.065 % by weight, such as from 0.00009 to 0.06 % by weight, such as from 0.00009 to 0.055 % by weight, such as from 0.00009 to 0.05 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00025 to 0.06 % by weight, such as from 0.000255 to 0.055 % by weight, such as from 0.00026 to 0.05 % by weight, such as from 0.000265 to 0.045 % by weight, such as from 0.00027 to 0.04 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a composition comprising the drier and anti-skinning agent system may comprise up to 1 % by weight of manganese and/or iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00007 to 0.00475 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00007 to 0.00475 % by weight, such as from 0.000075 to 0.0047 % by weight, such as from 0.00008 to 0.00465 % by weight, such as from 0.000085 to 0.0046 % by weight, such as from 0.00009 to 0.00455 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise at least 0.00007 % by weight, such as at least 0.000075 % by weight, such as at least 0.00008 % by weight, such as at least 0.000085 % by weight, such as at least 0.00009 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise up to 0.00475 % by weight, such as up to 0.0047 % by weight, such as up to 0.00465 % by weight, such as up to 0.0046 % by weight, such as up to 0.00455 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00007 to 0.00475 % by weight, such as from 0.00007 to 0.0047 % by weight, such as from 0.00007 to 0.00465 % by weight, such as from 0.00007 to 0.0046 % by weight, such as from 0.00007 to 0.00455 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.000075 to 0.00475 % by weight, such as from 0.000075 to 0.0047 % by weight, such as from 0.000075 to 0.00465 % by weight, such as from 0.000075 to 0.0046 % by weight, such as from 0.000075 to 0.00455 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and antiskinning agent system may comprise from 0.00008 to 0.00475 % by weight, such as from 0.00008 to 0.0047 % by weight, such as from 0.00008 to 0.00465 % by weight, such as from 0.00008 to 0.0046 % by weight, such as from 0.00008 to 0.00455 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.000085 to 0.00475 % by weight, such as from 0.000085 to 0.0047 % by weight, such as from 0.000085 to 0.00465 % by weight, such as from 0.000085 to 0.0046 % by weight, such as from 0.000085 to 0.00455 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00009 to 0.00475 % by weight, such as from 0.00009 to 0.0047 % by weight, such as from 0.00009 to 0.00465 % by weight, such as from 0.00009 to 0.0046 % by weight, such as from 0.00009 to 0.00455 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00025 to 0.0022 % by weight, such as from 0.000255 to 0.0021 % by weight, such as from 0.00026 to 0.0020 % by weight, such as from 0.000265 to 0.0019 % by weight, such as from 0.00027 to 0.0018 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a composition comprising the drier and anti-skinning agent system may comprise up to 1 % by weight of iron based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.0008 to 0.07 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.0008 to 0.07 % by weight, such as from 0.00085 to 0.065 % by weight, such as from 0.0009 to 0.06 % by weight, such as from 0.00095 to 0.055 % by weight, such as from 0.001 to 0.05 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise at least 0.0008 % by weight, such as at least 0.00085 % by weight, such as at least 0.0009 % by weight, such as at least 0.00095 % by weight, such as at least 0.001 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and antiskinning agent system may comprise up to 0.07 % by weight, such as up to 0.065 % by weight, such as up to 0.06 % by weight, such as up to 0.055 % by weight, such as up to 0.05 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.0008 to 0.07 % by weight, such as from 0.0008 to 0.065 % by weight, such as from 0.0008 to 0.06 % by weight, such as from 0.0008 to 0.055 % by weight, such as from 0.0008 to 0.05 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and antiskinning agent system may comprise from 0.00085 to 0.07 % by weight, such as from 0.00085 to 0.065 % by weight, such as from 0.00085 to 0.06 % by weight, such as from 0.00085 to 0.055 % by weight, such as from 0.00085 to 0.05 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.0009 to 0.07 % by weight, such as from 0.0009 to 0.065 % by weight, such as from 0.0009 to 0.06 % by weight, such as from 0.0009 to 0.055 % by weight, such as from 0.0009 to 0.05 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.00095 to 0.07 % by weight, such as from 0.00095 to 0.065 % by weight, such as from 0.00095 to 0.06 % by weight, such as from 0.00095 to 0.055 % by weight, such as from 0.00095 to 0.05 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.001 to 0.07 % by weight, such as from 0.001 to 0.065 % by weight, such as from 0.001 to 0.06 % by weight, such as from 0.001 to 0.055 % by weight, such as from 0.001 to 0.05 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.0016 to 0.024 % by weight, such as from 0.0017 to 0.023 % by weight, such as from 0.0018 to 0.022 % by weight, such as from 0.0019 to 0.021 % by weight, such as from 0.002 to 0.020 % by weight of manganese based on the total solid weight of the oxidatively drying binder.
  • a composition comprising the drier and anti-skinning agent system may comprise up to 1 % by weight of manganese based on the total weight of the solid oxidatively drying binder Iron ligand complex
  • the drier and anti-skinning agent system may comprise a primary drier agent comprising an iron ligand complex, which may comprise iron and a nitrogen donor ligand.
  • the nitrogen donor ligand may comprise tridentate, tetradentate, pentadentate and hexadentate nitrogen donor ligands. For example, selected from the group comprising tetradentate, pentadentate, and hexadentate nitrogen donor ligands.
  • Primary drier agents comprising an iron ligand complex may comprise a nitrogen donor ligand according to formula (VI): wherein R 8 and R 9 each independently represent an alkyl, an aryl, or a group containing heteroatoms (e.g.
  • R 10 and R 11 each independently represent hydrogen, an alkyl, an aryl, an alkylaryl, an ether, a heteroaryl, an alkylaminoalkyl, a heteroaryl alkyl, or an ester group;
  • R 12 and R 13 each independently represent hydrogen, a halogen, OH, an alkoxy, an amide, an amine, or an aminoalkyl; and wherein X 1 represents a carbonyl or an alkylene.
  • R 8 or R 9 may independently be substituted with one or more substituents, each independently represent an alkyl, an aryl, and/or an aryl alkyl group.
  • R 8 and R 9 each may independently represent heteroaryl, heteroaryalkyl, alkylaminoalkyl; wherein heteroaryl may be selected from the group consisting of pyridyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl, such as pyridin-2yl.
  • R 10 and R 11 may each independently represent hydrogen, an alkyl or an ester group.
  • Primary drier agents comprising an iron ligand complex may comprise a nitrogen donor ligand according to formula (VI*) or formula (VI**):
  • Primary drier agents comprising an iron ligand complex may comprise a nitrogen donor ligand, “(L)”; wherein the ligand is present in one or more forms selected from [Fe(L)CI], [Fe(L)CI]CI, [Fe(L)(H2O)](PF 6 )2,[Fe(L)]Cl2, [Fe(L)CI]PF 6 or [Fe(L)(H 2 O)](BF 4 )2.
  • Primary drier agents comprising an iron ligand complex may include compounds of formula (V
  • Primary drier agents comprising an iron ligand complex may include iron(1 +),chloro[dimethyl- 9,9-dihydroxy-3-methyl-2,4-di(2-pyridyl-kN )- 7 -[(2-pyridinyl-kN )methyl]-3, 7-diazabicyclo[3.3 .1 ]nonane-1 , 5-dicarboxylate-kN3, kN7],chloride( 1-).
  • the drier and anti-skinning agent system comprises an iron ligand complex
  • the drier and anti-skinning agent system may comprise a further drying agent comprising an organic salt of manganese and/or cerium.
  • the drier and anti-skinning agent system of the invention comprises an iron ligand complex
  • the drier and anti-skinning agent system may comprise a further drying agent comprising the carboxylate salt of manganese and/or cerium.
  • Drying agents comprising the carboxylate salt of manganese and/or cerium can be prepared according to known procedures or can be obtained commercially. Examples of suitable commercially available drying agents based on carboxylate salts of manganese and/or cerium include Octa-Soligen® Manganese 10 (Borchers) and Duroct Cerium 12% (Dura).
  • the drier and anti-skinning agent system of the invention may comprise a primary drying agent comprising a manganese ligand complex.
  • the primary drying agent comprising a manganese ligand complex may comprise a ligand of formula (IX):
  • each R 20 are identical or different from each other, independently represents an alkyl, a heteroaryl, an aryl, an arylalkyl, or an alkylaryl group.
  • the ligand of formula (IX) is also referred to as a TACN-Tx ligand.
  • the ligand of formula (IX) may be 1 ,4,7-trimethyl-1 ,4,7-tri-azacyclononane.
  • Primary driers comprising a manganese ligand complex may include complexes of formula (VII): wherein each R 1 * are identical or different from each other, and independently represent an alkyl, an alkenyl, or an alkynyl group; wherein n is an integer from 1 to 5 (i.e. 1 , 2, 3, 4, or 5), such as from 2 to 5, such as 2; wherein X, Y, and Z are identical or different from each other, and represent an R 2 *COO _ group; and wherein each R 2 * are identical or different from each other, and independently represent a hydrogen, an alkyl, an alkenyl, an alkynyl, a heteroalkyl or an arylalkyl group.
  • each R 1 * may be identical or different from each other and represent an alkyl.
  • Each R 1 * may represent a methyl group.
  • each R 2 * may be identical or different from each other and represent an alkyl group.
  • Primary drier agents comprising a manganese ligand complex may include compounds of formula (Vl *’):
  • R’ each represent an R 2 *COO _ group.
  • R’ may represent CH2 (CH2)3CH(C2H5)CO2 _ or CHsCC ⁇ '.
  • Primary drier agents comprising a manganese ligand complex may include tri-p-(2- ethylhexanoato-0)-bis(N,N',N"trimethyl-1 ,4, 7-triazacyclononane-N ,N' ,N")di-manganese and p- (acetato-0)-di-p-(2-ethylhexanoatoO)-bis(N, N' ,N"-trimethyl-1 ,4, 7-triazacyclononane-N, N' ,N")di- manganese.
  • the drier and anti-skinning agent system comprises a manganese ligand complex
  • the drier and anti-skinning agent system may comprise a further drying agent comprising an organic salt of manganese and/or cerium.
  • the drier and anti-skinning agent system comprises a manganese ligand complex
  • the drier and anti-skinning agent system may comprise a further drying agent comprising the carboxylate salt of manganese and/or cerium.
  • Drying agents comprising the carboxylate salt of manganese and/or cerium can be prepared according to known procedures or can be obtained commercially.
  • suitable commercially available drying agents based on carboxylate salts of manganese and/or cerium include Octa-Soligen® Manganese 10 (Borchers) and Duroct Cerium 12% (Dura). COORDINATION AND/OR AUXILIARY DRYING AGENT
  • the drier and anti-skinning agent system may further comprise a coordination drying agent and/or an auxiliary drying agent.
  • Coordination driers may enhance the homogeneous through drying of a coating film by interaction with the carboxyl and hydroxyl groups in a polymeric binder. This way, coordination driers can bridge two or more polymer chains.
  • the carboxyl and hydroxyl groups may be initially present in the binder molecule or formed during the autoxidation process.
  • Typical coordination driers may be selected from zirconium (Zr), strontium (Sr), aluminium (Al), bismuth (Bi), lanthanum (La), and/or neodymium (Nd) based metal driers.
  • Auxiliary driers are also referred to synonymously as secondary driers. These metal driers exist in a single oxidation state and are not catalytically active by themselves. However, secondary driers may affect the rate-of-dry by interacting with the primary drying agent. Typical secondary driers may be selected from calcium (Ca), barium (Ba), zinc (Zn), potassium (K) and/or lithium (Li) metal soaps.
  • the drier and anti-skinning agent system comprises an anti-skinning agent.
  • a coating composition comprising the drier and anti-skinning agent system may comprise 0.1 to 6% by weight of the anti-skinning agent, based on the total weight of a coating composition, such as 0.1 to 5% by weight of the anti-skinning agent, based on the total weight of a coating composition.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise from 0.2 to 5% by weight of the anti-skinning agent, for example from 0.2 to 4.5 % by weight, for example from 0.5 to 3.5 % by weight, based on the total weight of a coating composition.
  • the drier and anti-skinning agent system may further comprise an anti-skinning agent comprising an alkanolamine of formula (I): wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl, or an arylalkyl; wherein each R 3 and R 4 independently represent hydrogen, or an alkyl; wherein m represents 0 or 1 ; and wherein n represents an integer from 1 to 10.
  • an anti-skinning agent comprising an alkanolamine of formula (I): wherein each R 1 and R 2 independently represent hydrogen, an alkyl, alkenyl, an aryl, or an arylalkyl; wherein each R 3 and R 4 independently represent hydrogen, or an alkyl; wherein m represents 0 or 1 ; and wherein n represents an integer from 1 to 10.
  • the alkanolamine of formula (I) may be selected from one or more of ethanolamine, 1 -amino- 2-propanol, 3-amino-1 -propanol, 2-amino-1 -butanol, 4-amino-1 -butanol, 2-(methylamino)ethanol, 2- (ethylamino)ethanol, 2-(n-propylamino)ethanol, 2-(lsopropylamino)ethanol, 2-(n-butylamino)ethanol, 2- (tert-butylamino)ethanol, 2-(n-hexylethanol)amine, 2-(n-octylethanol)amine, 2-dimethylaminoethanol, 2-(diethylamino)ethanol, 2-(diisopropylamino)ethanol, 2-(dibutylamino)ethanol, 2- (dioctylamino)ethanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1 -
  • the alkanolamine of formula (I) may be selected from one or more of 2-dimethylaminoethanol, 1 -[bis[3-(dimethylamino)propyl]amino]-2-propanol, and 2-dimethylamino-2-methylpropanol.
  • the alkanolamine of formula (I) may be selected from one or more of 1-dimethylamino-2- propanol and 3-(dimethylamino)-1 -propanol.
  • the alkanolamine of formula (I) may comprise 2-dimethylaminoethanol.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise at least 0.1%, at least 0.2%, at least 0.3%, at least 0.5% or at least 0.8% by weight of the alkanolamine of formula (I), based on the total weight of a coating composition.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise up to 5%, up to 4%, up to 3% up to 2.5% or up to 2% by weight of the alkanolamine of formula (I), based on the total weight of a coating composition.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise 0.1 to 5 % by weight of the alkanolamine of formula (I), based on the total weight of a coating composition.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.2 to 4% by weight of the alkanolamine of formula (I), such as from 0.3 to 2.5 % by weight, for example from 0.5 to 2 % by weight, based on the total weight of a coating composition.
  • the drier and anti-skinning agent system may further comprise an anti-skinning agent comprising a mercaptan of formula (II): wherein R 5 represents an alkyl or an arylalkyl; wherein X represents a methylene or a carbonyl group; and wherein Y represents methylene group or oxygen. When X is a carbonyl group, Y may be oxygen.
  • the mercaptan of formula (II) may be selected from one or more of isooctyl 3- mercaptopropionate (IOMP), n-butyl 3-mercaptopropionate (BMP), methyl 3-mercaptopropionate, n- dodecyl mercaptan (DDM), f-dodecyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, sec-octyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, n-hexyl mercaptan, n-amyl mercaptan, n- butyl mercaptan, and f-butyl mercaptan.
  • IOMP isooctyl 3- mercaptopropionate
  • BMP n-butyl 3-mercap
  • the drier and anti-skinning agent system of the invention may further comprise an antiskinning agent comprising a mercaptan of formula (V): wherein R 5 represents an alkyl or an arylalkyl.
  • the mercaptan of formula (II) or formula (V) may be selected from one or more of isooctyl 3- mercaptopropionate (IOMP), n-butyl 3-mercaptopropionate (BMP), and methyl 3-mercaptopropionate.
  • IOMP isooctyl 3- mercaptopropionate
  • BMP n-butyl 3-mercaptopropionate
  • methyl 3-mercaptopropionate methyl 3-mercaptopropionate
  • the mercaptan of formula (II) or formula (V) may comprise isooctyl 3-mercaptopropionate (IOMP).
  • R 5 of the mercaptan of formula (II) or formula (V) may comprise a linear or branched Ci to Cs alkyl, which may be unsubstituted.
  • R 5 of the mercaptan of formula (II) or formula (V) may be CH3.
  • R 5 of the mercaptan of formula (II) or formula (V) may be -CH2(CH2)nCH3 wherein n is an integer from 1 to 10, such as from 1 to 5, such as 2.
  • the R 5 of the mercaptan of formula (II) or formula (V) may be - CH2(CH 2 )nCH 2 CH(CH3)2 wherein n is an integer from 1 to 10, such as 3 to 6, such as 4.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise at least 0.05%, at least 0.1 %, at least 0. 3%, at least 0.5%, or at least 0.8% by weight of the mercaptan of formula (II) or (V), based on the total weight of a coating composition.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise up to 5%, up to 4%, up to 3% up to 2.5% or up to 2% by weight of the mercaptan of formula (II) or (V), based on the total weight of a coating composition.
  • a coating composition comprising the drier and anti-skinning agent system may comprise from 0.05 to 5 % by weight of the mercaptan of formula (II) or (V), based on the total weight of a coating composition.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise from 0.05 to 4 % by weight of the mercaptan of formula (II) or (V), such as from 0.3 to 3.5 % by weight, for example from 0.5 to 3 % by weight, based on the total weight of a coating composition.
  • the drier and anti-skinning agent system of the invention may further comprise an antiskinning agent comprising a diketone of formula (III): or a diketone of formula (IV): where p represents 0, 1 or 2; wherein each of R 6 and R 7 independently represent an alkyl, an aryl, or an arylalkyl; and wherein W represents an alkylene group, optionally substituted with one or more substituents selected from the group comprising an alkyl, -OH, and a halogen.
  • an antiskinning agent comprising a diketone of formula (III): or a diketone of formula (IV): where p represents 0, 1 or 2; wherein each of R 6 and R 7 independently represent an alkyl, an aryl, or an arylalkyl; and wherein W represents an alkylene group, optionally substituted with one or more substituents selected from the group comprising an alkyl, -OH, and a halogen.
  • the drier and anti-skinning agent system of the invention may further comprise an antiskinning agent comprising a diketone of formula (III) or formula (IV) (as shown herein above), wherein p represents 1 or 2.
  • the diketone of formula (III) and/or formula (IV) may be selected from one or more of 2,3- butanedione, 2,3-hexanedione, 2,4-pentanedione, 3,5-heptanedione, 2,4-dimethyl-3,5-heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, 5,5-dimethyl-2,4-heptanedione, 1- cyclobutylbutane-1 ,3-dione, 1 ,3-cyclohexanedione, 5-ethylcyclohexane-1 ,3-dione, and 4- cyclopentene-1 ,3-dione.
  • the diketone of formula (III) may be 2,4-pentanedione.
  • a coating composition comprising the drier and anti-skinning agent system of the invention may comprise from 0.1 to 5 % by weight of the diketone of formula (III) or formula (IV), based on the total weight of a coating composition.
  • the drier and anti-skinning agent system of the invention may comprise from 0.2 to 5% by weight of the diketone of formula (III) or formula (IV), such as from 0.3 to 4.5 % by weight, for example from 0.5 to 4 % by weight, based on the total weight of a coating composition.
  • a coating composition comprising an oxidatively drying binder, and the drier and anti-skinning agent system of the invention.
  • the coating composition may be solve nt- borne.
  • the coating composition may comprise from 0.1 to 10 % by weight of anti-skinning agent, based on the total weight of the coating composition.
  • the coating composition may comprise from 3.5 to 9% by weight of the anti-skinning agent, for example from 4.5 to 8 % by weight, for example from 5 to 7.5 % by weight, based on the total weight of the coating composition.
  • the coating composition may comprise from 0.1 to 5 % by weight of anti-skinning agent, based on the total weight of the coating composition.
  • the coating composition may comprise from 0.2 to 5% by weight of the anti-skinning agent, for example from 0.2 to 4.5 % by weight, for example from 0.5 to 3.5 % by weight, based on the total weight of the coating composition.
  • the oxidatively drying binder may be an autooxidizable alkyd binder.
  • the autooxidizable alkyd binder may be any suitable auto-oxidisable alkyd binder.
  • the term “oxidatively drying binder”, or “autooxidizable alkyd binder” are used interchangeably.
  • alkyd binder or “alkyd resin” are used interchangeably.
  • Suitable autoxidisable alkyd resins are in general the reaction product of the esterification of polyhydric alcohols with polybasic acids (or their anhydrides) and unsaturated fatty acids (or glycerol esters thereof).
  • the oxidatively drying binder dries and/or cures at least partially, suitably predominantly and suitably substantially entirely by auto-oxidisable methods.
  • the oxidatively drying binder may comprise hybrid drying and/or curing mechanisms, wherein the binder is operable to dry and/or cure at least partially, suitably predominantly, by an auto-oxidisable mechanism and also operable to dry and/or cure partially by an alternative mechanism.
  • the oxidatively drying binder may also include the ability to dry and/or cure by UV cure technology, moisture cure technology, and/or temperature cure technology.
  • the drying/curing capacity of the oxidatively drying binder may comprise at least 50%, such as at least 75% oxidatively drying mechanisms.
  • the oxidative curing potential of a binder can be measured by iodine number analysis; silicon cure functionality can be measured by hydrolysis of the Si-alkoxy (using strong alkaline media, for example) to determine mol Si-alkoxy/gram resin.
  • suitable polycarboxylic acids include citraconic acid, citric acid, fumaric acid, mesaconic acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, succinic acid, pyromellitic acid, their anhydrides or esters and combinations thereof.
  • the polycarboxylic acids may comprise dicarboxylic acids.
  • polyol compounds examples include ethylene glycol, 1 ,3-propane diol, 1 ,6- hexanediol. glycerol, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol, etherification products of these compounds, such as di-, tri- and tetrapentaerythritol, and combinations thereof.
  • the fatty acids may comprise polyunsaturated fatty acids, for example those derived from linseed oil, tung oil, tall oil, sunflower oil, soybean oil as well as from other drying or semi-drying oils.
  • the oils from which the fatty acids are derived may be drying or semi-drying oils.
  • the oils may have iodine values of 100-130 mg/g, such as of 1 10-120 mg/g.
  • Unsaturated groups may also be present in the polyols and/or polycarboxylic acids or other building blocks used.
  • Alkyd resins are well-known in the art and need not be further described herein. The properties are primarily determined by the nature and the ratios of the alcohols and acids used and by the degree of condensation. Suitable alkyds include long oil, very long oil and medium oil alkyd resins e.g. derived from 45 to 85 wt% of fatty acids, such as derived from 45 to 70 wt% of fatty acids. As used herein, the term "long oil alkyd” refers to alkyd with an oil content of between 60 and 75 wt%, and a fatty acid content of 57 to 70 wt%.
  • the term “medium oil alkyd” refers to alkyd with an oil content of between 45 wt% and 60 wt%, and a fatty acid content of 42 to 57 wt%.
  • the term “very long oil alkyd” refers to alkyd with an oil content of between 75 and 85 wt%, and a fatty acid content of 70 to 80 wt%.
  • the alkyd may comprise a medium oil alkyd.
  • the alkyd may comprise a long oil alkyd.
  • the alkyd may comprise a very long oil alkyd.
  • the alkyd may comprise the condensation product of soybean oil fatty acids, benzoic acid, pentaerythritol and phthalic anhydride having CAS number 6722-76-3.
  • the composition of the long oil and medium oil alkyd may be modified.
  • polyurethane modified alkyds silicone modified alkyds, styrene modified alkyds, acrylic modified alkyds (e.g. (meth)acrylic modified alkyds), vinylated alkyds, polyamide modified alkyds, and epoxy modified alkyds or mixtures thereof are also suitable alkyd resins.
  • the autoxidisable alkyd binder may comprise from a medium or long oil unmodified alkyd, a silicone modified alkyd, a polyurethane modified alkyd, acrylic modified alkyd, polyamide modified alkyd, an epoxy modified alkyd, or a combination thereof.
  • the alkyd binder may comprise a long oil (unmodified) alkyd, a silicone modified alkyd, a polyurethane modified alkyd, acrylic modified alkyd, polyamide modified alkyd, an epoxy modified alkyd, or a combination thereof.
  • the amount of alkyd binder present may typically range from 10 to 98 % by weight, such as from 15 to 90 % by weight, such as from 20 to 80 % by weight, such as from 25 to 70 % by weight based on the total weight of the coating composition.
  • the coating composition may comprise at least 30% by weight of the alkyd binder based on the total weight of the coating composition, such as at least 40%, 50% or 60% by weight of the total weight of the coating composition.
  • the alkyd binder may comprise between 40 and 60% by weight of the total weight of the coating composition, such as 50% by weight of the total weight of the coating composition.
  • the alkyd binder may have a solids content of between 5 and 100%, such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%, whereby the solids content is defined as the non-volatile solids content or non-volatile matter or nvm.
  • solids content refers to the proportion of non-volatile material contained in a binder or formulation. As reported herein, the solids content of the alkyd binder was measured according to ISO3251 . All values for the solids content of the alkyd binder were measured in this way (unless specified otherwise).
  • the coating compositions may comprise further components, such as colorants.
  • the colorant component of the coating composition may comprise an inorganic or organic, transparent or nontransparent pigment.
  • Non-limiting examples of such pigments are titanium dioxide, iron oxides, mixed metal oxides, bismuth vanadate, chromium oxide green, ultramarine blue, carbon black, lampblack, monoazo and disazo pigments, anthraquinones, isoindolinones, isoindolines, quinophthalones, phthalocyanine blues and greens, dioxazines, quinacridones and diketo-pyrrolopyrroles; and extender pigments including silica, barium sulfate, magnesium silicate, calcium silicate, mica, micaceous iron oxide, calcium carbonate, zinc oxide, aluminium hydroxide and aluminium silicate, gypsum, feldspar, talcum, kaolin, and the like.
  • the amount of pigment that can be used to form the coating composition is understood to
  • the coating compositions may include other additives, for example catalysts, other pigments and pigment pastes, dyes, fillers, stabilizers, thixotropic agents, anti-sagging agents, anti- oxidants, antifouling agents, anti-gelling agents, bactericides, fungicides, algaecides, insecticides, anti-settling agents, antifoaming agents, slip agents, flow and levelling agents, rheological modifiers, photoinitiators, UV-absorbers, synergists, HALS-radical scavengers, corrosion inhibitors, matting agents, waxes, mineral oils, flame retardants, anti-static agents, loss of dry inhibitors, optical brighteners, adhesion promoters, diluents, elastomers, plasticizers, air release agents, desiccants, anti-crater additives, reinforcing agents, dispersing aids, substrate wetting agents, odorants, corrosion-inhibitive pigments, additional hardeners and additional
  • the coating compositions may include surface active agents, such as any of the well-known anionic, cationic or nonionic surfactants or dispersing agents.
  • surface active agents such as any of the well-known anionic, cationic or nonionic surfactants or dispersing agents.
  • suitable additives that may be added to the coating composition may be found in Additives Guide, Paint & Coatings Magazine, June 2013, hereby incorporated by reference. If desired, other resinous materials can be utilized in conjunction with the aforementioned alkyd resins.
  • the metal drier combinations and optionally colorants, pigments and extenders and optionally other additives may be formulated into the coating compositions by mixing and, if appropriate, dispersing and grinding with the liquid binder.
  • the coating composition may be formulated as a one package coating composition, also referred herein as a one-component (1 K) coating composition.
  • a "1 K” or “one package” composition will be understood as referring to a composition wherein all of the components are maintained in the same container after manufacture, during storage, etc.
  • a “two package” or “2K” composition will be understood as referring to a composition wherein two components are maintained separately until just prior to application.
  • a “multi package” or “multicomponent” composition will be understood as referring to a composition wherein various components are maintained separately until just prior to application.
  • the coating composition according to the invention can be used and/or formulated as varnish, lacquer, paint, stain, enamel, printing ink or floor covering and similar compositions which contain auto- oxidisable alkyd resins.
  • the present invention also relates to a substrate having applied to at least a portion thereof a coating composition of the present invention.
  • the present invention also relates to a substrate having a coating on at least a portion thereof, the coating being derivable from a coating composition of the present invention.
  • the coating compositions can be applied to various substrates including wood, paper, foam, and synthetic materials (such as plastics including elastomeric substrates), leather, textiles, glass, ceramic, metals (such as iron, steel and aluminium), concrete, cement, brick, and the like.
  • substrates including wood, paper, foam, and synthetic materials (such as plastics including elastomeric substrates), leather, textiles, glass, ceramic, metals (such as iron, steel and aluminium), concrete, cement, brick, and the like.
  • substrates partially or fully coated with a coating composition of the present invention.
  • the substrates may be pre-treated before application of the coating composition.
  • the substrates may be post-treated after application of the coating composition, for example with any other compositions.
  • any known method can be used to apply the coating compositions to a substrate.
  • Non-limiting examples of such application methods are spreading (e.g. with paint pad or doctor blade, or by brushing or rolling), spraying (e.g. air-fed spray, airless spray, hot spray, and electrostatic spray), flow coating (e.g. dipping, curtain coating, roller coating, and reverse roller coating), and electrodeposition (see generally, R. Lambourne, Editor, Paint and Surface Coating: Theory and Practice, Eilis Horwood, 1987, page 39 et seq.).
  • the coating compositions can be applied and fully cured at ambient temperature conditions in the range of from -10°C to 50°C. Curing of the coating compositions typically can proceed very rapidly, and in general can take place at a temperature within the range of from -10°C to +50°C, such as from 0°C to 40 °C, such as from 3 to 25°C. However, the coating compositions may be cured by additional heating.
  • the coating compositions may be used as a single coating, a top coating, a base coating in a two-layered system, or a layer of a multi-layered system including a clear top coating composition, colorant layer and base coating composition, or as a primer layer.
  • a typical opaque system may comprise: 1 or 2 layers primer and 1 or 2 layers of topcoat (a total of 3 layers).
  • Alternative opaque systems may comprise: 1 primer layer, 1 layer of mid coat and 1 layer topcoat.
  • Examples of transparent systems may comprise 1 layer of impregnant and 3 layers of topcoats or 3 layers of topcoat for maintenance work.
  • a coating derivable from a coating composition refers to a cured coating (film), derivable from the uncured (wet) coating composition.
  • the skin-free time tests were performed in closed jars, filled to 40% of the volume and having an air packed head space of 60%.
  • the jars containing the paint products were stored at 23 °C and examined at specified time intervals for signs of skin formation.
  • a skin on the surface of the composition was considered to have formed when it had sufficient tensile strength to support a gentle indentation by a spatula.
  • Anti-skinning performance was defined as the number of days at which skin formation was first observed.
  • Run back the film flows back together when the stylus moves through it and no groove is formed. This phase is characterised by the evaporation of the solvent from the paint.
  • Gel tear The stylus rips the surface skin of the film. The film is starting to surface dry but is not through dry.
  • An acceptable anti-skinning performance of a composition is demonstrated by a composition that forms a skin after 20 days or more, for example.
  • a generally less acceptable anti-skinning performance of a composition is demonstrated by a composition that forms a skin in under 20 days.
  • Nuodex® Drycoat complex of manganese bis(2-ethylhexanoate) and N,N',N"-trimethyl-1 ,4,7- triazacyclononane (cas: 1381939-25-8, EC: 937-913-7) equivalent to 1% of Mn, commercially available from Venator.
  • Borchi® OXY-Coat contains 1 wt% Fe-complex (bispidon ligand), equivalent to 0,09 wt% Fe, dissolved in propylene glycol, commercially available from Borchers, comprising the complex Iron (1+),chloro[dimethyl-9,9-dihydroxy-3-methyl-2,4-di-(2-pyridyl-kN)-7-[(2-pyridinyl-kN)methyl]-3,7- diazabicyclo[3.3.1]nonane-1 ,5-dicarboxylate-kN3,kN7]-,chloride(1-) (CAS nr. 478945-46-9).
  • Octa-Soligen® Manganese 10 a metal drier comprising manganese bis(2-ethylhexanoate) equivalent to 10 wt% of Mn, commercially available from Borchers.
  • Duroct Cerium 12% a metal drier comprising cerium tris(2-ethylhexanoate) equivalent to 12 wt% of Ce, commercially available from Dura.
  • didodecyl 3,3'-thiodipropionate (CAS nr. 123-28-4), pentaerythritol tetrakis(3-mercaptopropionate) (CAS nr. 7575-23-7) are commercially available from Sigma-Aldrich.
  • Ascinin® Anti Skin 1240 Anti-skinning agent for oxidatively curing coating compositions, containing 1-5% by weight of N,N-diethylhydroxylamine (CAS nr. 3710-84-7) and 45-55% by weight of 2-dimethylaminoethanol (CAS nr. 108-01-0), commercially available from Borchers.
  • Borchers® Deca Cobalt 10 is a metal drier comprising metal salts of neodecanoic acid (having a Co metal content of 10% by weight), suitable for solvent borne oxidatively drying coating compositions and commercially available from Borchers.
  • EGEDry® IronOct is an iron-based drier composed of a solution of a metallic soap of 2-ethyl hexanoic acid in aliphatic solvents (having an iron content of 10% by weight), commercially available from Eg e- Ki my a.
  • Base paint 1 without the drier and anti-skinning agent system of the invention was prepared by mixing the constituents listed in Table 1 .
  • Coating compositions were prepared by mixing together the constituents listed in Table 1 with a drier and anti-skinning agent system according to the invention or with a comparative drier and antiskinning agent system, as shown in Table 2.
  • Table 2 The results of Table 2 demonstrate that coating compositions comprising a drier and antiskinning agent system according to the invention provide better anti-skinning activity, thereby improving the storage stability of the composition, without compromising the drying performance of the coating composition.
  • Examples 1-4 of Table 2 comprise an iron ligand complex based primary drier, manganese octoate as the further drying agent, and an anti-skinning agent comprising isooctyl 3- mercaptiopropionate and: 2-dimethylaminoethanol (Example 1), 1-dimethylamino-2-propanol (Example 2), 3-(dimethylamino)-1 -propanol (Example 3) and 2-(dimethylamino)-2-methyl-1 -propanol (Example 4).
  • compositions demonstrated superior storage stability and drying time compared to the comparative examples (Comparative Examples 1 to 3), which did not comprise a drier and anti-skinning agent system according to the invention.
  • coating compositions comprising an iron ligand complex based primary drier, a manganese based further drying agent, and an anti-skinning agent comprising an alkanolamine of formula (I) and a mercaptan of formulas (II) and (V) provide compositions with improved storage stability and shorter drying times.
  • Coating compositions were prepared by mixing together the constituents listed in Table 1 (Base Paint 1) with a drier and anti-skinning agent system according to the invention or with a comparative drier and anti-skinning agent system, as shown in Table 3.
  • Table 3 Table 3
  • Example 6 of Table 3 comprises an iron ligand complex based primary drier, manganese octoate as the further drying agent, and an anti-skinning agent comprising isooctyl 3- mercaptiopropionate and 2-dimethylaminoethanol.
  • the composition of Example 6 in Table 3 demonstrated superior storage stability as well as a good drying time compared to Comparative Examples 4-6, which did not comprise a drier and anti-skinning agent system according to the invention.
  • coating compositions comprising an iron ligand complex based primary drier, manganese octoate as the further drying agent, and an anti-skinning agent comprising an alkanolamine of formula (I) and a mercaptan of formulas (II) or (V) provide compositions with improved storage stability and shorter drying times.
  • the chain transfer agent isooctyl-3-mercaptopropionate has a positive effect on the contradictory properties of the coating composition: drying time and an anti-skinning efficacy.
  • thiol ethers such as didodecyl 3,3'-thiodipropionate (Comparative Example 5) and polythiols having two or more thiol groups such as pentaerythritol tetrakis(3-mercaptopropionate) (Comparative Example 6) are not effective as anti-skinning agents in combination with 2-dimethylaminoethanol and manganese octoate.
  • Comparative Example 4 demonstrates that coating compositions with drier systems comprising an iron ligand complex based primary drier and an anti-skinning agent comprising only an alkanolamine yield compositions with good storage stability but long drying times.
  • Coating compositions were prepared by mixing together the constituents listed in Table 1 (Base Paint 1) with a drier and anti-skinning agent system according to the invention or with a comparative drier and anti-skinning agent system, as shown in Table 4.
  • Table 4 Table 4
  • Example 7 of Table 4 comprises an iron ligand complex based primary drier, cerium ethylhexanoate as the further drying agent, and an anti-skinning agent comprising 2- dimethylaminoethanol and isooctyl 3-mercaptiopropionate.
  • Example 8 of Table 4 comprises an iron ligand complex based primary drier, cerium ethylhexanoate as the further drying agent, and an antiskinning agent comprising 2-dimethylaminoethanol and 2,4-pentanedione.
  • the compositions of Examples 7 to 9 in Table 4 demonstrated superior storage stability as well as a good drying time compared to Comparative Example 7, which did not comprise a drier and anti-skinning agent system according to the invention.
  • compositions comprising an iron ligand complex based primary drier, cerium ethylhexanoate as the further drying agent, and an anti-skinning agent comprising an alkanolamine of formula (I) and a mercaptan of formulas (II) and (V) or an anti-skinning agent comprising an alkanolamine of formula (I) and a diketone of formula (III) provide compositions with improved storage stability and shorter drying times.
  • Coating compositions were prepared by mixing together the constituents listed in Table 1 (Base Paint 1) with a drier and anti-skinning agent system according to the invention as shown in Table 5.
  • Table 5 Table 5
  • Example 1 and Example 5 are reprinted in Table 5 to aid direct comparison, but for the avoidance of doubt, they are the same as those detailed in Table 2, above.
  • Example 10 demonstrates that compositions of the invention comprising a drier and anti-skinning agent system comprising a primary drier based on an iron ligand complex, an anti-skinning agent comprising dimethylaminoethanol and isooctyl 3-mercaptopropionate, and a manganese octoate further drier provide excellent antiskinning performance and excellent drying performance.
  • compositions of the invention comprising a drier and anti-skinning agent system comprising both a primary drier based on an iron ligand complex and a primary drier based on a manganese ligand complex, and an anti-skinning agent comprising dimethylaminoethanol and isooctyl 3-mercaptopropionate provide excellent anti-skinning performance and excellent drying performance.
  • a base paint absent any anti-skinning agents and metal driers was prepared by grinding in a bead mill and mixing the constituents together as listed in Table 6.
  • Example 16 of Table 7 and Example 5 of Table 2 comprise an iron or manganese ligand complex based primary drier, and an anti-skinning agent comprising isooctyl 3-mercaptiopropionate and 2-dimethylaminoethanol.
  • the compositions of Example 16 in Table 7 and Example 5 of Table 2 demonstrated superior storage stability and drying time compared to Comparative Examples 8-10, which did not comprise a drier and anti-skinning agent system according to the invention.
  • coating compositions comprising an iron or manganese ligand complex based primary drier, and an anti-skinning agent comprising an alkanolamine of formula (I) and a mercaptan of formulas (II) or (V) provide compositions with improved storage stability and shorter drying times.
  • Examples 16 and 17 demonstrate that a combination of 2-dimethylethanolamine and isooctyl 3-mercaptopropionate is successful in oxidatively drying binder (alkyd) based coating formulations containing manganese ligand complexes, such as Nuodex Drycoat, as the sole primary drier.
  • Comparative Examples 8-10 contain drier systems that do not comprise an iron or manganese ligand complex based primary drier.
  • the results of Comparative Examples 8-10 of Table 7 demonstrate that anti-skinning compositions comprising 2-dimethylethanolamine and isooctyl 3-mercaptopropionate are not effective in oxidatively drying binder (alkyd) based coating compositions in the absence of iron and manganese ligand complexes as the primary drier.
  • Primary driers such as organic salts of manganese, iron, vanadium and cerium do not enhance the anti-skinning and/or drying time of the compositions successfully compared to iron or manganese ligand complex based primary driers (Comparative Examples 8-10).
  • Example 20 demonstrates that oxidatively drying binder based compositions of the invention comprising a drier and anti-skinning agent system comprising a primary drier based on an iron ligand complex and a primary drier based on a manganese ligand complex and an anti-skinning agent comprising isooctyl 3-mercaptopropionate provide excellent anti-skinning performance and excellent drying performance.
  • Example 21 demonstrates that oxidatively drying binder based compositions of the invention comprising a drier and anti-skinning agent system comprising a primary drier based on an iron ligand complex and a manganese based further drying agent and an anti-skinning agent comprising isooctyl 3-mercaptopropionate provide excellent anti-skinning performance and excellent drying performance.
  • Attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

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Abstract

L'invention concerne un système d'agent siccatif et anti-peau pour une composition de revêtement à base de liant séchant par oxydation comprenant : a. un agent de séchage comprenant un complexe de ligand de fer et/ou un complexe de ligand de manganèse ; et b. un agent anti-peau comprenant i. une alcanolamine de formule (I) dans laquelle chaque R1 et R2 représentent indépendamment un hydrogène, un alkyle, un alcényle, un aryle ou un arylalkyle ; chaque R3 et R4 représentant indépendamment un hydrogène, ou un alkyle ; m représentant 0 ou 1 ; et n représentant un nombre entier de 1 à 10 ; et ii. (A) et/ou (B), (A) étant un mercaptan de formule (II) dans laquelle R5 représente un alkyle ou un arylalkyle ; dans laquelle X représente un groupe méthylène ou carbonyle ; et où Y représente un groupe méthylène ou un oxygène ; et où (B) est une dicétone de formule (III) ou une dicétone de formule (IV) où p représente 0, 1 ou 2 ; et où chacun de R6 et R7 représente indépendamment un alkyle, un aryle ou un arylalkyle ; et où W représente un groupe alkylène, éventuellement substitué par un ou plusieurs substituants choisis dans le groupe comprenant un alkyle, -OH et un halogène.
EP24704007.4A 2023-02-09 2024-02-08 Système d'agent siccatif et anti-peau pour une composition de revêtement Pending EP4662282A1 (fr)

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DE19962670B4 (de) * 1999-12-23 2006-06-22 Manfred Gawol Neue Additive zur Vermeidung von Hautbildung an oxidativ-trocknenden Lacken und Farben
DE10010427A1 (de) * 2000-03-03 2001-09-06 Borchers Gmbh Neue Additive zur Vermeidung von Hautbildung an lufttrocknenden Lacken
KR101423796B1 (ko) * 2006-07-07 2014-07-28 유니레버 엔.브이. 액체 경화
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AU2024218228A1 (en) 2025-08-21
CO2025010802A2 (es) 2025-11-19
WO2024165699A1 (fr) 2024-08-15
MX2025009240A (es) 2025-11-03
EP4414430A9 (fr) 2024-11-20

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