EP1485438A1 - Agents de revetement aqueux a base de epoxybutene-polyethers - Google Patents

Agents de revetement aqueux a base de epoxybutene-polyethers

Info

Publication number
EP1485438A1
EP1485438A1 EP03739501A EP03739501A EP1485438A1 EP 1485438 A1 EP1485438 A1 EP 1485438A1 EP 03739501 A EP03739501 A EP 03739501A EP 03739501 A EP03739501 A EP 03739501A EP 1485438 A1 EP1485438 A1 EP 1485438A1
Authority
EP
European Patent Office
Prior art keywords
water
weight
acid
groups
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03739501A
Other languages
German (de)
English (en)
Inventor
Martin Melchiors
Jan Weikard
Rolf Gertzmann
Helmut Greiving
Ulrich Freudenberg
Peter J. Miller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Covestro LLC
Original Assignee
Bayer MaterialScience AG
Bayer MaterialScience LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2002106565 external-priority patent/DE10206565A1/de
Application filed by Bayer MaterialScience AG, Bayer MaterialScience LLC filed Critical Bayer MaterialScience AG
Priority claimed from US10/368,194 external-priority patent/US6696531B1/en
Publication of EP1485438A1 publication Critical patent/EP1485438A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/6795—Unsaturated polyethers
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/14—Unsaturated oxiranes

Definitions

  • the invention relates to water-dilutable polyurethanes which have structural units derived from 3,4-epoxy-1-butene, and to aqueous dispersions which contain these polyurethanes, a process for their preparation and use as aqueous oxidatively drying and / or UV-crosslinking coating compositions ,
  • EP-A 0 859 021 describes compounds with pendant vinyl groups which, by reacting (a) compounds which contain at least one vinyl group and at least one epoxy group, (b) a polybasic compound or its anhydride and optionally (c) a CH-acidic compound are prepared and their epoxidized derivatives.
  • WO 00/66646 discloses oil-free, oxidatively drying polyester resins which are obtained by derivatizing carboxyl-functional polyesters with 3,4-epoxy-1-butene, and drying the use of these resins in combination with an organic solvent and a drying catalyst in room temperature - the coatings.
  • WO 00/66649 discloses coating compositions based on polyether alcohols, which by ring-opening polymer tion of 3,4-epoxybutene can be prepared with water or alcohols.
  • the polyether alcohols produced in this way can serve as reactive thinners or binders in oxidatively drying coatings and as building blocks for such binders.
  • a disadvantage of the aqueous one-component lacquers previously known in lacquer technology is that, for example, the drying of oxidatively crosslinking water lacquers at room temperature often proceeds only slowly, even with the addition of siccatives as drying accelerators, and only moderate film hardness is achieved.
  • UV-curing aqueous one-component paints on the other hand, have an inadequate
  • This object was achieved by providing a water-thinnable polymer containing urethane groups, which has the structural units of 3,4-epoxy-1-butene and which can be used as the basis for a one-component aqueous dispersion.
  • the repeat units AI, A2 or mixtures A1 / A2 are in the polymer
  • n, m, p each represent integers from 3 to 100.
  • AI or A2 repeat units are distributed differently in the co-polymer.
  • the content of Al and / or A2 units in the polymer according to the invention is 2 to 80% by weight, preferably 5 to 50% by weight, particularly preferably 8 to 35% by weight.
  • the structural units AI and / or A2 contained in the polymers according to the invention can be obtained by opening the epoxy ring of 3,4-epoxy-1-butene. It is possible to add 3,4-epoxy-1-butene (single or multiple) to nucleophilic centers of a polymer or oligomer chain by opening the epoxy ring, e.g. an addition to COOH, OH or NH functional chain ends. On the other hand, it is also possible to use a polyether alcohol oligomer or polymer with one or more OH groups, prepared by ring-opening polymerization of 3,4-epoxy-1-butene, optionally in the presence of other monomers polymerizable under these conditions, such as e.g. Ethylene oxide, propylene oxide or
  • the structural units AI and / or A2 are preferably introduced into the polyurethanes by incorporating hydroxy-functional polyether polyols.
  • the polyether polyols can be composed entirely of repeating units Al and / or A2 (homopolymer) or else as a copolymer with other monomers polymerizable under these conditions, for example with ethylene oxide, propylene oxide or butylene oxide.
  • a macroinitiator containing repeating units from the above-mentioned comonomers can be used for the production of polyether alcohols by homopolymerizing 3,4-epoxy-1-butene.
  • Suitable catalysts for the production of the polyether alcohols are, for example, KOH, trifluoromethanesulfonic acid or their salts with yttrium or other lanthanide metals, palladium (0) compounds corresponding to US Pat. No. 5,393,867, such as tetrakistrisphenylphosphine-palladium (O).
  • DMC catalysts and the polymerization of epoxides with such catalysts are e.g. in EP-A 0 700 949.
  • the polymer according to the invention contains 1 to 40% by weight of urethane groups [NHCOO], preferably 2 to 30% by weight of urethane groups, particularly preferably 5 to 25% by weight and very particularly preferably 15 to 25% by weight of urethane groups.
  • the polymers according to the invention contain a total of 9 to 100 meq / lOOg of ionic and / or potentially ionic groups in order to achieve dispersibility or solubility in an aqueous medium.
  • the content of the ionic and / or potentially ionic groups is preferably in total 20 to 60 meq / 100 g, particularly preferably in total 25 to 50 meq / 100 g.
  • the water-dilutable polymer according to the invention is preferably a reaction product A) containing the components (al) 5 to 80% by weight, preferably 10 to 60% by weight, of polyisocyanates,
  • chain stopper 0 to 20% by weight chain stopper,.
  • chain extenders which have at least two groups which are reactive toward isocyanate groups and which are different from (a2), (a3) and (a4).
  • the water-dilutable polymers according to the invention have an average molecular weight M n of 1,000 to 50,000, preferably 1,600 to 10,000.
  • the polyisocyanates are the compounds known in the polyurethane or paint field, such as aliphatic, cycloaliphatic or aromatic diisocyanates.
  • Q being a hydrocarbon radical having 4 to 40 C atoms, preferably 4 to 20 C atoms.
  • Q is preferably an aliphatic C 4 -C 2 radical, a cycloaliphatic C 6 -C 5 radical, an aromatic C 6 -C 5 radical or an araliphatic C -C 5 radical.
  • diisocyanates are, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-diisocyanatodicyclohexyl methane, 4,4'-diisocyanate 2,2) - propane, 1,4-diisocyanatobenzene, 2,4- or 2,6-diisocyanatotoluene or mixtures of these isomers, 4,4'- or 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato- diphenyl (2,2) propane, p-xylylene diisocyanate and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl
  • polyisocyanates which contain carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea groups, iminooxadiazinedione groups, uretdione groups or biuret groups, and also 4-isocyanato-methyl-1, 8-octane diisocyanate (nonane triisocyanate).
  • Component (a2) preferably has an average molecular weight M n of 400 to 5000, particularly preferably 800 to 2000.
  • the hydroxyl number or amine number is generally 22 to 400, preferably 50 to 200 and particularly preferably 80 to 160 mg KOH / g ,
  • Suitable polyols (a2) are the compounds known from polyurethane chemistry, such as, for example, polyether polyols, polyester polyols, polycarbonate polyols, polyester amide polyols, polyamide polyols, epoxy resin polyols and their reaction products with CO 2 , polyacrylate polyols and similar compounds.
  • polyurethane chemistry such as, for example, polyether polyols, polyester polyols, polycarbonate polyols, polyester amide polyols, polyamide polyols, epoxy resin polyols and their reaction products with CO 2 , polyacrylate polyols and similar compounds.
  • polyols which can also be used in a mixture, are described, for example, in DE-A 20 20 905,
  • the compounds of component (a2) can also contain primary or secondary amino groups (partially or completely) as NCO-reactive groups.
  • suitable as component (a2) are aspartic acid esters of the above-mentioned molecular weight, as listed, for example, in EP-A 0 403 921, pp. 4-5.
  • Such secondary amines can also be used as a mixture with the polyols.
  • Preferred polyols are the polyether and polyester polyols, particularly preferred are those which have only terminal OH groups and have a functionality of less than or equal to 3, preferably from 2.8 to 2.
  • Preferred polyesters are the known polycondensates of di- and optionally poly (tri, tetra) ols and mono-, di- and optionally poly (tri, tetra) carboxylic acids or hydroxycarboxylic acids or lactones.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
  • suitable diols are ethylene glycol,
  • polyols to be used here examples include trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • Suitable di- or polycarboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, methyl acid, malaconic acid, malaconic acid, itaconic acid, malta acid, 3,3-diethylglutaric acid, 2,2-dimethylsuccinic acid, trimellitic acid or pyromellitic acid.
  • Anhydrides of these acids can also be used if they exist.
  • the present invention the
  • Suitable hydroxycarboxylic acids for the production of a polyester polyol with terminal hydroxyl are, for example, hydroxycaproic acid, hydroxybutyric acid,
  • Suitable lactones are e.g. Caprolactone, butyrolactone and the like.
  • Polyethene polyols which contain all or part of Al and / or A2 repeating units and also polyoxyethylene polyols, polyoxypropylene polyols, polyoxybutylene polyols or polytetrahydrofurans with terminal OH groups are very particularly preferred.
  • polymers according to the invention can contain polyoxyalkylene ethers which are free from Al and / or A2 repeating units, but carry at least one hydroxyl or amino group per molecule, such as e.g. can be produced from an alcohol and from polyethylene oxide / polypropylene oxide blocks with a molecular weight of 400 to 4000.
  • component (a2) contains, at least in part, an oligoester or polyester which contains mono- and / or polyunsaturated fatty acids.
  • Suitable fatty acids are e.g. Coconut oil fatty acid, soybean oil fatty acid, safflower oil fatty acid, castor fatty acid, ricinic acid, peanut oil fatty acid, tall oil fatty acid or conjuene fatty acid.
  • Suitable other monocarboxylic acids are e.g. Benzoic acid, tert-butylbenzoic acid, hexahydrobenzoic acid,
  • Polyester acrylates containing hydroxyl groups and having an OH content of 30 to 300 mg KOH / g are preferably used.
  • a total of 7 groups of monomer components can be used in the preparation of the hydroxy-functional polyester acrylates:
  • (cyclo) alkanediols e.g. dihydric alcohols with (cyclo) aliphatically bound hydroxyl groups in the molecular weight range 62 to 286, such as ethanediol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol , 1, 6-hexanediol, neopentyl glycol, cyclohexane-l, 4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, diols containing ether oxygen, such as, for example Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene, polypropylene or polybutylene glycols with a maximum molecular weight of 2000, preferably 1000 and particularly
  • Mono alcohols such as Ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
  • monocarboxylic acids e.g. Benzoic acid, cyclohexane carboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, natural and synthetic fatty acids.
  • Acrylic acid methacrylic acid or dimeric acrylic acid.
  • Particularly preferred hydroxyl-containing polyester acrylates contain the reaction product of at least one component from group 1 or 2 with at least one component from group 4 or 5 and at least one component from group 7.
  • polyester acrylates to be used according to the invention, to also be generally known from the prior art, for example in Progress in
  • proportionate polyethylene glycols and / or methoxypolyethylene glycols can be incorporated as the alcohol component.
  • examples of compounds which may be mentioned are polyethylene glycols started on alcohols, polypropylene glycols and their block copolymers and the monomethyl ethers of these polyglycols.
  • Polyethylene glycol 1500 and / or polyethylene glycol is preferred.
  • epoxies are epoxides (glycidyl ether) of monomeric, oligomeric or polymeric bisphenol-A, bisphenol-F, hexanediol and / or butanediol. This reaction can be used in particular to increase the OH number of the polyester acrylate, since one OH group is formed in each case in the epoxy-acid reaction.
  • polyester acrylates in the sense of the present invention is described, for example, in DE-A-4 040 290, DE-A-3 316 592 and PKT Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints , Vol. 2, 1991, SITA Technology, London, pp. 123-135.
  • the acid number of the polyester acrylates is less than or equal to 20 mg KOH / g, preferably less than or equal to 10 mg KOH / g and particularly preferably less than or equal to 5 mg KOH / g.
  • epoxy acrylates containing hydroxyl groups polyether acrylates containing hydroxyl groups or polyurethane acrylates containing hydroxyl groups with OH contents of 20 to 300 mg KOH / g can also be used, as well as their
  • the polymer according to the invention thus preferably contains (meth) acrylic ester double bonds in addition to the allylic double bonds present from the structural units in Al and / or A2.
  • Compounds suitable as component (a3) are those which have at least one group which is reactive toward isocyanate groups and at least one ionic and / or potentially ionic group.
  • Potentially ionic are understood to be those groups which are capable of forming an ionic group.
  • Ionic or potentially ionic groups are, for example, carboxyl, sulfonic acid, phosphoric acid or phosphonic acid groups or their corresponding anions.
  • Carboxyl (at) and / or sulfone (at) groups are preferred.
  • Suitable components (a3) are described, for example, in US Pat. No. 3,412,054, columns 1 and 2, US Pat. No. 3,640,924, column 3 and in DE-A 26 24 442, pages 25 to 26, to which reference is made here.
  • compounds (a3) containing amino groups such as, for example, ⁇ , ⁇ -diaminovaleric acid or 2,4-diamino-toluenesulfonic acid (5). Mixtures of these compounds (a3) can also be used.
  • Particularly preferred compounds (a3) are alcohols which have at least one
  • Carboxyl group preferably contain 1 to 3 carboxyl groups per molecule.
  • Examples include hydroxypivalic acid, dihydroxycarboxylic acids, such as ⁇ , ⁇ -dialkylolalkanoic acids, in particular ⁇ , ⁇ -dimethylolalkanoic acids, such as 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylol pentanoic acid, dihydroxysuccinic acid, also polyhydroxy acids, such as gluconic acid. 2,2-Dimethylolpropionic acid is very particularly preferred.
  • the low molecular weight polyols and / or secondary polyamines (a4) optionally used to construct the polymers according to the invention generally stiffen the polymer chain. They have a molecular weight of 62 to 400, preferably from 62 to 200 and can contain ahphatic, alicychic or aromatic groups.
  • Suitable components (a4) are low molecular weight polyols with up to about 20 carbon atoms per molecule, e.g. Ethylene glycol, diethylene glycol, 1,2-
  • Triols such as trimethylolpropane and / or glycerin can also be used.
  • polyols which contain a maximum of 5 epoxybutene units (A1 / A2) started on water, short-chain polyols or polyamines and have an average molecular weight of less than 400.
  • the polymer according to the invention can optionally also contain building blocks (a5) which are located at the chain ends and terminate them, so-called chain stoppers.
  • Suitable components (a5) are derived from mono-functional compounds which react with NCO groups, e.g. Monoamines, preferably mono-secondary amines or monoalcohols. Examples include methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine or their substituted derivatives. Amidamines from diprimary amines and monocarboxylic acids, monoketimines from diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
  • Monoamines preferably mono-secondary amines or monoalcohols. Examples include methylamine, ethylamine,
  • suitable components (a5) are mono-hydroxy-functional esters of acrylic and / or methacrylic acid, so-called (meth) acrylates.
  • suitable components (a5) are mono-hydroxy-functional esters of acrylic and / or methacrylic acid, so-called (meth) acrylates.
  • suitable compounds are the mono- (meth) acrylates of dihydric alcohols, such as ethanediol, the isomeric propanediols and butanediols or (meth) acrylates of polyhydric alcohols, such as, for example, trimethylolpropane, glycerol and pentaerythritol, which on average contain a free hydroxyl group.
  • Preferred compounds (a5) are those which have active hydrogen
  • NCO groups Contain NCO groups of different reactivity.
  • These are, for example, compounds which, in addition to a primary amino group, also contain secondary amino groups or, in addition to an OH group, also COOH groups or, in addition to an amino group (primary or secondary), also OH groups, the latter being preferred.
  • Examples include primary / secondary amines, such as 3-amino-1-methylamino-propane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, mono-hydroxycarboxylic acids, such as hydroxyacetic acid, Lactic acid or malic acid, furthermore alkanolamines such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine and particularly preferably diethanolamine.
  • Aspartic acid esters based on the abovementioned are also suitable
  • the polymer according to the invention can also contain building blocks (a6) which are derived from so-called chain extenders.
  • building blocks (a6) which are derived from so-called chain extenders.
  • chain extenders there are the known, preferably difunctional, NCO groups reactive and preferred
  • the preparation of the polymers according to the invention is described in the prior art, for example in EP-A 0 355 682, EP-A 0 427 028 or DE-A 39 01 190.
  • the preparation can be carried out in such a way that an isocyanate-functional prepolymer is first produced and an OH- and / or NH-functional compound is obtained in a second reaction step by reaction with compounds (a5) and / or (a6) , as disclosed for example in EP-A 0 355 682.
  • the preparation can also take place in such a way that the one containing OH groups
  • Polyurethane resin is formed directly by reacting components (al) to (a6), e.g. described in EP-A 0 427 028.
  • the polymer A) according to the invention is preferably prepared in such a way that first a polyurethane prepolymer is formed from the components (a1, polyisocyanates), (a2, polyols) and optionally component (a4, low molecular weight polyols) and components (a3) manufactures, which contains on average at least 1.7, preferably 2 to 2.5 free isocyanate groups per molecule and then then completely or partially reacts this prepolymer with the components (a5) and / or (a6) in a non-aqueous system.
  • the polyisocyanate is used in excess in the process according to the invention over the polyols (a2) to (a4), so that a product with free isocyanate groups results.
  • These isocyanate groups are terminal and / or pendant, preferably terminal.
  • the amount of polyisocyanate is expediently so large that the equivalent ratio of isocyanate groups to the total number of OH groups in the polyols (a2) to (a4) is 1.05 to 2.0, preferably 1.1 to 1.6.
  • the prepolymer is normally prepared at temperatures of 40 ° to 140 ° C., depending on the reactivity of the isocyanate used.
  • Suitable catalysts as are known to the person skilled in the art for accelerating the NCO-OH reaction, can be used to accelerate the urethanization reaction. Examples are tert. Amines such as triethylamine, organotin compounds such as dibutyltin oxide, dibutyltin dilaurate or tin bis (2-ethylhexanoate) or other organometallic compounds.
  • the urethanization reaction is preferably carried out in the presence of solvents which are inactive towards isocyanates. Solvents which are compatible with water, such as ethers, ketones and esters, and N-methylpyrrolidone, are particularly suitable for this. The amount of this solvent advantageously does not exceed 25% by weight and is preferably in the range from 5 to 15
  • polyurethane resin based in each case on the sum of polyurethane resin and solvent.
  • the polyisocyanate can be added quickly to the solution of the other components.
  • the prepolymer or its solution is then reacted with the compound according to (a5) and / or (a6), the temperature advantageously being in the range from 0 ° to 90 ° C., preferably from 20 ° to 60 ° C., until the NCO Content in the prepolymer has practically dropped to zero.
  • the compound (a5) is used in a deficit or in a slight excess, the amounts mostly being 40 to 110% by weight, preferably 60 to 105% by weight, of the required stoichiometric
  • Amount If less reactive diisocyanates are used to prepare the prepolymer, this reaction can also take place in water at the same time as the neutralization.
  • a portion of the (non-neutralized) COOH groups preferably 5 to 30% by weight, can optionally be reacted with difunctional compounds reactive with COOH groups, such as diepoxides.
  • the prepolymer can also be reacted with (a5) in part (based on the isocyanate content) before the remaining isocyanate groups are reacted completely or in part with component (a6) after the dispersion.
  • the neutralization of the carboxyl groups can take place both before the dispersing step by adding the neutralizing agent to the prepolymer and during the dispersing step by adding the neutralizing amine to the dispersing water.
  • the polymer A) according to the invention can also be prepared by reacting components (a1) to (a6) in a direct reaction to give an OH-functional one Resin.
  • the reaction conditions correspond to the conditions described for the preparation of the prepolymer containing NCO groups. Such a method is described, for example, in EP-A 0 427 028.
  • a further possibility for the production of the polyurethane polymer according to the invention consists of resins containing COOH and / or SO 3 H groups, which additionally contain one or more groups reactive with isocyanate, via di- or polyisocyanates with polyether alcohols, which contain at least a proportion of repeating units Al and / or contain A2 to implement.
  • Resins suitable for this purpose are, for example, vinyl polymers, polyesters, epoxies or hybrid resins (for example acrylate-grafted polyesters or polyurethanes), as are known from the prior art.
  • Tertiary amines are particularly suitable for neutralizing the resulting product containing COOH and / or SO 3 H groups, for example trialkylamines having 1 to 12, preferably 1 to 6, carbon atoms in each alkyl radical. Examples are trimethylamine,
  • the alkyl radicals can, for example, also carry hydroxyl groups, as in the case of the dialkylmonoalkanol, alkyldialkanol and trialkanolamines, e.g. Dimethylethanolamine, which preferably serves as a neutralizing agent.
  • Inorganic bases such as ammonia or sodium or
  • Potassium hydroxide can be used.
  • the neutralizing agent is usually used in a molar ratio to the acid groups of the prepolymer from 0.3: 1 to 1.3: 1, preferably from 0.5: 1 to 1: 1.
  • the neutralization of the COOH or S0 3 H groups can be done before, during or in
  • the neutralization step is carried out between room temperature and 100 ° C., preferably from 40 to 80 ° C. It can be carried out in any manner, for example by adding the water-containing neutralizing agent to the polyurethane resin or vice versa. However, it is also possible that the neutralizing agent is added first Add polyurethane resin and only then the water. In general, solids contents of 20 to 70% by weight, preferably 30 to 50% by weight, are obtained in this way.
  • the present invention also relates to aqueous dispersions
  • a mixture of several polymers (A) according to the invention can also be used.
  • Suitable organic cosolvents (B) are the conventional paint solvents known per se, such as, for example, ethyl acetate, butyl acetate, ethylene glycol monomethyl or ethyl ether acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2 -Butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, white spirit, mixtures which contain above all more highly substituted aromatics, as described, for example, under the names Solvent Naphtha, Solvesso ® (Exxon Mobil Chem. Comp., Houston), Cypar ® (Shell Chemicals, UK), cyclo Sol ® (Shell Chem.), Tolu
  • Sol ® (Shell Chem.), Shellsol ® (Shell Chem.) are commercially available, carbonic acid esters such as dimethyl carbonate, diethyl carbonate, 1, 2-ethylene carbonate and 1,2-propylene carbonate, lactones such as ß-propiolactone, ⁇ -butyrolactone, ⁇ -Caprolactone and ⁇ -methylcaprolactone, but also solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether acetate, N-methylpyrrolidone and N-methylcaprolactam, or any mixture of such solvents.
  • carbonic acid esters such as dimethyl carbonate, diethyl carbonate, 1, 2-ethylene carbonate and 1,2-propylene carbonate
  • lactones such as ß-propiolactone
  • ⁇ -butyrolactone ⁇ -Caprolactone
  • solvents such as propylene glycol
  • the organic cosolvents (B) can be added to the water-dilutable polymer containing urethane groups according to the invention or its dispersion subsequently or during production. Usually at least part of the organic Solvent added during the preparation or dispersion of the polymer according to the invention. For the production of low-co-or low-co-dispersions, it is also possible to use auxiliary solvents during the production process which are removed in a later step.
  • the dispersions containing the water-dilutable, urethane-containing polymers according to the invention are used either alone or in combination with other aqueous binders.
  • aqueous binders can e.g. B. of polyester, polyacrylate, polyepoxide or polyurethane polymers.
  • the combination with radiation-curable binders, e.g. in EP-A-0 753 531 is possible.
  • the dispersions containing the polymers according to the invention can be used as such or in combination with the auxiliaries and additives known from coating technology, such as e.g. Pigments, fillers and paint aids e.g. Anti-settling agents, defoaming and / or wetting agents, leveling agents, reactive thinners,
  • Plasticizers, catalysts, auxiliary solvents or thickeners can be used to produce coatings.
  • the present invention also relates to coating compositions comprising the water-dilutable polymers containing urethane groups according to the invention.
  • the dispersions containing the polymers according to the invention are used as binders for the production of coatings.
  • coatings can be applied to any substrates, e.g. Wood, metal, plastic, paper, leather, textiles, felt, glass or mineral substrates.
  • the production of oxidatively drying aqueous coatings is preferred, characterized in that the coating agent contains the water-thinnable, urethane group-containing polymers (A) as a binder.
  • Siccatives can be added to accelerate the oxidative crosslinking.
  • An advantage of the dispersions which contain the polymers (A) according to the invention is that the production of fast-drying coatings is possible without the addition of siccatives.
  • the coating agent contains, as a binder, the water-dilutable polymers (A) according to the invention (A) and one or more photoinitiators.
  • UV-curing coatings produced in this way are distinguished from the UV-curing lacquers of the prior art by particularly good shadow curing.
  • the problem frequently arises that UV-curing coatings are soft, sticky and / or not resistant in places where no or only a small dose of UV light acts.
  • Post-curing via a second mechanism that is not dependent on UV light is advantageous here.
  • Suitable photoinitiators are e.g. aromatic ketone compounds such as benzophenones, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michlers).
  • Ketone anthrone and halogenated benzophenones.
  • acylphosphine oxides such as. B. 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide, phenyl-glyoxylic acid ester, anthraquinone and its derivatives, benzil ketals and hydroxyalkylphenones. Mixtures of these compounds can also be used.
  • the coating compositions comprising the polymers (A) according to the invention can be applied in known ways, for example by brushing, pouring, knife coating, spraying, spraying, spinning, rolling or dipping.
  • the paint film can be dried at room temperature or elevated temperature, but also by baking at up to 200 ° C. Drying is preferably carried out at room temperature or only slightly above.
  • UV-curing constituents in the disper- contain ions the drying process can also include exposure to UV light.
  • the present invention also relates to substrates coated with coating compositions comprising the water-dilutable polymers (A) containing urethane groups.
  • the polyester resin thus obtained has a viscosity (determined as the flow time of a 75% strength solution of the polyester in xylene in a DLN 4 beaker at 23 ° C.) of 105 seconds and an OH number of 175 mg KOH / g.
  • 607 g of the polyester described above are placed in a 41-reaction vessel with a cooling, heating and stirring device and together with 58 g of dimethylol propionic acid, 150 g of a linear polyether diol with an OH number of 75 mg KOH / g, which is characterized by ring-opening Polymerization of 3,4-epoxy-1-butene with 3,4-dihydroxy-1-butene was prepared as a starter, 75 g of N-methylpyrrolidone, 75 g
  • IPDI l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
  • the linear polyether diol is obtained by adding a solution of 37 g (0.42 mol) of 3,4-di-hydroxy-1-butene, 600 g of 3,4-epoxy-1-butene and 1 ml of trimethyl orthobenzoate to 50 g of a DMC Catalyst according to EP-A 0 700 049, dissolved in 5 ml of toluene, at 120 ° C.
  • the rate of addition was chosen so that the
  • Reaction temperature does not exceed 155 ° C.
  • the reaction temperature will then kept at 150 ° C until the 3,4-epoxy-1-butene has completely reacted.
  • the aqueous urethane-modified polyester resin obtained in this way has an acid number of 26 mg KOH / g, an average particle size of 150 nm and a solids content of 45.6%.
  • 150 g of a linear polyether diol with an OH number of 73 mg KOH / g and a number average molecular weight of 1300, which by ring-opening polymerization of a mixture of 3,4-epoxy-1-butene and propylene oxide (molar ratio 50:50) with tripropylene glycol as Starter was prepared, 150 g of N-methylpyrrolidone and 22 g of triethylamine were heated to 80 ° C. and homogenized for 30 minutes. 185 g of l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) are then added with vigorous stirring, and the mixture is heated to 100 ° C. (using the exothermic nature of the reaction) and the mixture is kept as long this temperature until no more NCO groups can be determined.
  • IPDI l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
  • the linear polyether diol was prepared according to Example 1, except that the reaction of the catalyst, starter, propylene oxide and 3,4-epoxy-1-butene was carried out in an autoclave.
  • the aqueous urethane-modified polyester resin thus obtained has an acid number of 26 mg KOH / g, an average particle size of 170 nm and a solids content of 45.8%.
  • the linear polyether diol was prepared according to Example 1, except that the reaction of the catalyst, starter, propylene oxide and 3,4-epoxy-1-butene was carried out in an autoclave.
  • the aqueous urethane-modified polyester resin thus obtained has an acid number of 27 mg KOH / g, an average. Particle size of 200 nm and a solids content of 46.1%.
  • Example 1 602 g of the polyester from Example 1 are placed in a 41 reaction vessel with a cooling, heating and stirring device and together with 58 g of dimethylolpropionic acid, 150 g of the linear polyether diol of OH number 75 mg used in Example 1
  • the aqueous urethane-modified polyester resin thus obtained has an acid number of
  • the polyurethane dispersion produced in this way has an acid number (100%) of 25 mg KOH / g, an average particle size of 42 nm and a solids content of 37.2%.
  • 1126 g of the polyester precursor from Example 1 are placed in a 41 reaction vessel with a cooling, heating and stirring device and heated to 80 ° C. together with 87.5 g of dimethylolpropionic acid, 244 g of N-methylpyrrolidone and 33 g of triethylamine and 30 homogenized min. Then 286.5 g of l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) are added with vigorous stirring, the mixture is heated to 100 ° C. (using the exothermic nature of the reaction) and the mixture is kept as long as possible this temperature until no more NCO groups can be determined.
  • IPDI l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
  • aqueous urethane-modified polyester resin obtained has an acid number of 27 mg KOH / g and a solids content of 45%.
  • the dispersions of Examples 1-5 and Comparative Example 6 are ® with Octasoligen Co 7 aqua (cobalt siccative, 50% in water, Borchers GmbH) corresponding to a concentration of 0.06% Co metal on the solid resin (binder 100% ig), diluted with water to a run-out time of approx. 30 seconds (DIN 4 cup, 23 ° C) and applied with a squeegee to degreased glass plates or degreased steel sheets (dry film thickness 50 ⁇ m). After drying at room temperature, trouble-free paint films with good results are obtained
  • Desmodur ® W (product from Bayer AG, Leverkusen) can be added quickly. The temperature is kept at 80 ° C. before it is reduced from 4.4% to 70 ° C. when the NCO content of the prepolymer is reached and 19.6 g of triethylamine are added. After 10 minutes, 500 g of the prepolymer are placed in a second, equipped with a stirrer and filled with 670 g of water (20 ° C.) within 5 minutes
  • Piston transferred After 10 minutes of intensive stirring, within 5 minutes. a mixture of 5.2 g of hydrazine hydrate, 8.4 g of ethylenediamine and 74.4 g of water was added. The mixture is then stirred at 40 ° C. until no more NCO can be detected in the dispersion.
  • the polyurethane dispersion has an average particle size of 69 nm and a solids content of 35.3%.
  • the polyurethane dispersion has an average particle size of 70 nm and a solids content of 35.3%.
  • 0.2% Byk ® 346 (substrate wetting additive, Byk), 0.5% Byk ® 381 (leveling additive, Byk), 0.2% TS ® 100 (matting agent, Degussa,), 2.0% Aquamat ® 263 (wax / slip additive, from Byk) and 2.0% Acrysol ® RM 8 (5%, thickener, from Rohm & Haas) are knife-coated onto a glass plate with a doctor blade with a gap width of 200 ⁇ m and 7d dried at room temperature. You get a clear, shiny film with a pendulum hardness (drying 14 days at RT) of 80 seconds.
  • 339 g of polytetramethylene ether glycols with an OH number of 56 mg KOH / g, 248 g of the polyester oligomer precursor, 70 g of dimethylolpropionic acid, 34 g of 1,6-hexanediol and 34 g of N-methylpyrrolidone are heated to 70 ° C. and stirred until a clear solution is obtained.
  • 516 g of Desmodur ® W (Bayer AG, Leverkusen) are added and heated to 100 ° C. The mixture is stirred at this temperature until the NCO content is 4.1%.
  • the mixture is then cooled to 70 ° C. and 52.6 g of triethylamine are added.
  • Example 11 (according to the invention): UV-curing and oxidatively drying dispersion
  • the viscosity of the dispersion was 24.7 s flow time in DLN 4 beaker, the pH was determined to be 8.6, and the mean particle size after laser correlation spectroscopy measurement (Zetasizer 1000, Malvern Instruments, Malvern, UK) was 60.0 nm.
  • Irgacure ® 500 photoinitiator, Fa. Ciba, Lampertheim, DE
  • the dispersion is drawn onto a glass plate using a 150 ⁇ m bone doctor.
  • the coated glass plate is stored for 40 minutes at room temperature.
  • a clear, transparent and dry to the touch film is formed.
  • the coated glass plate is then moved at a speed of 5 m / min under a medium pressure mercury lamp (power 80 W / cm lamp length).
  • the film UV-cured in this way, shows a König pendulum hardness of 59 minutes 30 minutes after irradiation.
  • the pendulum hardness increases to 82 within 36 hours of storage at room temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne des polyuréthanes diluables dans l'eau, qui présentent des unités structurales dérivées de 3,4-époxy-butène, ainsi que des dispersions aqueuses contenant lesdits polyuréthanes. L'invention concerne également un procédé permettant de produire et d'utiliser lesdits polyuréthanes comme agents de revêtement aqueux à séchage par oxydation et/ou à réticulation par U.V.
EP03739501A 2002-02-18 2003-02-18 Agents de revetement aqueux a base de epoxybutene-polyethers Withdrawn EP1485438A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE2002106565 DE10206565A1 (de) 2002-02-18 2002-02-18 Wässrige Beschichtungsmittel auf Basis von Epoxybuten-Polyethern
DE10206565 2002-02-18
US10/368,194 US6696531B1 (en) 2003-02-18 2003-02-18 Process for preparing a polymer from 3,4-epoxy-1-butene
US368194 2003-02-18
PCT/EP2003/001613 WO2003068879A1 (fr) 2002-02-18 2003-02-18 Agents de revetement aqueux a base de epoxybutene-polyethers

Publications (1)

Publication Number Publication Date
EP1485438A1 true EP1485438A1 (fr) 2004-12-15

Family

ID=27735685

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03739501A Withdrawn EP1485438A1 (fr) 2002-02-18 2003-02-18 Agents de revetement aqueux a base de epoxybutene-polyethers

Country Status (7)

Country Link
EP (1) EP1485438A1 (fr)
JP (1) JP2005517761A (fr)
CN (1) CN1293119C (fr)
AU (1) AU2003210298A1 (fr)
CA (1) CA2476476A1 (fr)
HK (1) HK1081216A1 (fr)
WO (1) WO2003068879A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1840150B1 (fr) * 2006-03-31 2010-03-31 Sony Deutschland Gmbh Procede pour preparer de poly(ethylene oxyde - alkylene oxyde) copolymeres
DE102006054237A1 (de) * 2006-11-17 2008-05-21 Bayer Materialscience Ag Polyurethan-modifizierte Alkydharzdispersionen
DE102010009896A1 (de) * 2010-03-02 2011-09-08 Bayer Materialscience Ag Wässrige Polyurethandispersionen
US10907005B2 (en) 2012-09-25 2021-02-02 Battelle Memorial Institute Aqueous prepolymer dispersions
CA2951904A1 (fr) 2014-06-11 2015-12-17 Battelle Memorial Institute Compositions de polyol de bio-huile alcoxyle
CN115028832B (zh) * 2022-04-12 2023-08-01 浙江科技学院 一种水性聚天门冬氨酸酯树脂的制备方法及水性pae聚脲涂料

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3991036A (en) * 1973-02-28 1976-11-09 Uniroyal Inc. Preparation of polyurethane using 1,2,3,4,4a,5,7,7a-Octahydrothieno[3,4-b]py
CN87102902A (zh) * 1987-04-17 1988-10-26 水电部华东勘测设计院 亲水性聚氨酯涂料及制备方法
WO2000066649A1 (fr) * 1999-05-04 2000-11-09 Eastman Chemical Company Compositions de revetement a base d'alcool de polyether preparees a partir de 3,4-epoxy-1-butene.
DE19930961A1 (de) * 1999-07-05 2001-01-11 Bayer Ag Polyurethan-Dispersionen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03068879A1 *

Also Published As

Publication number Publication date
HK1081216A1 (en) 2006-05-12
CN1646647A (zh) 2005-07-27
CA2476476A1 (fr) 2003-08-21
JP2005517761A (ja) 2005-06-16
AU2003210298A1 (en) 2003-09-04
CN1293119C (zh) 2007-01-03
WO2003068879A1 (fr) 2003-08-21

Similar Documents

Publication Publication Date Title
EP2218739B2 (fr) Systèmes de revêtement aqueux à base d'acrylate d'uréthane physique sec
EP2513178B1 (fr) Dispersions de polyuréthane-acrylate peu visqueuses
EP2396356B1 (fr) Systèmes de revêtement aqueux à base d'acrylates d'uréthane physiquement siccatifs
EP2316867B1 (fr) Dispersions de polyuréthane aqueuses sans étain
EP0355682B1 (fr) Utilisation de résines de polyuréthanes pour compositions aqueuses de charges
EP2113523B1 (fr) Systèmes de revêtement non agglomérants et durcissables par rayonnement à base de dispersions de polyuréthane hautement moléculaires aqueuses
EP2178939B1 (fr) Procédé de production de systèmes de revêtements durs à base de dispersions aqueuses de polyuréthane
EP1717257B1 (fr) Dispersions de polyuréthanes exemptes de N-méthyl-pyrrolidone à base de l'acide diméthylolpropionique
EP1350824B1 (fr) Dispersions de polyuréthanes à base de dialcanolamides d'acides gras
EP0436941B1 (fr) Composition aqueuse de revêtement, sa préparation et son utilisation
EP0654052B1 (fr) Agent de recouvrement diluable dans l'eau, a base de polyol et de polyisocyanate, procede de fabrication et utilisation
EP3580249B1 (fr) Composition de revêtement aqueux
JP4567679B2 (ja) 水希釈性ポリウレタン分散液
EP1599518A1 (fr) Agent de revetement aqueux a base de dispersions hybrides pur-pac
EP1311571B1 (fr) Dispersions aqueuses de polyisocyanates bloquees avec pyrazoles et revetements preparees de celle
AT500555B1 (de) Selbstvernetzende wässrige polyurethandispersionen
DE10206565A1 (de) Wässrige Beschichtungsmittel auf Basis von Epoxybuten-Polyethern
EP0562436B1 (fr) Composition de revêtement diluable à deux composants, procédé de sa préparation et son utilisation
EP1485438A1 (fr) Agents de revetement aqueux a base de epoxybutene-polyethers
EP3985043A1 (fr) Procédé de fabrication de dispersions aqueuses de polyuréthane à l'aide des acides aromatiques tri- ou tétracarboniques comme agents hydrophilisants

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040920

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO

17Q First examination report despatched

Effective date: 20070410

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RBV Designated contracting states (corrected)

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20080411