CA2216111C - Aqueous dispersions of transparent powder coating - Google Patents
Aqueous dispersions of transparent powder coating Download PDFInfo
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- CA2216111C CA2216111C CA002216111A CA2216111A CA2216111C CA 2216111 C CA2216111 C CA 2216111C CA 002216111 A CA002216111 A CA 002216111A CA 2216111 A CA2216111 A CA 2216111A CA 2216111 C CA2216111 C CA 2216111C
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- 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
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
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- 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
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
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- 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
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- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to an aqueous dispersion of a transparent powder coating, consisting of a solid powder component A and an aqueous component B, wherein component A is a transparent powder coating comprising (a) at least one epoxy group-containing binder having a content of glycidyl-containing monomers of from 30 to 45 %, preferably from 30 to 35 %, and optionally having a content of vinylaromatic compounds, preferably styrene;
(b) at least one crosslinking agent, preferably straight-chain aliphatic dicarboxylic acids and/or carboxy-functional polyesters; and (c) optionally catalysts, adjuvants, additives typical for transparent powder coatings, such as deaerating agents, levelling agents, W absorbers, radical scavengers and antioxidants;
and component B is an aqueous dispersion comprising (a) at least one nonionic thickener, preferably a nonionic associative thickener, and (b) optionally catalysts, adjuvants, defoamers, dispersion adjuvants, wetting agents, preferably carboxy-functional dispersants, antioxidants, UV absorbers, radical scavengers, biocides, small amounts of solvents and/or water retaining agents.
A further subject of the application is a process for pre-paring the dispersion of transparent powder coating, and its use for vehicle bodies.
(b) at least one crosslinking agent, preferably straight-chain aliphatic dicarboxylic acids and/or carboxy-functional polyesters; and (c) optionally catalysts, adjuvants, additives typical for transparent powder coatings, such as deaerating agents, levelling agents, W absorbers, radical scavengers and antioxidants;
and component B is an aqueous dispersion comprising (a) at least one nonionic thickener, preferably a nonionic associative thickener, and (b) optionally catalysts, adjuvants, defoamers, dispersion adjuvants, wetting agents, preferably carboxy-functional dispersants, antioxidants, UV absorbers, radical scavengers, biocides, small amounts of solvents and/or water retaining agents.
A further subject of the application is a process for pre-paring the dispersion of transparent powder coating, and its use for vehicle bodies.
Description
E. P .~--~;~-~ TE:
PAT 55511 $L R~ * T-E,z T i :A:
Aqueous dispersions of transparent powder coating The present invention relates to an aqueous dispersion of a transparent powder coating, which is particularly suitable as a coating for vehicle bodies coated with water-based basecoat.
Nowadays, for the purpose of coating vehicle bodies, liquid coating materials preferably are employed. Such materials cause numerous environmental problems due to their solvent content. This also applies to the use of water-based coating materials.
This is the reason why increased efforts have been made in recent years to employ powder coatings in the coating step.
However, the results have not been satisfying up to now; in particular, it is necessary to provide coatings with an increased thickness in order to obtain a uniform appearance.
On the other hand, the use of coating materials in powder form necessitates a different application technology. The piants designed for liquid coating materials cannot therefore be employed for the powders. Hence, an attempt is being made to develop aqueous dispersions of powder coatings, which may be processed by means of liquid-coating technologies.
US Patent 4,268,542, for example, discloses a process employing a powder coating slurry which is suitable for the coating of vehicles. In this process, a conventional powder coat is first applied to the bodywork, and the transparent coating slurry is applied as a second coat. In this transparent coating slurry based on acrylate resins, ionic thickeners are used which lead to a relatively high sensitivity of the applied coat to moisture, especially to condensation. Furthermore, in one of the examples these have a content of from 0.5 to 30 % of glycidyl-containing monomers.
Moreover, it is necessary to operate with high baking temperatures (over 160 C).
PAT 55511 $L R~ * T-E,z T i :A:
Aqueous dispersions of transparent powder coating The present invention relates to an aqueous dispersion of a transparent powder coating, which is particularly suitable as a coating for vehicle bodies coated with water-based basecoat.
Nowadays, for the purpose of coating vehicle bodies, liquid coating materials preferably are employed. Such materials cause numerous environmental problems due to their solvent content. This also applies to the use of water-based coating materials.
This is the reason why increased efforts have been made in recent years to employ powder coatings in the coating step.
However, the results have not been satisfying up to now; in particular, it is necessary to provide coatings with an increased thickness in order to obtain a uniform appearance.
On the other hand, the use of coating materials in powder form necessitates a different application technology. The piants designed for liquid coating materials cannot therefore be employed for the powders. Hence, an attempt is being made to develop aqueous dispersions of powder coatings, which may be processed by means of liquid-coating technologies.
US Patent 4,268,542, for example, discloses a process employing a powder coating slurry which is suitable for the coating of vehicles. In this process, a conventional powder coat is first applied to the bodywork, and the transparent coating slurry is applied as a second coat. In this transparent coating slurry based on acrylate resins, ionic thickeners are used which lead to a relatively high sensitivity of the applied coat to moisture, especially to condensation. Furthermore, in one of the examples these have a content of from 0.5 to 30 % of glycidyl-containing monomers.
Moreover, it is necessary to operate with high baking temperatures (over 160 C).
In the text which follows, the terms transparent powder coating dispersion and powder clearcoat are used synonymously.
The present invention provides an aqueous dispersion of a transparent powder coating, which may be applied to vehicle bodies by means of the conventional liquid-coating technology and which may particularly be baked even at temperatures of 130 C.
This is achieved by an aqueous dispersion of a transparent powder coating, consisting of a solid powder component A and an aqueous component B, wherein component A is a transparent powder coating comprising (a) at least one epoxy group-containing binder having a content of glycidyl-containing monomers of from 30 to 45%, preferably from 30 to 35%, and optionally having a content of vinylaromatic compounds, preferably styrene;
(b) at least one crosslinking agent, preferably straight-chain aliphatic dicarboxylic acids and/or carboxy-functional polyesters; and (c) optionally catalysts, adjuvants, additives typical for transparent powder coatings, such as deaerating agents, levelling agents, UV absorbers, radical scavengers and antibxidants;
and component B is an aqueous dispersion comprising (a) at least one nonionic thickener; and (b) optionally catalysts, adjuvants, defoamers, dispersion adjuvants, wetting agents, preferably carboxy-functional dispersants, antioxidants, UV absorbers, radical scavengers, small amounts of solvents, levelling agents, biocides and/or water retaining agents.
The epoxy-functional binder for the solid transparent powder coating used for the preparation of the dispersion comprises, for example, epoxy group-containing polyacrylate resins which are preparable by copolymerisation of at least one ethylenically unsaturated monomer containing at least one epoxy group within the molecule and at least one further ethylenically unsaturated monomer containing no epoxy group within the molecule, at least one of the monomers being an ester of acrylic acid or methacrylic acid.
Such epoxy group-containing polyacrylate resins are, for example, known from EP-A-299 420; DE-B-22 14 650;
DE-B-27 49 576; US-A-4,091,048 and US-A 3,781,379.
Examples of ethylenically unsaturated monomers containing no epoxy group within the molecule are alkyl esters of acrylic acid and methacrylic acid containing 1 to 20 carbon atoms in the alkyl radical, particularly methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.
Further examples of ethylenically unsaturated monomers containing no epoxy groups within the molecule are acid amides, for example acrylamide and methacrylamide, vinylaromatic compounds, such as styrene, methylstyrene and vinyltoluene, nitriles, such as acrylonitrile and methacrylonitrile, vinyl halides and vinylidene halides, such as vinyl chloride and vinylidene fluoride, vinyl esters, for example vinyl acetate, and hydroxyl-containing 3a monomers, for example hydroxyethyl acrylate and hydroxyethyl methacrylate.
The epoxy group-containing polyacrylate resin usually has an epoxy equivalent weight of from 400 to 2500, preferably from 420 to 700, a number-average molecular weight of from 2000 to 20,000, preferably from 3000 to 10,0000 (determined by gel permeation chromatography using a polystyrene standard) and a glass transition temperature (TG) of from 30 to 80 C, preferably from 40 to 70 C, more preferably from 40 to 60 C (measured using differential scanning calorimetry (DSC)).
The present invention provides an aqueous dispersion of a transparent powder coating, which may be applied to vehicle bodies by means of the conventional liquid-coating technology and which may particularly be baked even at temperatures of 130 C.
This is achieved by an aqueous dispersion of a transparent powder coating, consisting of a solid powder component A and an aqueous component B, wherein component A is a transparent powder coating comprising (a) at least one epoxy group-containing binder having a content of glycidyl-containing monomers of from 30 to 45%, preferably from 30 to 35%, and optionally having a content of vinylaromatic compounds, preferably styrene;
(b) at least one crosslinking agent, preferably straight-chain aliphatic dicarboxylic acids and/or carboxy-functional polyesters; and (c) optionally catalysts, adjuvants, additives typical for transparent powder coatings, such as deaerating agents, levelling agents, UV absorbers, radical scavengers and antibxidants;
and component B is an aqueous dispersion comprising (a) at least one nonionic thickener; and (b) optionally catalysts, adjuvants, defoamers, dispersion adjuvants, wetting agents, preferably carboxy-functional dispersants, antioxidants, UV absorbers, radical scavengers, small amounts of solvents, levelling agents, biocides and/or water retaining agents.
The epoxy-functional binder for the solid transparent powder coating used for the preparation of the dispersion comprises, for example, epoxy group-containing polyacrylate resins which are preparable by copolymerisation of at least one ethylenically unsaturated monomer containing at least one epoxy group within the molecule and at least one further ethylenically unsaturated monomer containing no epoxy group within the molecule, at least one of the monomers being an ester of acrylic acid or methacrylic acid.
Such epoxy group-containing polyacrylate resins are, for example, known from EP-A-299 420; DE-B-22 14 650;
DE-B-27 49 576; US-A-4,091,048 and US-A 3,781,379.
Examples of ethylenically unsaturated monomers containing no epoxy group within the molecule are alkyl esters of acrylic acid and methacrylic acid containing 1 to 20 carbon atoms in the alkyl radical, particularly methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.
Further examples of ethylenically unsaturated monomers containing no epoxy groups within the molecule are acid amides, for example acrylamide and methacrylamide, vinylaromatic compounds, such as styrene, methylstyrene and vinyltoluene, nitriles, such as acrylonitrile and methacrylonitrile, vinyl halides and vinylidene halides, such as vinyl chloride and vinylidene fluoride, vinyl esters, for example vinyl acetate, and hydroxyl-containing 3a monomers, for example hydroxyethyl acrylate and hydroxyethyl methacrylate.
The epoxy group-containing polyacrylate resin usually has an epoxy equivalent weight of from 400 to 2500, preferably from 420 to 700, a number-average molecular weight of from 2000 to 20,000, preferably from 3000 to 10,0000 (determined by gel permeation chromatography using a polystyrene standard) and a glass transition temperature (TG) of from 30 to 80 C, preferably from 40 to 70 C, more preferably from 40 to 60 C (measured using differential scanning calorimetry (DSC)).
About 50 C is most preferred. Blends of two or more acrylate resins may also be employed.
The epoxy group-containing polyacrylate resin may be prepared in accordance with generally well-known methods by polymerisation.
Suitable crosslinking agents are carboxylic acids, in particular saturated straight-chain aliphatic dicarboxylic acids having 3 to 20 carbon atoms within the molecule. Most preferably, dodecane-1,12-dicarboxylic acid is used. In order to modify the properties of the final transparent powder coatings, other carboxyl-containing crosslinking agents may optionally be employed. As examples of such crosslinking agents there may be mentioned saturated branched or unsaturated straight-chain dicarboxylic acids and polycarboxylic acids as well as polymers having carboxyl groups.
Additionally, transparent powder coatings are suitable which contain an epoxy-functional crosslinking agent and an acid-functional binder.
As the acid-functional binder, suitable examples are acidic polyacrylate resins, which are preparable by copolymerizing at least one ethylenically unsaturated monomer containing at least one acid group within the molecule with at least one further ethylenically unsaturated monomer containing no acid group within the molecule.
The epoxy group-containing binder and the epoxy group-containing crosslinking agent, respectively, and the carboxyl-containing binder and the carboxyl-containing crosslinking agent, respectively, are usually employed in an amount such that there are 0.5 to 1.5 equivalents, preferably 0.75 to 1.25 equivalents, of carboxyl groups per equivalent of epoxy groups. The amount of carboxyl groups present may be determined by titration with an alcoholic KOH solution.
In accordance with the invention, the binder contains vinylaromatic compounds, particularly styrene. In order to limit the danger of fissure formation, the content is not, however, more than 35 o by weight. 10 to 25 % by weight is preferred.
The solid powder coatings optionally contain one or more catalysts suitable for epoxy resin curing. Suitable catalysts are phosphonium salts of organic or inorganic acids, quaternary ammonium compounds, amines, imidazole and imidazole derivatives. The catalysts are generally employed in amounts of from 0.001 s by weight to about 2 % by weight, based on the total weight of the epoxy resin and the cross-linking agent.
Examples of suitable phosphonium catalysts are ethyltriphenyl-phosphonium iodide, ethyltriphenylphosphonium chloride, ethyl-triphenylphosphonium thiocyanate, complex of ethyltriphenyl-phosphonium acetate and acetic acid, tetrabutylphosphonium iodide, tetrabutylphosphonium bromide and complex of tetra-butylphosphonium acetate and acetic acid. These and other suitable phosphonium catalysts are, for example, described in US-A 3,477,990 and US-A 3,341,580.
Suitable imidazole catalysts are, for example, 2-styryl-imidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2-butylimidazole. These and other imidazole catalysts are, for example, described in the Belgian Patent No. 756,693.
In addition, the solid powder coatings may optionally contain adjuvants and additives. These are exemplified by levelling agents, antioxidants, UV absorbers, radical scavengers, flow aids and deaerating agents, such as benzoin.
The solid powder coatings are prepared by known methods (see, for example, product information by the company BASF Lacke +
Farben AG, "Pulverlacke", 1990) by homogenizing and dispersing, for example by means of an extruder, screw-type kneading machine and the like. After their preparation, the b powder coatings are prepared for the dispersion operation by milling and optionally by sifting and screening.
The aqueous dispersion of the transparent powder coating can subsequently be prepared from the powder by wet milling or by introduction of dry-milled powder coating material, with stirring. Wet milling is particularly preferred.
The present invention also relates, accordingly, to a process for preparing an aqueous dispersion of a powder coating on the basis of the component A as described above, which is, in accordance with the invention, dispersed in a component B. The latter consists of an aqueous dispersion of catalysts, adjuvants, antifoams, antioxidants, wetting agents, UV
absorbers, radical scavengers, biocides, water retaining agents, small amounts of solvents and/or dispersion adjuvants, preferably carboxy-functional dispersion adjuvants.
As a further essential constituent, the aqueous component B of the powder coating dispersion contains at least one nonionic thickener a) . Preference is given to the use of nonionic associative thickeners a).
Structural features of such associative thickeners a) are:
aa) a hydrophilic structure which ensures adequate solu-bility in water, and ab) hydrophobic groups, which are capable of associative interaction in the aqueous medium.
Examples of hydrophobic groups employed are long-chain alkyl radicals, for example dodecyl, hexadecyl or octadecyl radicals, or alkaryl radicals, for example octylphenyl or nonylphenyl radicals.
Hydrophilic structures preferably employed are polyacrylates, cellulose ethers or, with particular preference, poly-urethanes, which contain the hydrophobic groups as polymer units.
Hydrophilic structures which are most preferred are poly-urethanes containing polyether chains as structural units, preferably comprising polyethylene oxide. In the synthesis of such polyetherpolyurethanes, the di- and/or polyisocyanates, preferably aliphatic diisocyanates, most preferably unsubsti-tuted or alkyl-substituted 1,6-hexamethylene diisocyanate, are used to link the hydroxyl-terminated polyether units to one another and to link the polyether units with the hydrophobic end-group units, which may for example be monofunctional alcohols and/or amines bearing the long-chain alkyl radicals or aralkyl radicals already mentioned.
Following the dispersion of component A in component B, milling is carried out optionally, the pH is adjusted to from 4.0 to 7.0, preferably from 5.5 to 6.5, and the mixture is filtered.
The mean particle size is between 1 and 25 m, preferably below 20 m, particularly preferably from 3 to 10 m. The solids content of the aqueous dispersion of the transparent powder coating is between 15 and 50 %.
Before or after the wet milling or the incorporation of the dry powder coating into the water, there may be added to the dispersion from 0 to 5% by weight of a blend of defoamers, of an ammonium and/or alkali metal salt, of a carboxy-functional or nonionic dispersion adjuvant, of a wetting agent and/or of a thickener mixture as well as of the other additives above.
Preferably, in accordance with the invention, defoamer, dispersion adjuvant, wetting agent and/or thickener are dispersed in water first. Then small portions of the transparent powder coating are stirred in. Then defoamer, dispersion adjuvant, thickener and wetting agent are dispersed into the mixture once again. Finally, small portions of the transparent powder coatings are stirred in again.
In accordance with the invention, the pH is preferably adjusted using ammonia or amines. The pH here may initially increase, so that a strongly basic dispersion is formed.
Within several hours or days, however, the pH falls again to the above-indicated values.
The dispersion of the transparent powder coating according to the invention may be used as a coating over basecoats preferably in the automotive industry. The clearcoat disper-sion is particularly suitable for water-based coating materials based on a polyester, polyurethane resin and an amino resin.
The dispersions of the transparent powder coating according to the invention may be applied by the methods known from the liquid-coating technology. In particular, the dispersions may be applied by means of spray coating methods. However, electrostatically assisted high-speed rotation or pneumatic application are also suitable.
The dispersions of the transparent powder coating are, after application to the basecoat, usually flashed off before baking. This is appropriately done at room temperature first and then at slightly elevated temperature. Usually, the elevated temperature is from 40 to 70 C, preferably 50 to 65 C. The flashoff is carried out for from 2 to 10 minutes, preferably 4 to 8 minutes, at room temperature. Flashing off is carried out again for the same period of time at elevated temperature.
The baking step may even be carried out at temperatures of 130 C. Baking may be carried out at 130 to 180 C, preferably at 135 to 155 C.
With the process according to the invention it is possible to obtain coats having a thickness of 30 to 50 m, preferably from 35 to 45 m. In accordance with the prior art, clearcoats of comparable quality could be obtained only by applying coats having a thickness of 65 to 80 m when employing transparent powder coatings.
Tr:e inver.tion is .:escribed in more detail below with reference to the examples:
1. Preparation of the acrylata resin 21.1 parts of xylene are fed into a vessel and heated to 130 C. At 130 C there are added, within a period of 4 h, via two sezarate feed vessels; initiator: 4.5 parts of THPEH (tert-butyl perethylhexanoate) in a mixture with 4.86 parts of xylene; and monomers: 10.78 parts of methyl methacrylate, 25.5 parts of n-butyl methacrylate, 17.39 parts of styrene and 23.95 parts of gZycidyl methacrylate. The mixturs is then heated to 180OC, and the solvent is stripped off under a reduced pressure < 100 mbar.
2. Preparation of the transparent powder coating 77.5 parts of acz-ylate resin, 18.8 parts of dodecane dicarboxylic acid (3cidic hardener), 2 parts of TinuvinTM
1130 (iJV absorber), 0.9. parts of Tinuvin 144 (HALS), 0.4 parts of AdditolTM xL 490 (levelling agent) and 0.,4 parts of benzoin (deaerating agent) are mixed intimately on a Henschel fluid mixer, and the mixture is extruded in a BUSS PLK 46 extruder, milled -in a Hosohawa ACM 2 rnill and screened by means of a 125 m sieve.
3. Preparation of the dispersion In 400 parts of dernineralized water, there are dispersed 0.6 parts of Troykyd D777 (defoamer), 0.6 parts of Crotan 731 K(dispersion adjuvant), 0.06 parts of SurfinolMTMN 6 (wetting agent) and 16.5 parts of RM8 (Rohm & Haas, nonionic, associative, polyurethane-based thickener).
Thereafter, 94 parts of the transparent powder coating are stirred in in small portions. A further 0.6 parts of Troykyd 0777, 0.6 par*-s of Orotan 731 K, 0.06 parts of Surfinol 7. 6 and 16.5 parts of RM8 are dispersed into the itixture. Finally, 49 parts of the transparent powder coating are stirred ir, in sna+l portions. The material is Mi1_ed _r_ i sand mil: for 3.5 h. The average particle size finally measured is 4 m. The material is filtered through a 50 m filter and, finally, 0.05 t Byk 345 (levelling agent) is added.
4. Application of the dispersion By means of a bowl-type spray gun, the slurry is appl-ied to steel panels coated with a water-based basecoat. The metal panel is flashed off for 5 minutes at room temperature and for 5 minutes at 60 C. Thereafter, the panel is baked for 30 minutes at a temperature of 140 C.
A high-gloss clearcoat film with a coat thickness of 40 m is produced which has MEK resistance (> 100 double strokes).
The clearcoat film possesses good resistance to condensa-tion.
The epoxy group-containing polyacrylate resin may be prepared in accordance with generally well-known methods by polymerisation.
Suitable crosslinking agents are carboxylic acids, in particular saturated straight-chain aliphatic dicarboxylic acids having 3 to 20 carbon atoms within the molecule. Most preferably, dodecane-1,12-dicarboxylic acid is used. In order to modify the properties of the final transparent powder coatings, other carboxyl-containing crosslinking agents may optionally be employed. As examples of such crosslinking agents there may be mentioned saturated branched or unsaturated straight-chain dicarboxylic acids and polycarboxylic acids as well as polymers having carboxyl groups.
Additionally, transparent powder coatings are suitable which contain an epoxy-functional crosslinking agent and an acid-functional binder.
As the acid-functional binder, suitable examples are acidic polyacrylate resins, which are preparable by copolymerizing at least one ethylenically unsaturated monomer containing at least one acid group within the molecule with at least one further ethylenically unsaturated monomer containing no acid group within the molecule.
The epoxy group-containing binder and the epoxy group-containing crosslinking agent, respectively, and the carboxyl-containing binder and the carboxyl-containing crosslinking agent, respectively, are usually employed in an amount such that there are 0.5 to 1.5 equivalents, preferably 0.75 to 1.25 equivalents, of carboxyl groups per equivalent of epoxy groups. The amount of carboxyl groups present may be determined by titration with an alcoholic KOH solution.
In accordance with the invention, the binder contains vinylaromatic compounds, particularly styrene. In order to limit the danger of fissure formation, the content is not, however, more than 35 o by weight. 10 to 25 % by weight is preferred.
The solid powder coatings optionally contain one or more catalysts suitable for epoxy resin curing. Suitable catalysts are phosphonium salts of organic or inorganic acids, quaternary ammonium compounds, amines, imidazole and imidazole derivatives. The catalysts are generally employed in amounts of from 0.001 s by weight to about 2 % by weight, based on the total weight of the epoxy resin and the cross-linking agent.
Examples of suitable phosphonium catalysts are ethyltriphenyl-phosphonium iodide, ethyltriphenylphosphonium chloride, ethyl-triphenylphosphonium thiocyanate, complex of ethyltriphenyl-phosphonium acetate and acetic acid, tetrabutylphosphonium iodide, tetrabutylphosphonium bromide and complex of tetra-butylphosphonium acetate and acetic acid. These and other suitable phosphonium catalysts are, for example, described in US-A 3,477,990 and US-A 3,341,580.
Suitable imidazole catalysts are, for example, 2-styryl-imidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2-butylimidazole. These and other imidazole catalysts are, for example, described in the Belgian Patent No. 756,693.
In addition, the solid powder coatings may optionally contain adjuvants and additives. These are exemplified by levelling agents, antioxidants, UV absorbers, radical scavengers, flow aids and deaerating agents, such as benzoin.
The solid powder coatings are prepared by known methods (see, for example, product information by the company BASF Lacke +
Farben AG, "Pulverlacke", 1990) by homogenizing and dispersing, for example by means of an extruder, screw-type kneading machine and the like. After their preparation, the b powder coatings are prepared for the dispersion operation by milling and optionally by sifting and screening.
The aqueous dispersion of the transparent powder coating can subsequently be prepared from the powder by wet milling or by introduction of dry-milled powder coating material, with stirring. Wet milling is particularly preferred.
The present invention also relates, accordingly, to a process for preparing an aqueous dispersion of a powder coating on the basis of the component A as described above, which is, in accordance with the invention, dispersed in a component B. The latter consists of an aqueous dispersion of catalysts, adjuvants, antifoams, antioxidants, wetting agents, UV
absorbers, radical scavengers, biocides, water retaining agents, small amounts of solvents and/or dispersion adjuvants, preferably carboxy-functional dispersion adjuvants.
As a further essential constituent, the aqueous component B of the powder coating dispersion contains at least one nonionic thickener a) . Preference is given to the use of nonionic associative thickeners a).
Structural features of such associative thickeners a) are:
aa) a hydrophilic structure which ensures adequate solu-bility in water, and ab) hydrophobic groups, which are capable of associative interaction in the aqueous medium.
Examples of hydrophobic groups employed are long-chain alkyl radicals, for example dodecyl, hexadecyl or octadecyl radicals, or alkaryl radicals, for example octylphenyl or nonylphenyl radicals.
Hydrophilic structures preferably employed are polyacrylates, cellulose ethers or, with particular preference, poly-urethanes, which contain the hydrophobic groups as polymer units.
Hydrophilic structures which are most preferred are poly-urethanes containing polyether chains as structural units, preferably comprising polyethylene oxide. In the synthesis of such polyetherpolyurethanes, the di- and/or polyisocyanates, preferably aliphatic diisocyanates, most preferably unsubsti-tuted or alkyl-substituted 1,6-hexamethylene diisocyanate, are used to link the hydroxyl-terminated polyether units to one another and to link the polyether units with the hydrophobic end-group units, which may for example be monofunctional alcohols and/or amines bearing the long-chain alkyl radicals or aralkyl radicals already mentioned.
Following the dispersion of component A in component B, milling is carried out optionally, the pH is adjusted to from 4.0 to 7.0, preferably from 5.5 to 6.5, and the mixture is filtered.
The mean particle size is between 1 and 25 m, preferably below 20 m, particularly preferably from 3 to 10 m. The solids content of the aqueous dispersion of the transparent powder coating is between 15 and 50 %.
Before or after the wet milling or the incorporation of the dry powder coating into the water, there may be added to the dispersion from 0 to 5% by weight of a blend of defoamers, of an ammonium and/or alkali metal salt, of a carboxy-functional or nonionic dispersion adjuvant, of a wetting agent and/or of a thickener mixture as well as of the other additives above.
Preferably, in accordance with the invention, defoamer, dispersion adjuvant, wetting agent and/or thickener are dispersed in water first. Then small portions of the transparent powder coating are stirred in. Then defoamer, dispersion adjuvant, thickener and wetting agent are dispersed into the mixture once again. Finally, small portions of the transparent powder coatings are stirred in again.
In accordance with the invention, the pH is preferably adjusted using ammonia or amines. The pH here may initially increase, so that a strongly basic dispersion is formed.
Within several hours or days, however, the pH falls again to the above-indicated values.
The dispersion of the transparent powder coating according to the invention may be used as a coating over basecoats preferably in the automotive industry. The clearcoat disper-sion is particularly suitable for water-based coating materials based on a polyester, polyurethane resin and an amino resin.
The dispersions of the transparent powder coating according to the invention may be applied by the methods known from the liquid-coating technology. In particular, the dispersions may be applied by means of spray coating methods. However, electrostatically assisted high-speed rotation or pneumatic application are also suitable.
The dispersions of the transparent powder coating are, after application to the basecoat, usually flashed off before baking. This is appropriately done at room temperature first and then at slightly elevated temperature. Usually, the elevated temperature is from 40 to 70 C, preferably 50 to 65 C. The flashoff is carried out for from 2 to 10 minutes, preferably 4 to 8 minutes, at room temperature. Flashing off is carried out again for the same period of time at elevated temperature.
The baking step may even be carried out at temperatures of 130 C. Baking may be carried out at 130 to 180 C, preferably at 135 to 155 C.
With the process according to the invention it is possible to obtain coats having a thickness of 30 to 50 m, preferably from 35 to 45 m. In accordance with the prior art, clearcoats of comparable quality could be obtained only by applying coats having a thickness of 65 to 80 m when employing transparent powder coatings.
Tr:e inver.tion is .:escribed in more detail below with reference to the examples:
1. Preparation of the acrylata resin 21.1 parts of xylene are fed into a vessel and heated to 130 C. At 130 C there are added, within a period of 4 h, via two sezarate feed vessels; initiator: 4.5 parts of THPEH (tert-butyl perethylhexanoate) in a mixture with 4.86 parts of xylene; and monomers: 10.78 parts of methyl methacrylate, 25.5 parts of n-butyl methacrylate, 17.39 parts of styrene and 23.95 parts of gZycidyl methacrylate. The mixturs is then heated to 180OC, and the solvent is stripped off under a reduced pressure < 100 mbar.
2. Preparation of the transparent powder coating 77.5 parts of acz-ylate resin, 18.8 parts of dodecane dicarboxylic acid (3cidic hardener), 2 parts of TinuvinTM
1130 (iJV absorber), 0.9. parts of Tinuvin 144 (HALS), 0.4 parts of AdditolTM xL 490 (levelling agent) and 0.,4 parts of benzoin (deaerating agent) are mixed intimately on a Henschel fluid mixer, and the mixture is extruded in a BUSS PLK 46 extruder, milled -in a Hosohawa ACM 2 rnill and screened by means of a 125 m sieve.
3. Preparation of the dispersion In 400 parts of dernineralized water, there are dispersed 0.6 parts of Troykyd D777 (defoamer), 0.6 parts of Crotan 731 K(dispersion adjuvant), 0.06 parts of SurfinolMTMN 6 (wetting agent) and 16.5 parts of RM8 (Rohm & Haas, nonionic, associative, polyurethane-based thickener).
Thereafter, 94 parts of the transparent powder coating are stirred in in small portions. A further 0.6 parts of Troykyd 0777, 0.6 par*-s of Orotan 731 K, 0.06 parts of Surfinol 7. 6 and 16.5 parts of RM8 are dispersed into the itixture. Finally, 49 parts of the transparent powder coating are stirred ir, in sna+l portions. The material is Mi1_ed _r_ i sand mil: for 3.5 h. The average particle size finally measured is 4 m. The material is filtered through a 50 m filter and, finally, 0.05 t Byk 345 (levelling agent) is added.
4. Application of the dispersion By means of a bowl-type spray gun, the slurry is appl-ied to steel panels coated with a water-based basecoat. The metal panel is flashed off for 5 minutes at room temperature and for 5 minutes at 60 C. Thereafter, the panel is baked for 30 minutes at a temperature of 140 C.
A high-gloss clearcoat film with a coat thickness of 40 m is produced which has MEK resistance (> 100 double strokes).
The clearcoat film possesses good resistance to condensa-tion.
Claims (10)
1. An aqueous dispersion of a transparent powder coating, consisting of a solid powder component A and an aqueous component B, wherein:
component A is a transparent powder coating, comprising:
(a) at least one epoxy group-containing binder having a content of glycidyl-containing monomers of from 30 to 45% by weight and optionally having a content of a vinylaromatic compound;
(b) at least one crosslinking agent; and (c) optionally a catalyst, an adjuvant, and an additive typical for transparent powder coatings;
and component B is an aqueous dispersion, comprising:
(a) at least one nonionic thickener containing as structural features:
(aa) a hydrophilic framework, and (ab) hydrophobic groups which are capable of associative interaction in the aqueous medium; and (b) optionally a catalyst, an adjuvant, a defoamer, a wetting agent, a dispersion adjuvant, an antioxidant, a UV absorber, a radical scavenger, a biocide, a small amount of a solvent, a levelling agent, a neutralizing agent, a water retaining agent or a mixture thereof.
component A is a transparent powder coating, comprising:
(a) at least one epoxy group-containing binder having a content of glycidyl-containing monomers of from 30 to 45% by weight and optionally having a content of a vinylaromatic compound;
(b) at least one crosslinking agent; and (c) optionally a catalyst, an adjuvant, and an additive typical for transparent powder coatings;
and component B is an aqueous dispersion, comprising:
(a) at least one nonionic thickener containing as structural features:
(aa) a hydrophilic framework, and (ab) hydrophobic groups which are capable of associative interaction in the aqueous medium; and (b) optionally a catalyst, an adjuvant, a defoamer, a wetting agent, a dispersion adjuvant, an antioxidant, a UV absorber, a radical scavenger, a biocide, a small amount of a solvent, a levelling agent, a neutralizing agent, a water retaining agent or a mixture thereof.
2. The aqueous dispersion of a transparent powder coating according to claim 1, wherein the pH is between 4.0 and 7Ø
3. The aqueous dispersion of a transparent powder coating according to claim 1 or 2, wherein the content of vinylaromatic compound is at most 35% by weight based on component (Aa).
4. The aqueous dispersion of a transparent powder coating according to any one of claims 1 - 3, wherein the epoxy-functional binder is an epoxy group-containing polyacrylate resin.
5. The aqueous dispersion of a transparent powder coating according to any one of claims 1- 4, wherein the particle size is at most 20 µm.
6. The aqueous dispersion of a transparent powder coating according to any one of claims 1 to 5, wherein the nonionic thickener (a) contains polyurethane chains as hydrophilic framework (aa).
7. The aqueous dispersion of a transparent powder coating according to claim 6, wherein the nonionic thickener (a) contains polyurethane chains with polyether units as hydrophilic framework (aa).
8. A process for preparing the aqueous dispersion of a transparent powder coating according to any one of claims 1 - 7, which comprises:
(I) preparing a dispersion from the solid, powder component A and the aqueous component B;
(II) optionally milling the dispersion prepared from components A and B; and (III) adjusting the pH of the dispersion to from 4.0 to 7.0, and filtering the dispersion.
(I) preparing a dispersion from the solid, powder component A and the aqueous component B;
(II) optionally milling the dispersion prepared from components A and B; and (III) adjusting the pH of the dispersion to from 4.0 to 7.0, and filtering the dispersion.
9. The process according to claim 8, wherein the aqueous dispersion of the transparent powder coating is prepared from the components A and B by wet milling.
10. Use of the aqueous dispersion of the transparent powder coating according to any one of claims 1- 7, for coating painted and unpainted vehicle bodies made of sheet metal or plastic by means of electrostatically assisted high-speed rotation or pneumatic application.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41929695A | 1995-04-10 | 1995-04-10 | |
| US08/419,296 | 1995-04-10 | ||
| PCT/EP1996/001480 WO1996032452A1 (en) | 1995-04-10 | 1996-04-04 | Aqueous dispersion of a transparent coating powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2216111A1 CA2216111A1 (en) | 1996-10-17 |
| CA2216111C true CA2216111C (en) | 2007-06-12 |
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ID=23661645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002216111A Expired - Fee Related CA2216111C (en) | 1995-04-10 | 1996-04-04 | Aqueous dispersions of transparent powder coating |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0820490B2 (en) |
| JP (1) | JPH11503478A (en) |
| KR (1) | KR19980703745A (en) |
| CN (1) | CN1181101A (en) |
| AT (1) | ATE181951T1 (en) |
| AU (1) | AU709658B2 (en) |
| BR (1) | BR9604948A (en) |
| CA (1) | CA2216111C (en) |
| DE (2) | DE59602397D1 (en) |
| ES (1) | ES2136400T5 (en) |
| SG (1) | SG54322A1 (en) |
| TW (1) | TW313580B (en) |
| WO (1) | WO1996032452A1 (en) |
| ZA (1) | ZA962618B (en) |
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| DE19727892A1 (en) * | 1997-07-01 | 1999-01-07 | Basf Coatings Ag | Aqueous powder coating dispersion, process for its preparation and use of the powder coating dispersion obtained |
| DE19736535C1 (en) * | 1997-08-22 | 1999-01-28 | Basf Coatings Ag | Base coat lacquer useful for lacquering vehicle especially car body |
| DE19744561A1 (en) * | 1997-09-20 | 1999-04-01 | Basf Coatings Ag | Powder-form paint for automobile body |
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| DE19835206A1 (en) * | 1998-08-04 | 2000-02-17 | Basf Coatings Ag | Aqueous powder clearcoat dispersion |
| DE19841408C2 (en) | 1998-09-10 | 2001-02-15 | Basf Coatings Ag | Powder clearcoat and aqueous powder clearcoat slurry and their use |
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| DE19846650A1 (en) | 1998-10-09 | 2000-04-13 | Basf Coatings Ag | Aqueous powder paint slurry, useful for the coating of motor vehicle bodies, comprises a hydroxyl group binding agent and a polyisocyanate crosslinking agent with stabilized surface isocyanate groups. |
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| DE19904330A1 (en) | 1999-01-28 | 2000-08-10 | Basf Coatings Ag | Aqueous coating material and module system for its production |
| DE19908018A1 (en) | 1999-02-25 | 2000-08-31 | Basf Coatings Ag | Powder slurry curable thermally and with actinic radiation, process for their preparation and their use |
| DE19908013A1 (en) | 1999-02-25 | 2000-08-31 | Basf Coatings Ag | With actinic radiation and optionally curable powder slurries, process for their preparation and their use |
| DE19909894A1 (en) | 1999-03-06 | 2000-09-07 | Basf Coatings Ag | Sol-gel coating for single-layer or multi-layer coatings |
| DE19914896A1 (en) | 1999-04-01 | 2000-10-05 | Basf Coatings Ag | Aqueous coating material, e.g. for painting cars or industrial substrates, contains a polyurethane binder based on bis-4-isocyanato-cyclohexyl-methane with a low trans-trans content, plus a crosslinker |
| DE19920141C1 (en) | 1999-05-03 | 2001-01-25 | Basf Coatings Ag | Low-yellowing aqueous powder clearcoat dispersions, process for the production of multi-layer coatings and use of polyvalents, inorganic acids and / or oxalic acid here |
| DE19921457B4 (en) | 1999-05-08 | 2006-05-04 | Basf Coatings Ag | Modular system for the production of aqueous coating materials, process for their preparation and use and coatings produced therewith |
| DE19932497A1 (en) | 1999-07-12 | 2001-01-18 | Basf Coatings Ag | Aqueous coating material, process for its preparation and its use |
| DE19940858A1 (en) | 1999-08-27 | 2001-03-01 | Basf Coatings Ag | Sol-gel coating for single-layer or multi-layer coatings |
| DE19953203A1 (en) | 1999-11-05 | 2007-12-06 | Basf Coatings Ag | Process for the preparation of multicoat color and / or effect paint systems using self-crosslinking graft copolymers of polyurethanes and novel self-crosslinking polyurethanes and their graft copolymers |
| DE19958726B4 (en) * | 1999-12-06 | 2004-01-15 | Basf Coatings Ag | Powder slurry and its use for producing a multicoat color and / or effect paint on a primed or unprimed substrate |
| DE19964282B4 (en) * | 1999-12-06 | 2004-01-29 | Basf Coatings Ag | Method for producing a color and / or effect multi-layer coating on a primed or unprimed substrate and multi-layer coatings that can be produced using the method |
| DE10001442A1 (en) | 2000-01-15 | 2001-10-18 | Basf Coatings Ag | Structurally viscous powder clearcoat slurry free of organic solvents, process for their production and their use |
| DE10004487A1 (en) | 2000-02-02 | 2001-08-16 | Basf Coatings Ag | Physically-, thermally- and/or light-curable, aqueous coating, adhesive or sealant composition, e.g. water-borne basecoat, contains a polyalkylene ether-terminated, aromatic bis-urethane-urea as rheology additive |
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| DE10041634C2 (en) | 2000-08-24 | 2002-10-17 | Basf Coatings Ag | Aqueous dispersion and its use for the production of coating materials, adhesives and sealants curable thermally and with actinic radiation |
| DE10055464B4 (en) | 2000-11-09 | 2006-06-14 | Basf Coatings Ag | Structural viscous, clear of organic solvents and external emulsifiers powder clearcoat slurry and their use |
| DE10108129A1 (en) * | 2001-02-21 | 2002-09-05 | Schenectady Europ Gmbh | Aqueous epoxy resin emulsions, process for their preparation and their use |
| DE10126651A1 (en) | 2001-06-01 | 2002-12-12 | Basf Coatings Ag | Use of copolymers with diphenylethylene units as emulsifiers for the production of powder slurry and coating powder for use in coating materials, adhesives and sealants, e.g. for painting cars |
| DE10130972C1 (en) | 2001-06-27 | 2002-11-07 | Basf Coatings Ag | Production of hard, scratch-resistant coatings, e.g. on automobile bodywork, using lacquer containing (meth)acrylate copolymer and photoinitiator, hardened by heat and irradiation in oxygen-depleted atmosphere |
| DE10135999A1 (en) | 2001-07-24 | 2003-02-20 | Basf Ag | Structurally viscous clear lacquer slurry, process for its preparation and its use |
| DE10353636A1 (en) * | 2003-11-17 | 2005-06-16 | Basf Coatings Ag | Thermally curable powder coatings, process for their preparation and their use |
| DE10353638A1 (en) | 2003-11-17 | 2005-06-23 | Basf Coatings Ag | Pseudoplastic, aqueous dispersions, process for their preparation and their use |
| DE102004027650A1 (en) | 2004-06-05 | 2006-01-05 | Basf Coatings Ag | Process for coating electrically conductive substrates |
| ATE448888T1 (en) | 2005-07-11 | 2009-12-15 | Akzo Nobel Coatings Int Bv | METHOD FOR ELECTROSTATIC POWDER COATING IN FLUID BED |
| DE102006038624A1 (en) | 2006-08-17 | 2008-03-06 | Tesa Ag | Method for fixing a component on a joining partner to be painted |
| CN101602825B (en) * | 2008-06-11 | 2013-05-15 | 德谦（上海）化学有限公司 | Acrylic acid color top-coat resin for plastic paint |
| DE102008054283A1 (en) | 2008-11-03 | 2010-06-02 | Basf Coatings Japan Ltd., Yokohama | Color and / or effect multi-layer coatings with pigment-free coatings as filler replacement, their preparation and use |
| DE102014007805A1 (en) | 2014-05-27 | 2015-12-03 | WindplusSonne GmbH | Solar absorber, process for its preparation and its use |
| DE102014013600A1 (en) | 2014-09-13 | 2016-03-17 | WindplusSonne GmbH | Solar absorber, process for its preparation and its use |
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| JPS5196835A (en) * | 1975-02-21 | 1976-08-25 | KINITSUNATOMAKUORUHOHO | |
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| JPS534048A (en) * | 1975-12-26 | 1978-01-14 | Dainippon Toryo Co Ltd | Method of forming multi-layer coating film |
| JPS5278939A (en) * | 1975-12-26 | 1977-07-02 | Dainippon Toryo Co Ltd | Application of thin coating film |
| JPS572367A (en) † | 1980-06-07 | 1982-01-07 | Kansai Paint Co Ltd | Water-dispersed thermosetting resin slurry paint composition |
| US4476271A (en) † | 1981-05-07 | 1984-10-09 | Dai Nippon Toryo Co., Ltd. | Aqueous dispersion type thermosetting coating composition |
| DE4107136A1 (en) * | 1991-03-06 | 1992-09-10 | Basf Lacke & Farben | METHOD FOR PRODUCING A MULTILAYER, PROTECTIVE AND / OR DECORATIVE PAINT |
| US5270416A (en) * | 1992-09-04 | 1993-12-14 | Ferro Corporation | Thermosetting glycidyl modified acrylic powder coatings |
| DE4310702A1 (en) * | 1993-04-01 | 1994-10-06 | Bayer Ag | Polyurethane-based thickener preparation and its use for thickening aqueous systems |
| US5379947A (en) * | 1993-11-09 | 1995-01-10 | Basf Corporation | Process for producing a powder coating composition |
| ES2140607T3 (en) * | 1994-11-28 | 2000-03-01 | Basf Corp | PROCEDURE FOR PRODUCING FLUID POWDER COATING COMPOSITIONS. |
-
1996
- 1996-04-02 ZA ZA962618A patent/ZA962618B/en unknown
- 1996-04-04 DE DE59602397T patent/DE59602397D1/en not_active Expired - Fee Related
- 1996-04-04 JP JP8530693A patent/JPH11503478A/en not_active Ceased
- 1996-04-04 ES ES96910953T patent/ES2136400T5/en not_active Expired - Lifetime
- 1996-04-04 DE DE19613547A patent/DE19613547C3/en not_active Expired - Fee Related
- 1996-04-04 WO PCT/EP1996/001480 patent/WO1996032452A1/en not_active Application Discontinuation
- 1996-04-04 CN CN96193192A patent/CN1181101A/en active Pending
- 1996-04-04 AT AT96910953T patent/ATE181951T1/en not_active IP Right Cessation
- 1996-04-04 AU AU53992/96A patent/AU709658B2/en not_active Ceased
- 1996-04-04 EP EP96910953A patent/EP0820490B2/en not_active Expired - Lifetime
- 1996-04-04 KR KR1019970707145A patent/KR19980703745A/en not_active Application Discontinuation
- 1996-04-04 BR BR9604948A patent/BR9604948A/en not_active IP Right Cessation
- 1996-04-04 CA CA002216111A patent/CA2216111C/en not_active Expired - Fee Related
- 1996-04-09 SG SG1996009052A patent/SG54322A1/en unknown
- 1996-05-15 TW TW085105717A patent/TW313580B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| ZA962618B (en) | 1996-10-11 |
| EP0820490A1 (en) | 1998-01-28 |
| DE19613547A1 (en) | 1996-11-07 |
| DE19613547C2 (en) | 1998-09-17 |
| ATE181951T1 (en) | 1999-07-15 |
| JPH11503478A (en) | 1999-03-26 |
| EP0820490B2 (en) | 2003-10-29 |
| WO1996032452A1 (en) | 1996-10-17 |
| AU5399296A (en) | 1996-10-30 |
| CA2216111A1 (en) | 1996-10-17 |
| KR19980703745A (en) | 1998-12-05 |
| ES2136400T3 (en) | 1999-11-16 |
| ES2136400T5 (en) | 2004-07-01 |
| TW313580B (en) | 1997-08-21 |
| CN1181101A (en) | 1998-05-06 |
| DE19613547C3 (en) | 2002-09-19 |
| BR9604948A (en) | 1998-06-09 |
| EP0820490B1 (en) | 1999-07-07 |
| SG54322A1 (en) | 1998-11-16 |
| AU709658B2 (en) | 1999-09-02 |
| DE59602397D1 (en) | 1999-08-12 |
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