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
  • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
  • C09D191/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
• • 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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
• • 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
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
  • C09D123/30—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by oxidation
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/03—Powdery paints
  • C09D5/033—Powdery paints characterised by the additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
  • C08L91/08—Mineral waxes

Definitions

• the present invention relates to the use of polyolefin waxes synthesized by means of metallocene catalysts as an additive in powder coatings and to a process for producing pigmented powder coatings.
• Binders e.g. Polyester resins which are crosslinked e.g. with epoxides, triglycidyl isocyanurate (TGIC),? -hydroxyalkylamine or blocked isocyanates (urethdione).
• TGIC triglycidyl isocyanurate
• urethdione blocked isocyanates
• Pigments and fillers unless they are clear coats.
• the pigments must have a correspondingly high thermal stability. Examples include phthalocyanines, quinacridones, azo pigments, perylene and perinone pigments, benzimidazolone pigments, anthraquinone pigments, isoindolinone and isoindoline pigments, anthanthrone pigments, dioxazine pigments, quinophthalone pigments, diketo-pyrrolo-pyrrole
• Additives such as Degassing agents, matting agents, antioxidants, tribo-additives, leveling agents, waxes to improve scratch resistance.
• waxes are used as additives in order to achieve the following effects:
• the wax additives used in a concentration of 0.01-10% by weight, based on the powder coating composition are usually polyolefin, PTFE, amide waxes, FT paraffins, montan waxes, natural waxes, macro- and microcrystalline paraffins , Sorbitan esters and metallocene waxes.
• Suitable polyolefin waxes are primarily polyethylene and polypropylene waxes. These can be broken down by thermal degradation of highly polymeric polyolefin Plastics or be produced by direct polymerization of appropriate monomers.
• High-pressure technologies can be used as the polymerization process, with ethylene, for example, being radically converted to wax at high pressures and temperatures.
• Ziegler processes in which the olefin is polymerized with the aid of organometallic catalysts at comparatively low pressures and temperatures.
• the low-pressure process allows the synthesis of copolymers by the joint polymerization of two or more olefins.
• metallocene compounds are used as organometallic catalysts.
• the latter contain titanium, zirconium or hafnium atoms as active species and are usually used in combination with cocatalysts, e.g. Organoaluminum or boron compounds, preferably aluminoxane compounds, are used.
• cocatalysts e.g. Organoaluminum or boron compounds, preferably aluminoxane compounds
• the polymerization is carried out in the presence of hydrogen as a molecular weight regulator.
• Metallocene processes are characterized in that waxes with a narrower molar mass distribution, more uniform comonomer incorporation, lower melting points and higher catalyst yields can be obtained compared to older Ziegler technology.
• Corresponding polymerization processes using metallocene catalysts for the production of polyolefin are growing e.g. in EP-A-0 571 882.
• EP-A-0 890 619 describes the use of metallocene polyolefin waxes in printing inks and lacquers. Powder coatings with their specific requirements regarding additives with waxes are not dealt with there.
• the object of the invention was to improve the performance properties of powder coatings by using a suitable dispersant.
• polyolefin waxes which are produced using metallocene catalysts were produced, are particularly advantageously suitable for use as additives in powder coatings.
• metallocene polyolefin waxes show improved effectiveness with regard to extrusion properties, matting effect, sliding behavior, film hardness, abrasion resistance and dispersion hardness.
• the invention therefore relates to the use of polyolefin waxes synthesized by means of metallocene catalysts as an additive in powder coatings.
• the polyolefin wax is preferably derived from olefins having 3 to 6 carbon atoms or from styrene.
• homopolymers of ethylene, propylene, copolymers of ethylene and propylene or copolymers of ethylene or propylene with one or more 1-olefins are suitable as polyolefin waxes.
• the 1-olefins can also carry an aromatic substitution.
• 1-olefins in addition to ethylene and propylene are 1-butene, 1-hexene, 1-octene or 1-octadecene and styrene.
• Homopolymers of ethylene or propylene or copolymers of ethylene with propylene or 1-butene are particularly preferred. If they are copolymers, they preferably consist of 70-99.9, in particular 80-99,% by weight of ethylene.
• the polyolefin waxes used according to the invention can be produced both by direct polymerization with metallocene catalysts and by thermal degradation of polyolefin plastics of the above composition produced using metallocene catalysts.
• Polyolefin waxes with a dropping point between 70 and 165 ° C., in particular between 100 and 160 ° C. are particularly preferably used Melt viscosity at 140 ° C (polyethylene waxes) or at 170 ° C (polypropylene waxes) between 10 and 10000 mPas, in particular between 50 and 5000 mPas, and a density at 20 ° C between 0.85 and 0.98 g / cm 3 .
• Preferred polyolefin waxes have a molecular weight distribution M w / M n ⁇ 5.
• Metallocene catalysts for the production of the polyolefin waxes or the polyolefin plastics used for the thermal degradation are chiral or nonchiral transition metal compounds of the formula M 1 L X.
• the transition metal compound M 1 L X contains at least one metal central atom M 1 to which at least one ⁇ ligand, for example a cyclopentadienyl ligand, is bonded.
• substituents such as halogen, alkyl, alkoxy or aryl groups can be bound to the metal central atom M 1 .
• M 1 is preferably an element of III., IV., V. or VI. Main group of the periodic table of the elements, such as Ti, Zr or Hf.
• Cyclopentadienyl ligand is understood to mean unsubstituted cyclopentadienyl radicals and substituted cyclopentadienyl radicals such as methylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl or octa-tetra-hydrofluoryl or octa-tetra-hydrofluoryl or octa.
• the ⁇ ligands can be bridged or unbridged, whereby single and multiple bridging - also via ring systems - are possible.
• metallocene also includes compounds with more than one metallocene fragment, so-called multinuclear metallocenes. These can have any substitution pattern and bridging variant.
• the individual metallocene fragments of such multinuclear metallocenes can be either of the same type or different from one another (EP-A-0 632 063).
• the polyolefin waxes used according to the invention can be used either as such or in polar modified form.
• a polar modification can be done, for example, by oxidation with air or oxygen-containing gases or by grafting unsaturated carboxylic acids such as maleic acid. Examples of the oxidative modification can be found in EP-A-0 890 583, examples of the modification with unsaturated carboxylic acids in EP-A-0 941 257.
• the polyolefin waxes according to the invention can be used both in pure form and as a mixture with other wax components which are not produced with metallocene catalysts in a proportion of 1-50% by weight. Mixing can take place in the melt or by mixing the components in solid form. The following blending components are possible:
• Additive a) is polyethylene glycol, molecular weight range preferably 10 to 50,000 daltons, in particular 20 to 35,000 daltons.
• the polyethylene glycol can be mixed in amounts of preferably up to 5% by weight of the composition containing metallocene wax.
• additive b) is Polyethylene homo- and copolymer waxes which were not produced by means of metallocene catalysis and which have a number average molecular weight of 700 to 10,000 g / mol at a dropping point between 80 and 140 ° C.
• additive c) is polytetrafluoroethylene with a molecular weight between 30,000 and 2,000,000 g / mol, in particular between 100,000 and 1,000,000 g / mol.
• additive d) is polypropylene homo- and copolymer waxes, which were not produced by means of metallocene catalysis and which have a number average molecular weight of 700 to 10,000 g / mol at a dropping point between 80 and 160 ° C.
• additive e) is amide waxes which can be prepared by reacting ammonia or ethylenediamine with saturated and / or unsaturated fatty acids.
• the fatty acids are, for example, stearic acid, tallow fatty acid, palmitic acid or erucic acid.
• additive f) is FT paraffins with a number average molecular weight of 400 to 800 g / mol at a dropping point of 80 to 125 ° C.
• Additive g) is preferably montan waxes including acid and ester waxes with a carbon chain length of the carboxylic acid from C 22 to C 3 6.
• ester waxes are preferably reaction products of montanic acids with monohydric or polyhydric alcohols having 2 to 6 carbon atoms, such as, for example, ethanediol, butane-1,3-diol or propane-1, 2,3-triol.
• additive h) is carnauba wax or candelilla wax.
• Additive i) is paraffins and microcrystalline waxes which are obtained from petroleum refining. The dropping points of such paraffins are preferably between 45 and 65 ° C, those of such microcrystalline waxes preferably between 73 and 100 ° C.
• additive j) is polar polyolefin waxes which can be prepared by oxidation of ethylene or propylene homopolymer and copolymer waxes or their grafting with maleic anhydride.
• Polyolefin waxes with a dropping point between 90 and 165 ° C., in particular between 100 and 160 ° C., a melt viscosity at 140 ° C. (polyethylene waxes) or at 170 ° C. (polypropylene waxes) between 10 and 10,000 mPas, in particular between, are particularly preferred for this 50 and 5000 mPas and a density at 20 ° C between 0.85 and 0.96 g / cm 3 .
• additive k) is reaction products of sorbitol (sorbitol) with saturated and / or unsaturated fatty acids and / or montanic acids.
• the fatty acids are, for example, stearic acid, tallow fatty acid, palmitic acid or erucic acid.
• Additive I) is preferably ground polyamides, for example polyamide-6, polyamide-6,6 or polyamide-12.
• the particle size of the polyamides is preferably in the range of 5-200 ⁇ m, in particular 10-100 ⁇ m.
• Additive m) is polyolefins, for example polypropylene, polyethylene or copolymers of propylene and ethylene of high or low density with molecular weights of preferably 10,000 to 1,000,000 D, in particular 15,000 to 500,000 D as number average for the molecular weight, the particle size of which Grinding is in the range of preferably 5-200 ⁇ m, in particular 10-100 ⁇ m.
• Additive n) is thermoplastic PTFE with a molecular weight of preferably 500,000 - 10,000,000 D, in particular 500,000 - 2,000,000 D as the number average, the particle size of which, by grinding, is preferably in the range 5-200 ⁇ m, in particular 10-100 ⁇ m.
• Additive o is an amphiphilic compound that generally lowers the surface tension of liquids.
• the wetting agents are, for example, alkyl ethoxylates, fatty alcohol ethoxolates, alkyl benzene sulfonates or betaines.
• Additive p) is silicates, which are not used as fillers or pigments in the recipes. Silicas or talc are preferably used.
• the mixing ratio of component a) to components b) to p) can be varied in the range from 1 to 50% by weight a) to 1 to 50% by weight b) to p). If a mixture of several of the components b) to p) is used, the quantity given applies to the sum of the quantities of these components.
• the waxes are used in micronized form for the purpose according to the invention.
• the use of polyolefin wax and optionally admixed auxiliaries and additives as ultra-fine powder with a particle size distribution dgo ⁇ 40 ⁇ m is particularly preferred.
• Another object of the invention is a process for the production of powder coatings from binders, pigments and fillers and conventional auxiliaries, characterized in that an additive according to the present invention is added.
• V comparative example all samples were micronized on DV 50 approx. 8 ⁇ m. r
• the waxes were mixed with the individual raw materials in a high-speed mixer, then the dry mixture was extruded on a laboratory twin-screw extruder (PC19-25 from APV) at 110 ° C and 250 rpm, ground to ⁇ 125 ⁇ m and on aluminum or steel sheet by a Spray gun applied with corona charging. After baking (15 minutes at 180 ° C), the coated sheets were stored in the climatic room for 24 hours and then the gloss (60 °) was measured.
• PC19-25 from APV laboratory twin-screw extruder
• the waxes were mixed with the individual raw materials in a high-speed mixer, then the dry mixture was extruded on a laboratory twin-screw extruder (PC19-25 from APV) at 110 ° C and 250 rpm, ground to ⁇ 125 ⁇ m and on aluminum or steel sheet by a Spray gun applied with corona charging. After baking (15 min. At 180 ° C), the coated sheets were stored in the climatic room for 24 hours and then the sliding friction (according to Altek) was measured.
• the waxes were mixed with the individual raw materials in a high-speed mixer, then the dry mixture was extruded on a laboratory twin-screw extruder (PC19-25 from APV) at 110 ° C at 250 rpm, ground to ⁇ 125 ⁇ m and on aluminum or steel sheet by a Spray gun applied with corona charging. After baking (15 minutes at 180 ° C), the coated sheets were stored in the climatic room for 24 hours, after which the pencil hardness (according to Wolff-Wilborn) was determined.
• the waxes were mixed with the individual raw materials in a high-speed mixer, then the dry mixture was extruded on a laboratory twin-screw extruder (PC19-25 from APV) at 110 ° C and 250 rpm, ground to ⁇ 125 ⁇ m and on aluminum or steel sheet by a Spray gun applied with corona charging. After baking (15 min. At 180 ° C) the coated sheets were stored in the climatic room for 24 hours, after which the abrasion test on the Taber Abraser was determined.
• the waxes were mixed with the individual raw materials in a high-speed mixer, then the mixture was extruded on a laboratory twin-screw extruder (PC19-25 from APV) at 110 ° C and 250 rpm, the metering quantity had to be adjusted to a power consumption of 70% on the extruder , then the throughput was recorded, then it was ground to ⁇ 125 ⁇ m and applied to aluminum or steel sheet using a spray gun with corona charging. After baking (15 min. At 180 ° C), the coated sheets were stored in the climatic room for 24 hours and then the dispersion hardness was determined via the color depth.
• PC19-25 from APV laboratory twin-screw extruder
• the waxes were mixed with the individual raw materials in a high-speed mixer, then the mixture was extruded on a laboratory twin-screw extruder (PC19-25 from APV) at 110 ° C, the dosage had to be adjusted to a power consumption of 60% at 250 rpm on the extruder , then the throughput was recorded.
• the waxes were mixed with the individual raw materials in a high-speed mixer, then the mixture was extruded on a laboratory twin-screw extruder (PC19-25 from APV) at 110 ° C., the dosage was adjusted to 3.0 and the power consumption was then measured.

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• 2002
  • 2002-04-12 DE DE10216118A patent/DE10216118A1/de not_active Withdrawn
• 2003
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  • 2003-04-04 US US10/511,358 patent/US20050176866A1/en not_active Abandoned
  • 2003-04-04 JP JP2003584189A patent/JP2006511626A/ja active Pending
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