Classifications

• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
  • C08F299/0442—Catalysts
  • C08F299/0464—Metals or metal containing compounds
• • 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

Definitions

• the present invention relates to a coating composition
• a coating composition comprising an oxidatively drying coating binder and a chelating ligand according to the following formula I:
• A1 and A2 both are an aromatic residue.
• R1 and R3 are covalently bonded groups, for example hydrogen or an organic group.
• R2 is a divalent organic radical.
• the chelating ligand can form a metal complex having a catalytic effect on the curing of oxidatively drying polymers, in particular alkyd resins.
• US 3,956,211 discloses an alkyd based composition with a compound similar to that of formula I including a divalent lead ion, a zirconium ion or a divalent ion of a metal of the first transition group, except for nickel.
• R1 and R3 are hydrogen. The effectiveness of these siccatives proved to be moderate.
• EP-A 1 114 836 discloses the use of compounds of formula I for the preparation of resins for urushi lacquers by oxidative polymerization of phenol-functional vegetable oils.
• the object of the invention is to improve the effectiveness of such chelating compounds.
• the object of the invention is achieved by a coating composition according to the opening paragraph, wherein at least one solubilizing group is covalently bonded to the compound of formula I. It has been found that by improving the solubility of the compound, its effectiveness is increased substantially as well. Although it was to be expected that the presence of a solubilizing group, typically having an electron-inductive effect, would disturb the chelate function, it has been found that the catalyzing effect is better than with prior art siccatives.
• non-polar solubilizing groups When used for compositions based on organic solvents, non-polar solubilizing groups are preferred. Suitable examples of such non-polar groups are aliphatic groups having at least four carbon atoms. Optionally, these groups may be branched alkyl groups, such as tert. butyl groups.
• the solubilizing group can be covalently bonded to A1 and/or A2 and/or can be R1 , R2 and/or R3. Preferably, both aromatic groups are provided with a solubilizing group.
• polyalkylene oxide groups such as polyethylene oxide or polypropylene oxide groups, are preferred.
• A1 and/or A2 are aromatic groups, for example derived from benzene or naphthalene, optionally substituted, e.g., with electron donating groups.
• A1 and/or A2 may be a heterocyclic aromatic group, derived from, for example, pyridine or quinoline.
• R2 can be a linear, branched, or cyclic organic compound, such as ethylene, propylene, isopropylene, butylene, tert. butylene, pentylene, hexylene, a cycloalkylene, such as cyclohexylene, cycloheptylene, etc.
• A1 , A2, R1 , R2 and/or R3 can be covalently bonded to a polymer, or to one or more further groups according to formula I.
• a preferred embodiment is a poly-chelate having at least two groups according to formula I mutually linked by R1 and/or R3.
• the metal ion can be a divalent ion of a metal which may for example be selected from the group of manganese, cobalt, copper, lead, zirconium, iron, lanthanium, cerium, vanadium, and calcium.
• the metal ion can be a trivalent or higher valency ion of a metal combined with one or more counterions.
• Suitable metals are for example manganese, cobalt, lead, zirconium, iron, lanthanium, and vanadium.
• suitable counterions are halogen ions, octoate, benzoxy or mixtures thereof.
• the coating composition can be solvent borne, water borne or solvent-free. If the composition is solvent borne, non-aromatic solvents are preferred.
• a suitable solvent is for example Shellsol ® D40, available from Shell.
• Typical oxidatively drying binders are alkyd resins. At least a part of the alkyd resin is oxidatively drying as a result of the incorporation of a large number of unsaturated, aliphatic compounds, at least a portion of which is polyunsaturated.
• the unsaturated aliphatic compounds preferably are unsaturated fatty acids, more particularly polyunsaturated fatty acids. Examples of fatty acids comprising one equivalent of unsaturated CC bonds are myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, and ricinoleic acid and mixtures thereof.
• fatty acids comprising two or more equivalents of unsaturated CC bonds include linoleic fatty acid, linolenic fatty acid, elaeostearic fatty acid, licanic fatty acid, arachidonic fatty acid, clupanodonic fatty. acid, nisinic fatty acid, and mixtures thereof.
• Fatty acids containing conjugated double bonds such as dehydrated castor oil fatty acid, wood oil fatty acid and/or calendula oil fatty acid, can be used as well.
• Fatty acids derived from soya oil are especially suitable.
• divalent polyol compounds examples include ethylene glycol, 1 ,3- propane diol, 1 ,6-hexane diol, 1 ,12-dodecane diol, 3-methyl-1 ,5-pentane diol,
• triols examples include glycerol, trimethylol ethane, and trimethylol propane.
• suitable polyols having more than 3 hydroxyl groups are pentaerythritol, sorbitol, and etherification products of the compounds in question, such as ditrimethylol propane and di-, tri-, and tetrapentaerythritol.
• polycarboxylic acids can be used as building blocks for the oxidatively drying polyunsaturated condensation products.
• suitable polycarboxylic acids include phthalic acid, citric acid, fumaric acid, mesaconic acid, maleic acid, citraconic acid, isophthalic acid, terephthalic acid, 5-tert.
• the carboxylic acids in question may be used as anhydr
• the oxidatively drying polyunsaturated condensation product may comprise other building blocks, which may for example be derived from monocarboxylic acids such as pivalic acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, 4-tert. butyl-benzoic acid, cyclopentane carboxylic acid, naphthenic acid, cyclohexane carboxylic acid, 2,4-dimethyl benzoic acid, 2-methyl benzoic acid, benzoic acid, 2,2-dimethylol propionic acid, tetrahydrobenzoic acid, and hydrogenated or non-hydrogenated abietic acid or its isomer.
• monocarboxylic acids such as pivalic acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, 4-tert. butyl-benzoic acid, cyclopentane carboxylic acid, naphthenic acid, cyclohexan
• the monocarboxylic acids in question may be used wholly or in part as thglyceride, e.g., as vegetable oil, in the preparation of the alkyd resin. If so desired, mixtures of two or more of such monocarboxylic acids or triglycerides may be employed.
• isocyanates may also be used as building blocks for the oxidatively drying polyunsaturated condensation product. Suitable isocyanates are for example diisocyanates, such as 1 ,6-hexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenyl diisocyanate, and dicyclo- hexylmethane diisocyanate. Triisocyanates can also be used.
• the unsaturated groups in the oxidatively drying polyunsaturated condensation product are preferably introduced by the fatty acids, but may, alternatively or additionally, be introduced by one or more of the polyols, carboxylic acids or anhydrides or other building blocks used, such as fatty mono-alcohols.
• the oxidatively drying polyunsaturated condensation product has pendant groups in an amount of more than 20%, preferably more than 50%, by weight of the condensation product. An amount of more than 65% is even more preferred.
• a specific example of a suitable alkyd is the condensation product of soya oil, phthalic anhydride, and pentaerythritol.
• the alkyd resins can be obtained by direct esterification of the constituent components, with the option of a portion of these components having been converted already into ester diols or polyester diols.
• the unsaturated fatty acids can be added in the form of a drying oil, such as sunflower oil, linseed oil, tuna fish oil, dehydrated castor oil, coconut oil, and dehydrated coconut oil.
• Transesterification with the polyols and, optionally, other building blocks will then give the final alkyd resin. This transesterification generally takes place at a temperature in the range of 115 to 250°C, optionally with solvents such as toluene and/or xylene also present.
• the reaction generally is carried out in the presence of a catalytic amount of a transesterification catalyst.
• transesterification catalysts suitable for use include acids such as p-toluene sulphonic acid, a basic compound such as an amine, or compounds such as calcium oxide, zinc oxide, tetraisopropyl orthotitanate, dibutyl tin oxide, and triphenyl benzyl phosphonium chloride.
• the oxidatively drying binder can be used in combination with other resins, for example acrylic resins or polyurethanes.
• the coating composition comprises at least 20 wt.% of oxidatively drying binder, more preferably more than 60% by weight of total binder.
• the average number molecular weight Mw of the binder will generally be above 150. Preferably, it will be higher than 1 ,000. For reasons of viscosity, the average number molecular weight will generally be below 120,000, preferably below 80,000.
• the compound according to formula I can first be reacted with a metal ion, to form a metal complex which is subsequently added as a drier to the coating composition.
• the compound according to formula I can be added separately, before, during or after the addition of a metal. In such case, complexing takes place in situ.
• the metal can for example be added in the form of a salt, e.g. halide salts, nitrates, or salts of organic acids such as octoates, hexanoates or naphthanates.
• a drying accelerator is used.
• a preferred example of such an accelerator is 2,2'-bipiridyl.
• Mn 12 Cem-AII ® LC siccative comprising 12 wt.% manganese, commercially available from OMG; Nuodex ® Ca 5 siccative comprising 5 wt.% calcium, available from
• Shellsol ® D40 aromate-free organic solvent available from Shell
• Zr 18 Hex-Cem ® siccative comprising 18 wt.% zirconium, commercially available from OMG.
• the drying time was measured as follows.
• the coating composition was applied on a glass plate with a draw bar (90 ⁇ m applicator). Curing took place at 10°C and 80% relative humidity in a climatized room under TL-055 light. Drying was tested by means of a BK Drying Recorder. The results obtained in this fashion are classified as follows: ,, ' Phase 1 : the line traced by the pin closes up again. The end of phase 1 is referred to as the "open time”.
• Phase 2 the pin traces a scratchy line. The end of phase 2 is referred to as the "dust-free time”.
• Phase 3 the pin traces a straight line in the paint which does not close up again.
• the end of phase 3 is referred to as the "tack-free time”.
• Comparative Example A was repeated using 2-hydroxy 5-methyl benzaldehyde instead of salicyl aldehyde. Again, the resulting ligand was added to Shellsol ® D40 at a temperature of 23°C. The solubilty of the ligand was less than 10 g/l.
• Comparative Example A was repeated using 2-hydroxy 3,5-di tert. butyl benzaldehyde in stead of salicyl aldehyde. Obtained was a ligand according to formula I having two tert. butyl substitutions on the two aromatic groups A1 and A2. The solubility in Shellsol ® D40 at a temperature of 23°C was higher than 20 g/l.
• Comparative Example A was repeated again, now using 2-hydroxy 5-dodecyl benzaldehyde instead of salicyl aldehyde. Obtained was a ligand according to formula I having a dodecyl substitution on the two aromatic groups A1 and A2.
• the solubility in Shellsol ® D40 at a temperature of 23°C was higher than 100 g/l.
• Comparative Example C An opaque cornposition was prepared comprising Setal ® 270 as a binder, Kronos ® 2310 as a pigment, and Shellsol ® D40 as a solvent. The pigment volume concentration was 15% and the total solids content was about 68% by weight of the complete formulation. In the composition, 0.5 parts by weight of Mn 12 Cem-All ® LC (relative to 100 parts by weight of the solid binder) was present as a siccative in combination with 4.5 parts by weight of Nuodex ® Ca and 5.2 parts by weight of Zr 18 Hex-Cem ® . The composition was applied on a glass substrate and the drying time was measured. The end of phase 1 occurred after 1 hour, the end of phase 2 after 14 hours, and the end of phase 3 after 18 hours.
• Example 3 The ligand as prepared in Example 2 was added to a composition as prepared in Comparative Example C. The composition was applied on a glass substrate and the drying time was measured. The end of phase 1 occurred after 0.8 hours, the end of phase 2 after 4.6 hours, and the end of phase 3 after 6.2 hours.

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• 2002
  • 2002-09-05 EP EP02800070A patent/EP1440130A1/de not_active Withdrawn
  • 2002-09-05 WO PCT/EP2002/009988 patent/WO2003029371A1/en not_active Ceased
  • 2002-09-05 PL PL02368373A patent/PL368373A1/xx unknown
  • 2002-09-05 HU HU0401681A patent/HUP0401681A2/hu unknown

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