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    • 专利摘要:
    polymer, use of the same, basecoat pigmented aqueous material, method for producing a multi-layer paint system and multi-layer paint system. The present invention relates to a polymer which can be prepared by reacting (a) dimer fatty acids with (b) at least one polyether of general structural formula (i), wherein r is a radial of C3 to C6 alkylene and n, therefore, it is selected in such a way that said polyether has an average molecular weight of 450 to 2200 g/mol, components (a) and (b) are used in a molar ratio of 0.7/2.3 to 1.3 /1.7 and the resulting polymer has an average molecular weight of 1500 to 5000 glmol and an acid number less than 10 mg koh/g. the invention further relates to a pigmented aqueous basecoat material comprising such polymer and the use of said polymer in pigmented aqueous basecoat materials. it further concerns a method for producing multi-layer paint systems and also multi-layer paint systems that can be produced by means of said method, furthermore, the present invention concerns the repair of imperfections in multi-layer paint systems.
    公开号:BR112014031698B1
    申请号:R112014031698-8
    申请日:2013-08-27
    公开日:2021-06-29
    发明作者:Peter Hoffmann；Bernhard Steinmetz；Jorn Lavalaye；Hardy Reuter
    申请人:Basf Coatings Gmbh；
    IPC主号:
    专利说明:

    [01] The invention concerns a new polymer. It further concerns a pigmented aqueous basecoat material comprising this polymer and the use of said polymer in pigmented aqueous basecoat materials. Additionally, it concerns a method for producing multi-layer paint systems and also multi-layer paint systems that can be produced by means of said method. Furthermore, the present invention concerns the correction of areas with imperfections in multilayer paint systems.
    [02] The state of the art has disclosed a set of methods to produce effective and/or multilayer color painting systems. From the state of the art (according to, for example, German patent application DE 199 48 004 A1, page 17, line 37, page 19, line 22, or German patent DE 100 43 405 C1, column 3, paragraph [0018 ], and column 8, paragraph [0052], up to column 9, paragraph [0057], together with column 6, paragraph [0039], up to column 8, paragraph [0050]), the method to be followed is known, the which comprises: (1) applying an aqueous pigmented basecoat material to a substrate; (2) forming a polymer film from the coating material applied in stage (1); (3) apply a clearcoat material to the resulting basecoat film and subsequently (4) cure the basecoat film together with the clearcoat film.
    [03] This method is widely practiced, for example, both in the original finish (OEM) of motor vehicles and in the painting of metal and plastic parts for installation on or in the vehicle. In the course of these operations, under certain conditions, problems relating to adhesion occur, particularly between basecoat and clearcoat. In addition, the method is also used for refinishing motor vehicle bodies. This is a reference not only for OEM motor vehicle refinishing, but also for motor vehicle refinishing, which takes place, for example, in a workshop. A particular problem here is the adhesion between the original finish and the basecoat that is used for refinishing.
    [04] Therefore, an object of the present invention was to provide a polymer that can be used to produce coatings that do not have the prior art disadvantages identified above. This concerns an improvement in adhesion both in painting metallic and plastic substrates and in automotive refinishing. An important factor in painting metallic and plastic substrates as well as in the adhesion of the basecoat to the substrate is the adhesion between the basecoat and clearcoat. In the case of automotive refinishing, an important factor, along with the adhesion between basecoat and clearcoat, is the adhesion between basecoat and original finish. This should be improved especially for use in automotive OEM refinishing.
    [05] The problems with adhesion are especially highlighted when the coated substrates are exposed to the elements of the weather. The object of the present invention was, therefore, also to provide coatings that still have outstanding adhesion properties, even after being exposed to the elements of time.
    [06] In the case of exposure due to inclement weather, poor adhesion is also manifested, particularly in an incidence of blisters and swelling. Therefore, a further object of the present invention was to prevent or reduce the incidence of blisters and swelling.
    [07] This object was achieved by means of a polymer that can be prepared by reacting (a) dimer fatty acids with (b) at least one polyether of general structure formula (I)
    wherein R is a C3 to C6 alkylene radical and n is therefore selected such that said polymer has an average molecular weight of 450 to 2200 g/mol, components (a) and (b) are employed in a proportion molar from 0.7/2.3 to 1.3/1.7 and the resulting polymer has an average molecular weight of 1500 to 5000 g/mol and an acid number < 10 mg KOH/g.
    [08] The condition by which n is selected such that said polymer has an average molecular weight of 450 to 2200 g/mol can be illustrated as follows: where, for example, R is a tetramethylene radical and the average molecular weight should be 1000 g/mol, n is, on average, between 13 and 14. Component (a):
    [09] Dimeric fatty acids are mixtures prepared by oligomerization of unsaturated fatty acids. Starting materials used can be C12 to C22 unsaturated fatty acids.
    [10] In the context of the present invention, the use of C18 fatty acids is preferred. Particular preference is given to the use of C18 fatty acids and very particular preference to the use of linolenic, linoleic and/or oleic acid.
    [11] Depending on the reaction regime, the oligomerization referred to above produces a mixture comprising mainly molecules, but also trimeric as well as monomeric molecules and other by-products. Purification is usually by distillation. Commercial dimeric fatty acids generally contain at least 80% by weight of dimeric molecules, up to 19% by weight of trimeric molecules and no more than 1% by weight of monomeric molecules and other by-products.
    [12] In the context of the present invention it is preferred to use dimeric fatty acids consisting of an extension of at least 90% by weight of dimeric molecules, less than 5% by weight of trimeric molecules and less than 5% by weight of molecules monomeric and other by-products. It is particularly preferred to use dimeric fatty acids which consist of a range of 95% to 98% by weight of dimeric molecules, less than 5% by weight of trimeric molecules and less than 1% by weight of monomeric molecules and other by-products. Equally and particularly preferred is the use of dimeric fatty acids which consist of an extension of at least 98% by weight of dimeric molecules, less than 1.5% by weight of trimeric molecules and less than 0.5% by weight of monomeric molecules and other by-products.
    [13] Depending on the reaction regime, dimeric fatty acids include both aromatic and aliphatic molecular fragments. Aliphatic molecular fragments can be further divided into cyclic and linear fragments, which in turn can be saturated or unsaturated. By means of hydrogenation it is possible to convert the unsaturated aliphatic molecular fragments into the corresponding saturated aliphatic molecular fragments.
    [14] In the context of the present invention, it is preferable to use those dimeric fatty acids that almost exclusively comprise saturated aliphatic molecular fragments and thus preferably have an iodine number < 10 g/100 g.
    [15] Particularly preferred dimeric fatty acids are those consisting of an extension of at least 98% by weight of dimeric molecules, less than 1.5% by weight of trimeric molecules and less than 0.5% by weight of molecules monomeric and other by-products and which additionally have an iodine number < 10 g/100 g.
    [16] Dimeric fatty acids whose use is especially preferred include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976 and Radiacid 097, from Oleon, Pripol 1006, Pripol 1009, Pripol 1012 and Pripol 1013, from Unichema, Empol 1009 , Empol 1061 and Empol 1062, from Cognis and Unidyme 10 and Unidyme TI, from Arizona Chemical. Component (b):
    [17] As component (b) at least one polyether of general structural formula (I) is used
    wherein R is a C3 to C6 alkylene radical. The index n must be selected, in each case, in such a way that said polyether has an average molecular weight of 450 to 2200 g/mol. More preferably, it has an average molecular weight of from 700 to 1400 g/mol and most preferably from 800 to 1200 g/mol. Average molecular weight is measured by permeation chromatography facing a polymethyl methacrylate standard; eluent: tetrahydrofuran.
    [18] In the polyether for use according to the invention all n radicals R can be the same. Similarly, however, it is also possible that different types of R radicals are present. All R radicals are preferably the same.
    [19] R is preferably a C3 to C4 alkylene radical. More preferably, it is an isopropylene radical or a tetramethylene radical.
    [20] With very particular preference, the polyether for use according to the invention is polypropylene glycol or polytetrahydrofuran.
    [21] The preparation of the polymer of the invention has no peculiarities. Esterification is usually accomplished by means of a water separator. In this case, components (a) and (b) are used in a molar ratio from 0.7/2.3 to 1.3/1.7, preferably from 0.8/2.2 to 1.2/1, 8 and most preferably 0.9/2.1 to 1.1/1.9. The reaction is discontinued when the polymer of the invention has an acid number of < 10 mg KOH/g. Preferably, it has an acid number of < 7.5 mg KOH/G and most preferably < 5 mg KOH/g. The acid number here is determined by means of DIN 53402.
    [22] The resulting polymer has an average molecular weight of 1500 to 5000 g/mol, preferably 2000 to 4500 g/mol and most preferably 3000 to 4000 g/mol. Average molecular weight is measured by gel permeation chromatography facing a polymethyl methacrylate standard; eluent: tetrahydrofuran.
    [23] The water solubility of the polymers of the invention is low. If they are used in aqueous systems, they accumulate at the interfaces, due to their incompatibility, and are therefore able to contribute to an improvement in adhesion to adjacent layers.
    [24] If an average molecular weight of 5000 g/mol is exceeded, then the solubility of the polymers of the invention in aqueous systems becomes so low that they tend to crystallize and may experience precipitation. If the average molecular weight falls below 1500 g/mol, then the water solubility of said polymer is increased to such an extent that it is no longer able to accumulate in sufficient concentration at the interfaces. In that case, an improvement in adherence can no longer be achieved.
    [25] Particularly preferred embodiments are specified below: a) in a particularly preferred embodiment of the polymer of the invention, the dimeric fatty acid is prepared from linolenic, linoleic and/or oleic acid, consisting of an extension of at least 98% by weight of dimeric molecules, less than 1.5% by weight of trimeric molecules and less than 0.5% by weight of monomeric molecules and other by-products and has an iodine number of < 10 g/100 g. b) in another particularly preferred embodiment of the polymer of the invention, the polyether for use according to the invention is polypropylene glycol or polytetrahydrofuran and additionally has an average molecular weight of from 800 to 1200 g/mol. c) in another particularly preferred embodiment of the polymer of the invention, components (a) and (b) are used in a molar ratio of from 0.9/2.1 to 1.1/1.9. d) in another particularly preferred embodiment of the polymer of the invention, it has an acid number of < 5 mg KOH/g. e) in another particularly preferred embodiment of the polymer of the invention, it has an average molecular weight of 3000 to 4000 g/mol.
    [26] In an especially preferred embodiment of the polymer of the invention, all the characteristics indicated in a) to e) are carried out in combination.
    [27] The present invention further relates to a pigmented aqueous basecoat material comprising at least one polymer of the invention.
    [28] A basecoat material is an intermediate color imparting coating material that is used in motor vehicle finishing and general industrial coating. It is usually applied to a metal or plastic substrate that has been penetrated by a primer or surface primer, and occasionally it is even applied directly to the plastic substrate. Used substrates may also include existing finishers, which may also need to be pre-treated (by sandblasting, for example). It is now quite usual for more than one basecoat film to be applied. In such a case, therefore, a first basecoat film constitutes the substrate for a second. In order to protect a basecoat film against particular weather-related effects, at least one additional clearcoat film is applied over it.
    [29] The sum total of percentage fractions by weight, based on the total weight of the pigmented aqueous basecoat material, of all polymers according to the invention is preferably 0.1% to 30% by weight, most preferably 1% to 20% by weight and most preferably from 1.5% to 15% by weight or even 2% to 12% by weight.
    [30] Where the amount of polymer of the invention is below 0.1% by weight, it may be that no improvement in adhesion is achieved. Where the amount is more than 30% by weight, there can be disadvantages under certain circumstances, such as an incompatibility of said polymer in the basecoat material, for example. Such incompatibility can be manifested, for example, in uneven flow and, therefore, in flotation or sedimentation.
    [31] As already described above, the polymer of the invention has low solubility in aqueous systems. Therefore, it is preferably used directly in the preparation of the pigmented aqueous basecoat material and not just added, after preparation, to another complete basecoat material otherwise.
    [32] In a preferred embodiment, the sum total of the percentage fractions by weight of all polymers according to the invention is 0.1% to 30% by weight, based on the total weight of the pigmented aqueous basecoat material. Where preferred embodiments of the polymers of the invention are used, the sum total of the percentage fractions by weight of all preferred embodiments of the polymers of the invention is preferably 0.1% to 30% by weight, based on the total weight of the pigmented aqueous material. base coat. With particular preference, the pigmented aqueous basecoat material exclusively comprises, as polymers of the invention, preferred embodiments of the polymers of the invention.
    [33] In a preferred embodiment, the sum total of the percentage fractions by weight of all polymers according to the invention is from 1% to 20% by weight, based on the total weight of the pigmented aqueous basecoat material. Where preferred embodiments of the polymers of the invention are used, the sum total of the percentage fractions by weight of all preferred embodiments of the polymers of the invention is preferably from about 1% to 20% by weight, based on the total weight of the pigmented aqueous material. base coat. With particular preference, the pigmented aqueous basecoat material exclusively comprises, as polymers of the invention, preferred embodiments of the polymers of the invention.
    [34] In an especially preferred embodiment, the sum total of the percentage fractions by weight of all polymers according to the invention is from 1.5% to 15% by weight, based on the total weight of the pigmented aqueous basecoat material. Where preferred embodiments of the polymers of the invention are used, the sum total of the percentage fractions by weight of all preferred embodiments of the polymers of the invention is preferably from about 1.5% to 15% by weight, based on the total weight of the material. pigmented aqueous base coat. With particular preference, the pigmented aqueous basecoat material exclusively comprises, as polymers of the invention, preferred embodiments of the polymers of the invention.
    [35] In a special and similarly preferred embodiment, the sum total of the percentage fractions by weight of all polymers according to the invention is from 2% to 12% by weight, based on the total weight of the pigmented aqueous basecoat material . Where preferred embodiments of the polymers of the invention are used, the sum total of the percentage fractions by weight of all preferred embodiments of the polymers of the invention is preferably from about 2% to 12% by weight, based on the total weight of the pigmented aqueous material. base coat. With particular preference, the pigmented aqueous basecoat material exclusively comprises, as polymers of the invention, preferred embodiments of the polymers of the invention.
    [36] Examples of preferred embodiments of the polymers of the invention in this context include the following particularly preferred embodiments: a) In a particularly preferred embodiment of the polymer of the invention, the dimeric fatty acid is prepared from linolenic, linoleic and/or oleic acid , consists of an extension of at least 98% by weight of dimeric molecules, less than 1.5% by weight of trimeric molecules and less than 0.5% by weight of monomeric molecules and other by-products and has an iodine number. of < 10 g/100 g. b) in another particularly preferred embodiment of the polymer of the invention, the polyether for use according to the invention is polypropylene glycol or polytetrahydrofuran and additionally has an average molecular weight of from 800 to 1200 g/mol. c) in another particularly preferred embodiment of the polymer of the invention, components (a) and (b) are used in a molar ratio of from 0.9/2.1 to 1.1/1.9. d) in another particularly preferred embodiment of the polymer of the invention, it has an acid number of < 5 mg KOH/g. e) in another particularly preferred embodiment of the polymer of the invention, it has an average molecular weight of 3000 to 4000 g/mol.
    [37] As a further example of embodiments of the polymers of the invention which are preferred in this context, mention may be made of that embodiment in which all of the characteristics indicated a) to e) are performed in combination.
    [38] The basecoat materials used in accordance with the invention comprise color and/or effect pigments. Such color pigments and effect pigments are known to persons skilled in the art and are described, for example, in Rompp-Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 176 and 451. The fraction of pigments it may be, for example, in the range of from 1% to 40% by weight, preferably from 2% to 30% by weight, more preferably from 3% to 25% by weight, based on the total weight of the pigmented aqueous coating material base.
    [39] For the purposes of the present invention it is preferred to use basecoat materials which, as binders, comprise physically, thermally or both thermally and actinic radiation curable binders.
    [40] In addition to the polymer of the invention, the pigmented aqueous basecoat materials of the invention particularly preferably comprise at least one polyurethane resin. Such coating materials comprising polyurethane resin may also typically be cured physically, thermally or either thermally or by actinic radiation.
    [41] In the context of the present invention, the term "physical cure" denotes the formation of a film through solvent release from polymer solutions or polymer dispersions. Normally uncrosslinked agents are needed for this purpose.
    [42] In the context of the present invention, the term "thermal cure" denotes heat-initiated crosslinking of a coating film, where in the nearby coating material either a separate crosslinking agent or even self-crosslinking binders are employed. The crosslinking agent comprises reactive functional groups which are complementary to the reactive functional groups present in the linkers. This is commonly referred to by those skilled in the art as external crosslinking. Where complementary reactive functional groups or self-reactive functional groups, that is, groups that react with groups of the same type, are already present in the binding molecules, the ligands are self-crosslinked. Examples of suitable complementary reactive functional groups and self-reactive functional groups are known from German patent application DE 199 30 665 A1, page 7, line 28, page 9, line 24.
    [43] In the context of the present invention, actinic radiation means electromagnetic radiation, such as near infrared (NIR), UV radiation, more particularly UV radiation, and particular radiation, such as electron radiation. Cure using UV radiation is usually initiated by radical or cationic photoinitiators.
    [44] Where thermal curing and actinic light curing are employed together, the term “double cure” is also used.
    [45] In the present invention, preferred basecoat materials are those that are physically curable and those that are curable thermally or both thermally and also by actinic radiation, in other words, by "double cure".
    [46] Preferred pigmented aqueous basecoat materials are those which comprise a polyurethane resin binder and, as a crosslinking agent, an amino resin or a blocked or unblocked polyisocyanates, preferably an amino resin. Among the amino resins, melamine resins are preferred.
    [47] The polyurethane resin preferably present can be ionically and/or non-ionically stabilized, hence hydrophilically. In preferred embodiments of the present invention, the polyurethane resin is ionically stabilized by hydrophilicity. Preferred polyurethane resins are linear or contain branching. Particular preference is given to a polyurethane resin in which olefinically unsaturated monomers have been polymerized. The polyurethane resin (A) here can be present in addition to the polymer being originated from the polymerization of the olefinically unsaturated monomers, without those monomers being covalently bonded to each other. However, it is also possible that the polyurethane resin (A) is covalently bonded to the polymer originated from the polymerization of the olefinically unsaturated monomers. Olefinically unsaturated monomers are monomers preferably containing acrylate and/or methacrylate groups. It is also preferred that monomers containing acrylate and/or methacrylate groups are used in combination with additional olefinically unsaturated components which do not contain any acrylate or methacrylate groups. Olefinically unsaturated monomers bonded to polyurethane resin (A) are more preferred monomers containing acrylate groups or methacrylate groups, producing polyurethane (meth)acrylates. Most particularly preferably, the polyurethane resin is a polyurethane (meth)acrylate. The polyurethane resin preferably present is physically or thermally curable, or curable thermally and by actinic radiation. More particularly, it is curable thermally or both thermally and by actinic radiation. The polyurethane resin particularly preferably comprises reactive functional groups, by means of which external crosslinking is possible.
    [48] Suitable saturated or unsaturated polyurethane resins are described, for example, in German patent application DE 199 14 896 A1, column 1, lines 29 to 49, and column 4, line 23 to column 11, line 5; German patent application DE 199 48 004 A1, page 4, line 19, page 13, line 48; European patent application EP 0 634 431 A1, page 3, line 38, page 8, line 9; or - international patent application WO 92/15405, page 2, line 35, page 10, line 32.
    [49] For the preparation of the polyurethane resin, it is preferred to make use of the aliphatic, cycloaliphatic, aliphatic, cycloaliphatic, aromatic, aliphatic-aromatic and/or cycloaliphatic-aromatic polyisocyanates known to the person skilled in the art.
    [50] As the alcohol component to prepare the polyurethane resins, it is preferred to use the relatively high molecular weight, saturated and unsaturated and low molecular weight polyols and also, optionally, monoalcohols in smaller amounts, which are known to the skilled person. in technique. Low molecular weight polyols are used more particularly diols and, in smaller amounts, triols for the purpose of introducing branching. Examples of suitable polyols of relatively high molecular weight are saturated or olefinically unsaturated polyester polyols and/or polyether polyols. Relatively high molecular weight polyols used are, more particularly, polyester polyols, especially those with a number average molecular weight of 400 to 5000 g/mol (measured by gel permeation chromatography against a standard of polymethyl methacrylate, with tetra -hydrofuran as eluent).
    [51] For hydrophilic stabilization and/or to increase dispersibility in aqueous media, the preferably present polyurethane resin may comprise certain ionic groups and/or groups that can be converted to ionic groups (potentially ionic groups). Such polyurethane resins are referred to in the context of the present invention as ionically stabilized hydrophilic polyurethane resins. Also present may be non-ionic hydrophilic modifying groups. Preference is given, however, to the hydrophilic ionically stabilized polyurethanes. More specifically the modifying groups are - functional groups that can be converted to cations by means of neutralizing agents and/or quartering agents and/or cationic groups (cationic modification) or - functional groups that can be converted to anions by means of agents of neutralizing and/or anionic groups (anionic modification), and/or - nonionic hydrophilic groups (nonionic modification).
    [52] As the person skilled in the art is aware, the functional groups for cationic modification are, for example, primary, secondary and/or tertiary amino groups, secondary sulfide groups and/or tertiary phosphine groups, tertiary amino groups and more particularly secondary sulfide groups (functional groups that can be converted to cationic groups by neutralizing agents and/or quaternizing agents). Also of note are the cationic groups prepared from the aforementioned functional groups using neutralizing agents and/or agents known to the person skilled in the art, such as the quaternary phosphonium groups of quaternary ammonium groups primary, secondary tertiary sulfonium groups, tertiary and/or quaternization, more particularly quaternary ammonium groups and tertiary sulfonium groups.
    [53] Functional groups for anionic modification are, as is known, for example, carboxylic, sulfonic and/or phosphonic acid groups, carboxylic acid groups (more particularly functional groups that can be converted to anionic groups by agents neutralizing) and also anionic groups prepared from the aforementioned functional groups using a neutralizing agent known to the person skilled in the art, such as carboxylate, sulfonate and/or phosphonate groups.
    [54] Functional groups for nonionic hydrophilic modification are preferably poly(oxyalkylene) groups, more particularly poly(oxyethylene) groups.
    [55] Ionically hydrophilic modifications can be introduced into the polyurethane resin by monomers that (potentially) comprise the ionic groups. Nonionic modifications are introduced, for example, through the incorporation of poly(ethylene) oxide polymers as side groups or end groups of the polyurethane molecules. Hydrophilic modifications are introduced, for example, through compounds comprising at least one group which is reactive with isocyanate groups, preferably at least one hydroxyl group. To introduce the ionic modification, it is possible to use monomers that, as well as the modifying groups, comprise at least one hydroxyl group. To introduce the non-ionic modifications, it is preferred to use the alkoxypoly(oxyalkylene) alcohols and/or polyetherdiols which are known to the person skilled in the art.
    [56] The polyurethane resin can preferably be a graft polymer. More particularly, it is a polyurethane resin grafted with olefinically unsaturated compounds, preferably olefinically unsaturated monomers. In this case, therefore, the polyurethane is grafted, for example, with side groups and/or side chains that are based on olefinically unsaturated monomers. The groups or chains in question are particularly more side chains based on poly(meth)acrylates. Poly(meth)acrylates in the context of the present invention are polymers or polymeric radicals which comprise acrylate-containing monomers and/or methacrylate groups, and preferably consist of acrylate-containing monomers and/or methacrylate groups. Poly(meth)acrylates based side chains are side chains that are constructed during graft polymerization with monomers that contain (meth)acrylate groups. In this case, during graft polymerization, preferably more than 50 mol%, more particularly more than 75 mol%, more particularly 100 mol% of monomers containing (meth)acrylate groups are used, based on the amount. total monomers used in graft polymerization.
    [57] The described side chains are introduced into the polymer preferably after preparing a dispersion of primary polyurethane resin. In this case, the polyurethane resin present in the primary dispersion may comprise pendant and/or terminal olefinically unsaturated groups, whereby graft polymerization with the olefinically unsaturated compounds then proceeds. The grafting polyurethane resin can therefore be an unsaturated polyurethane resin (A). Graft polymerization is that in case of a radical polymerization of olefinically unsaturated reagents. It is also possible, for example, for olefinically unsaturated compounds used for graft polymerization to comprise at least one hydroxyl group. In this case, it is also possible initially for the olefinically unsaturated compounds to be bound by these hydroxyl groups by reaction with free isocyanate groups of the polyurethane resin. This bonding occurs instead of or in addition to the reaction of radicals of olefinically unsaturated compounds with any pendant and/or terminal olefinically unsaturated groups that may be present in the polyurethane resin. This is again followed by graft polymerization by means of radical polymerization as described above above. In each case, polyurethane resins are obtained which are grafted with olefinically unsaturated compounds, preferably olefinically unsaturated monomers.
    [58] As olefin unsaturated compounds with which the polyurethane resin (A) is preferably grafted it is possible to use virtually all of the radical polymerizable, olefin unsaturated, and organic monomers that are available to the person skilled in the art for these purposes. A number of classes of preferred monomers can be cited as examples: - hydroxyalkyl esters of (meth)acrylate acid of other carboxylic acids unsaturated by alpha and beta ethylene, - alkyl acid (meth)acrylate esters and/or cycloalkyl esters of up to 20 carbon atoms in the alkyl radical, - ethylene unsaturated monomers comprising at least one acid group, more particularly and precisely a carboxyl group, such as (meth)acrylic acid, - vinyl esters of alpha-branched monocarboxylic acids and with 5 to 18 carbon atoms, - reaction products of (meth)acrylic acid with the glycidyl Estes of an alpha-branched monocarboxylic acid with 5 to 18 carbon atoms, - other ethylene unsaturated monomers, such as olefins (for example , ethylene), (meth)acrylamides, vinyl aromatic hydrocarbons (styrene, for example), and vinyl compounds such as vinyl chloride and/or vinyl ethers such as vinyl ethyl ethers.
    [59] Preference is given to the use of monomers containing (meth)acrylate groups, and thus the grafted side chains are poly(meth)acrylate-based side chains.
    [60] The pendant and/or terminal olefinically unsaturated groups into which the polyurethane resin, by means of graft polymerization with which the olefinically unsaturated compounds is able to proceed, are introduced into the polyurethane resin, preferably by means of certain monomers, which as well as an olefinically unsaturated group also comprise, for example, at least one group reactive with isocyanate groups. And hydroxyl groups, primary and secondary amino groups are also preferred. Hydroxyl groups are especially preferred.
    [61] Of course, the described monomers, whereby the pendant and/or terminal olefinically unsaturated groups can be introduced into the polyurethane resin can also be employed without the polyurethane resin being further grafted with then olefinically unsaturated compounds. Preferred, however, is the polyurethane resin to be grafted with olefinically unsaturated compounds.
    [62] The polyurethane resin preferably present can be a self-crosslinking and/or externally crosslinked binder. The polyurethane resin preferably comprises the reactive functional groups of external crosslinking, through which it is possible. In this case, the pigmented water-based coating material preferably comprises at least one crosslinking agent. More particularly, the externally crosslinking reactive functional groups through which it is possible are hydroxyl groups. For the purposes of the method of the invention, it is possible with particular advantage to use polyurethane-polyhydroxyl functional resins. This means that the polyurethane resin contains, on average, more than one hydroxyl group per molecule.
    [63] Polyurethane resin is prepared by the typical methods of polymer chemistry. This means, for example, the polymerization of polyisocyanates and polyols to polyurethanes, and the graft polymerization which follows thereafter, preferably with olefinically unsaturated compounds. These techniques are known to the person skilled in the art and can be adapted individually. Examples of preparation processes and reaction conditions are found in EP 0 521 928 B1, page 2, line 57 to page 8, line 16.
    [64] By film-forming solids is meant the non-volatile weight fraction of the basecoat material, excluding any pigments and fillers. Film-forming solids can be determined as follows: A sample of the pigmented water-based coating material (approximately 1 g) is mixed with 50 to 100 times the amount of tetrahydrofuran and then stirred for about 10 minutes. Insoluble pigments and any fillers are then removed by filtration, and the residue is washed with a little THF, after which the THF is removed from the resulting filtrate on a rotary evaporator. The filtered residue is dried at 120°C for two hours and the film-forming solids that result in this drying operation are weighed.
    [65] The polyurethane resin content is preferably between 5% and 80%, more preferably between 8% and 70%, and most preferably between 10% and 60% by weight, based in each case on the forming solids of basecoat material film.
    [66] The polyurethane resin preferably present preferably has a number average molecular weight of 200 to 30,000 g/mol, more preferably 2000 to 20,000 g/mol (measured by means of gel permeation chromatography against a standard of polymethyl methacrylate; tetrahydrofuran is used as eluent). Furthermore, it also has, for example, a hydroxyl number from 0 to 250 mg KOH / g, but more particularly from 20 to 150 mg KOH / g. The acid number of the polyurethane resin is preferably from 5 to 200 mg KOH/g, more particularly from 10 to 40 mg KOH/g. The hydroxyl number is determined in accordance with DIN / ISO 4629, the acid number in accordance with DIN 53402.
    [67] The pigmented water-based coating material to be used may further comprise at least one polyester, more particularly a polyester with a number average molecular weight of 400 to 5000 g/mol (measured by means of permeation chromatography of gel against a standard of polymethyl methacrylate; tetrahydrofuran is used as fluid). Corresponding polyesters are described in document DE 4009858, in column 6, line 53, column 7, line 61 and column 10, line 24 to column 13, line 3.
    [68] Preferably, in addition, a thickening agent is present. Suitable thickeners are inorganic thickeners from the group of phyllosilicates. In addition to the inorganic thickening agents, however, it is also possible to use one or more organic thickeners. These organic thickeners are preferably selected from the group consisting of (meth)acrylic to acid (meth)acrylate copolymer of thickeners such as, for example, the commercial product Viscalex HV30 (Ciba, BASF), and polyurethane thickeners, such as, for example, the commercial product DSX® 1550 by Cognis. The thickeners used are different from the binders used.
    [69] Suitable additives of the kind mentioned above are known, for example, from - German patent application DE 199 48 004 A1, page 14, line 4, page 17, line 5; - German patent DE 100 43 405 C1, column 5 - German patent DE 100 43 405 C1, column 5, paragraphs [0031] to [0033].
    [70] They are used in conventional and known amounts.
    [71] The content of the base coating materials used according to the invention can vary from solids according to the needs of each individual case. First and foremost the solids content is guided by the viscosity, which is required for application, more particularly spray application, and so can be adjusted by the person skilled in the art based on his general knowledge of the art, with the Appropriate assistance from one where a few rangefinder tests.
    [72] The solids content of the basecoat materials is preferably 5% to 70%, more preferably 8% to 60% and particularly preferably 12% to 55% by weight.
    [73] By solids content is meant the fraction by weight that remains as a residue after evaporation under defined conditions. In the present specification, the solids have been determined according to DIN EN ISO 3251. For this coating material it is evaporated at 130 °C for 60 minutes.
    [74] The basecoat materials used in accordance with the invention can be prepared by using mixing methods and mixing kits that are conventional and known for producing basecoat materials.
    [75] A further aspect of the present invention is a method of producing a multi-layer paint system by (1) applying a pigmented aqueous basecoat material to a substrate; (2) forming a polymer film from the coating material applied in stage (1); (3) apply a clearcoat material to the resulting basecoat film and subsequently (4) cure the basecoat film together with the clearcoat film, which is characterized by the fact that in stage (1) a pigmented aqueous basecoat material is used which comprises the polymer of the invention. All the details given above for the polymer of the invention and the pigmented aqueous coating material can also be applied to the use of the invention. This applies, additionally, not least, to all preferred, most preferred and most preferred features.
    [76] Said method is preferably used to produce multi-layer color paint systems, effect paint systems, and color and effect paint systems.
    [77] The pigmented aqueous basecoat material used in accordance with the invention is typically applied to metallic or plastic substrates that have been pretreated with a primer or primer-leveler segment. Said basecoat material can optionally be applied directly to the plastic substrate.
    [78] If a metallic substrate is to be coated, it is preferably coated with an electrodeposition coating before the primer or primer-surfacer is applied.
    [79] If a plastic substrate is to be coated, it is also preferred that pretreatment be applied before the primer or primer-surfacer. The techniques most commonly employed in such pretreatment are flaming, plasma treatment, and corona discharge. It is preferable to use flames.
    [80] The application of the water-based to pigmented coating material used according to the invention to a metallic substrate can take place in the film thicknesses that are customary within the automotive industry, in the range, for example, from 5 to 100 micrometers, preferably 5 to 60 micrometers. This is done by methods employing application spraying, such as, for example, compressed air spraying, airless spraying, high speed rotation, or electrostatic spray application (ESTA), alone or in conjunction with application by hot spray, such as hot air spray, for example.
    [81] After the pigmented water-based coating material has been applied, it can be dried using known techniques. For example, one-component basecoat materials can be flammable at room temperature for 1 to 60 minutes and subsequently optionally dried, preferably at slightly elevated temperatures of 30 to 80°C. Intermittent and drying for the purposes of the present invention means evaporation of organic solvents and/or water, whereby the coating material becomes drier, but is not yet cured, or there is still no formation of a coating film completely reticulated.
    [82] A typical commercial clear coating material is then similarly applied by common techniques, the film thicknesses being again situated within the usual ranges, such as 5 to 100 micrometers, for example.
    [83] After application of clear coating material, which can be flammable at room temperature for 1 to 60 minutes, for example, and optionally dries. The clear coat material is then cured together with the applied pigmented base coat material. Here, for example, crosslinking reactions take place, to produce a multilayer color and/or the effect of the ink system of the invention on a substrate. Curing preferably takes place thermally at temperatures from 60 to 200 °C. Thermally curing basecoat materials are preferably those which additionally comprise a polyurethane resin binder as a cross-linking agent and an amino resin or a blocked or unblocked polyisocyanate, preferably an amino resin. Among amine resins, melamine resins are preferred.
    [84] Coated plastic substrates are basically the same way as for metallic substrates. Here, however, curing generally takes place at much lower temperatures, from 30 to 90 °C. Therefore, it is preferable to use the two-component clear coating materials. Furthermore, it is preferred to use basecoat materials which comprise a polyurethane resin binder but without a crosslinking agent.
    [85] With the aid of the method of the invention, it is possible to coat metallic and non-metallic substrates, especially plastic substrates, preferably in car bodies or parts thereof.
    [86] The method of the invention can be used, in addition, for double coat finishing in OEM. This means that a substrate that has been coated using the method of the invention is painted a second time, again using the method of the invention.
    [87] The invention further relates to multi-layer paint systems, which are producible by the method described above. These multi-layer paint systems will be referred to below as multi-layer paint systems of the invention.
    [88] All the above-mentioned details relating to the polymer of the invention, to the pigmented water-based coating material, and to the method of the invention also apply correspondingly with respect to the said multi-layer paint system. This also applies not least with respect to all preferred, most preferred, most preferred features.
    [89] The multi-layer paint systems of the invention are preferably multi-layer color paint systems, effect paint systems and effect and color paint systems.
    [90] A further aspect of the invention concerns the method of the invention, where said substrate from stage (1) is a multilayer paint system that has areas of imperfection.
    [91] The method of the invention is accordingly suitable for repairing defects in areas of multi-layer paint systems. Areas of defect or film defects are, in general, and about disturbances in the coating, generally named according to their shape or appearance. The person skilled in the art is aware of a multitude of possible types of such film defects. They are described, for example, in Rompp-Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 235, "Filmfehler" ["Film defects"].
    [92] Multilayer paint systems produced using the method of the invention may also exhibit such defect areas. In a preferred embodiment of the method of the invention, therefore, the stage substrate (1) is a multi-layer paint system of the present invention which has defect areas.
    [93] These multi-layer paint systems are preferably produced on motor vehicle bodies or parts thereof, by means of the above-described method of the invention, as part of automotive OEM finishing. When these defect areas appear directly after OEM coating, they are remedied directly. Hence the term OEM car refinish is also used. Where only the small defect areas require remediation, a repair is carried out not for the whole body (double coating), but just for the "spot", as it is called. This operation is called "in-place repair". Particularly preferred, therefore, is the use of the method of the invention for repairing defects in areas of multi-layer paint systems of the present invention in OEM automotive refinish.
    [94] As the remedied area does not differ, in terms of color, from the rest of the original finish, it is preferred for the water-based coating material used in step (1) of the method of the invention to resolve the defect areas to be the same as used in the method of the invention to produce the multi-layer paint system of the present invention.
    [95] The indications given above regarding the polymer of the invention and as to pigmented water-based coating materials therefore also apply in relation to the use as discussed of the method of the invention for repairing defects in areas of a paint system multilayers. This applies in particular also to all the preferred, most preferred and most preferred features specified. It is further preferred that the multi-layer paint systems of the invention which are to be corrected are multi-color paint systems, paint effect systems and color and effect paint systems.
    [96] The above-described defect areas on the multi-layer paint system of the present invention can be remedied by the method of the invention described above. To this end, the surface of the multi-layer paint system that is to be corrected can initially be sanded. This is followed by applying the pigmented water-based coating material to the defect area in the original finish by air spraying. Following application of the pigmented water-based coating material, it can be dried by known techniques. For example, the basecoat material can be dried at room temperature for 1 to 60 minutes, and subsequently can be dried at slightly elevated temperatures, if desired, from 30 to 80°C. Intermittent and drying in the context of the present invention means the evaporation of organic solvents and/or water, but not in such a way as to completely cure the coating material. In the context of the present invention, it is preferable for the basecoat material to comprise a polyurethane resin binder as a cross-linking agent and an amino resin, preferably a melamine resin.
    [97] Subsequently, a commercial clear coating material is applied, through techniques that are similarly common. After application of the clear coating material, which can be flammable at room temperature for 1 to 60 minutes, for example, and optionally dries. The clear coat material is then cured together with the applied pigmented base coat material.
    [98] In the case of what is known as the low cooking temperature, curing preferably takes place at temperatures of 20 to 90 °C. Here it is preferable to use two-component clear coating materials. If, as described above, a polyurethane resin is used as the binding agent and yet an amino resin is used as the crosslinking agent, then at these temperatures there is only a low level of crosslinking of the basecoat film as a result. of the amino resin. In addition to its function as a curing agent, the amino resin in this case also serves for plasticization and is able to help pigment wetting. As well as amino resins, nonblocked isocyanates can also be used. Depending on the nature of the isocyanate used, they crosslink from temperatures as low as 20°C.
    [99] In the case of what is called high-temperature cooking, curing is preferably carried out at temperatures of 130-150 °C. Here, both one-component and two-component lacquer materials are used. If, as described above, a polyurethane resin is used as the binding agent and yet an amino resin is used as the cross-linking agent, then at these temperatures there is cross-linking in the basecoat film as a result of the amino resin.
    [100] Another aspect of the present invention is the use of the polymer of the invention in aqueous pigmented basecoat materials for the purpose of promoting adhesion. By this is meant adhesion promotion with respect to aqueous pigmented basecoat materials which do not contain any polymer of the invention.
    [101] The polymer of the invention can be used to promote coating adhesion to metallic and plastic substrates. It can also be used in car refinishing. By car refinishing is meant both OEM car refinishing and car refinishing of the type that takes place in a workshop, for example.
    [102] In that said aqueous pigmented basecoat material are used in the finishing of metallic and plastic substrates, the use of the polymer of the present invention more particularly results in an improved adhesion between the basecoat film and the clear coating film immediately adjacent to it. The polymer of the invention is therefore preferably used to promote adhesion between the basecoat film and clearcoat film in coating metallic and plastic substrates.
    [103] When said pigmented water-based coating materials are used in automotive refinish, the use of the polymer of the present invention more particularly results in an improvement in adhesion between the basecoat material and the original finish. The polymer of the invention is therefore also preferably used to promote adhesion between basecoat and original finish in automobile paint, more preferably in OEM automobile paint.
    [104] The adhesion problem is particularly noticeable when coated substrates are exposed to the elements. Such weathering conditions can be simulated by heat-humidity and storage conditions. This refers to the storage of coated substrates in a climatic chamber in accordance with the CH test conditions of DIN EN ISO 6270-2: 2005-09.
    [105] Consequently, the polymers of the invention are also used more particularly to improve adhesion after storage in heat and moisture. Adhesion is investigated preferably by means of a steam jet test according to test method A of DIN 55662: 2009-12.
    [106] If coated substrates are exposed to weathering, any poor adhesion manifests itself not least in the occurrence of blistering and swelling. The polymers of the invention are therefore also more particularly for reducing or preventing the occurrence of bubbles and swelling. The presence of such blisters and swelling can be assessed visually.
    [107] The invention is explained below using examples. Examples
    [108] The dimeric fatty acid used contains less than 1.5% by weight of trimeric molecules, 98% by weight of dimeric molecules and an iodine number of < 10 g/100 g. It is prepared based on linolenic, linoleic and oleic acids. Polyester 1 (P1):
    [109] Prepared according to Example D, column 16, lines 37 to 59 of DE 4009858 A. Polyester 2 (P2):
    [110] Prepared according to Example 5, page 18, paragraph 150, DE 102009018249 A1. Inventive binder 1 (BI1):
    [111] In a 4 l stainless steel reactor, equipped with an anchor stirrer, thermometer, condenser, thermometer for general temperature measurement and water separator, 2 mol of polyTHF1000, 579.3 g of dimeric fatty acid (1 mol ) and 51 g of cyclohexane were heated to 100°C in the presence of 2.1 g of di-n-butyltin oxide (Axion® CS 2455, from Chemtura). Heating was continued slowly until condensation began. At a maximum overall temperature of 85 °C, heating was continued, gradually up to 220 °C. The progress of the reaction was monitored via determination of the acid number. When an acid number of < 3 ng KOH/g was reached, remaining cyclohexane was removed by vacuum distillation. This yielded a viscous resin. Condensed amount (water): 34.9 g Number of acid: 2.7 mg KOH/g Solids content (60 min. at 130 °C): 100.0% Molecular weight (calibration: PMMA standards): Mn: 3900 g/mol Mw: 7200 g/mol Viscosity: 5549 mPas (measured at 23°C with a Brookfield CAP 2000+ rotary viscometer, spindle 3, shear rate: 1333 s-1) Inventive binder 2 (BI2):
    [112] The same used for the synthesis of BI1 binder, 2 mol of polypropylene glycol with an average molecular weight of 900 g/mol (Pluriol P900, BASF SE) and 1 mol of dimeric fatty acid were esterified in the presence of 1.9 g of di-n-butyltin oxide (Axion® CS 2455, from Chemtura). This yielded a viscous resin. Condensed amount (water): 35.2 g Number of acid: 0.3 mg KOH/g Solids content (60 min. at 130 °C): 100.0% Molecular weight (calibration: PMMA standards): Mn: 3400 g/mol Mw: 7000 g/mol Viscosity: 2003 mPas (measured at 23 °C with a Brookfield CAP 2000+ rotary viscometer, spindle 3, shear rate: 1333 s-1) Non-inventive binder 1 (BC1):
    [113] Analogously to the above experiment, 2 mol of dimeric fatty acid and 1 mol of polyTHF1000 were esterified in the presence of 1.7 di-n-butyltin oxide (Axion® CS 2455, from Chemtura). This yielded a viscous resin. Condensed amount (water): 34.7 g Acid number: 54.6 mg KOH/g Solids content (60 min. at 130 °C): 100.0% Molecular weight (calibration: PMMA standards): Mn: 2800 g/mol Mw: 8100 g/mol Viscosity: 19 793 mPas (measured at 23 °C with a Brookfield CAP 2000+ rotary viscometer, spindle 3, shear rate: 307 s-1)
    [114] Analogously to the above experiment, 1 mol of propylene glycol with an average molecular weight of 900 g/mol (Pluriol P900, BASF SE) and 2 mol of dimeric fatty acid were esterified in the presence of 1.6 g of dioxide -n-butyltin (Axion® CS 2455, from Chemtura). This yielded a viscous resin. Condensed amount (water): 34.6 g Number of acid: 57.2 mg KOH/g Solids content (60 min. at 130 °C): 100.0% Molecular weight (calibration: PMMA standards): Mn: 2400 g/mol Mw: 5800 g/mol Viscosity: 7790 mPas (measured at 23 °C with a Brookfield CAP 2000+ rotary viscometer, spindle 3, shear rate: 507 s-1) Examples of paint formulations 1. Preparation of a silver water-based coating material 1.
    [115] The components listed in Table A under "aqueous phase" were stirred together in the stated order to form an aqueous mixture. In the next step, an organic mixture was prepared from the components listed under “organic phase”. The organic mixture was added to the aqueous mixture. The resulting mixture was then stirred for 10 minutes and adjusted using deionized water and dimethylethanolamine to a pH of 8 and a spray viscosity of 58 mPas, with a shear load of 1000 s-1, measured using a rotary viscometer ( Mettler-Toledo Rheomat RM 180 instrument) at 23°C. Table A:

    E1 water-based coating material:
    [116] To prepare the inventive water-based coating material E1 a coating material was prepared analogously to the preparation of the water-based coating material 1, using BI1 instead of polyester P1 in both the aqueous and in the organic phase. E2 water-based coating material:
    [117] To prepare the non-inventive water-based coating material E2 a coating material was prepared analogously to the preparation of the water-based coating material 1, using BI1 instead of polyester P1 in both the aqueous phase and in the organic phase. E3 water-based coating material:
    [118] To prepare the inventive water-based coating material E3 a coating material was prepared analogously to the preparation of the water-based coating material 1, using BI1 instead of polyester P1 in both the aqueous and in the organic phase. E4 water-based coating material:
    [119] To prepare the non-inventive water-based coating material E4 a coating material was prepared analogously to the preparation of the water-based coating material 1, using BC2 instead of polyester P1 in both the aqueous phase and in the organic phase. Table 1: Compositions of waterborne basecoat materials 1 and E1 to E4.


    [120] The percent by weight figures in Table 1 are based on the total weight of the water-based base coat material. Comparison between waterborne basecoat material 1 and waterborne basecoat materials E1 to E4.
    [121] In order to determine the stability relative to the occurrence of blisters and swelling after storage with heat and moisture, the multi-layer paint systems were produced according to the following general procedure: A steel panel with dimensions of 10 x 20 cm, coated with a standard cathodic electrocoat (Cathoguard® 800, from BASF Coatings GmbH), was coated with a standard medium gray surface primer (ALG 670173, from Hemmelrath). After preliminary drying of the aqueous surface primer for a period of 10 minutes at 80 °C, it was oven baked at a temperature of 190 °C for a period of 30 minutes.
    [122] Each water-based basecoat material in Table 1 was then applied pneumatically. The resulting water-based basecoat film was flashed at room temperature for 2 minutes and then dried for 10 minutes in an air oven at 70 °C. A standard two-component clear coat material (Progloss® 345 from BASF Coatings GmbH) was applied to the dry water-based basecoat film. The resulting clearcoat film was flashed for 20 minutes at room temperature. Subsequently, the water-based base coat film and clear coat film were cured in an air oven at 160 °C for 30 minutes. The present system represents an original oven baked system and is referred to below as the original finish.
    [123] The original finish is blasted with an abrasive paper, after which each of the water-based basecoat materials from Table 1 is pneumatically applied to this blasted original finish. The resulting water-based basecoat film was flashed at room temperature for 2 minutes and then dried for 10 minutes in an air oven at 70 °C. A so-called two-component clear coat material at 80 °C (FF230500 2K stress-resistant refinish clear coat from BASF Coatings GmbH) was applied over the water-based and dried basecoat film. The resulting clearcoat film was flashed at room temperature for 20 minutes. Subsequently, the water-based base coat film and clear coat film were cured in an air oven at 80 °C for 30 minutes.
    [124] The steel panels thus treated were then stored for a period of 10 days in a climatic chamber in accordance with CH test conditions of DIN EN ISO 6270-2:2005-09. Subsequently, 24 after removing the climate chamber panels, they were inspected for bubbles and swelling.
    [125] The occurrence of bubbles was evaluated as follows, using a combination of 2 values: - the number of bubbles was evaluated using a quantity distribution from 1 to 5, with m1 meaning very few bubbles and m5 meaning many bubbles . - the size of the bubbles was evaluated using a size distribution, again from 1 to 5, with g1 denoting very small bubbles and g5 denoting very large bubbles. - the designation m0g0 therefore denotes a bubble-free finish after storage under heat and humidity and represents a satisfactory result in terms of bubble formation. Table 2: Bubble formation and swelling of waterborne basecoat material 1 and waterborne basecoat materials E1 to E4.
    Key: m = number of bubbles g = size of sat bubbles. = unsatisfactory result. = unsatisfactory result
    [126] The results confirm that, when using the polyesters of the invention, there are no longer any bubbles after exposure to heat and moisture and there is no longer any visible dilation. 2 Preparation of a red water-based basecoat material 1.
    [127] The components listed in Table B under “aqueous phase” were stirred together in the stated order to form an aqueous mixture. In the next step an organic mixture was prepared from the components listed under “organic phase”. The organic mixture was added to the aqueous mixture. The resulting mixture was then stirred for 10 minutes and adjusted using deionized water and dimethylethanolamine to a pH of 8 and a spray viscosity of 85 mPas under a shear load of 1000 s-1, measured using a rotary viscometer ( Mettler-Toledo Rheomat RM 180 instrument) at 23°C. Table B:

    Preparation of the red paste:
    [128] The red paste was prepared from 45.0 parts by weight of a polyurethane acrylate dispersion, prepared according to international patent application WO 91/1552, binder dispersion A, and from 21.0 parts by weight of Paliogen® red L 3885, 0.7 parts by weight of dimethylethanolamine, 2.5 parts by weight of 1,2-propylene glycol and 30.8 parts by weight of deionized water. Preparation of carbon black paste:
    [129] The carbon black slurry was prepared from 25 parts by weight of a polyurethane acrylate dispersion, prepared according to the international patent application WO 91/15528, binder dispersion A, and from 10 parts by weight of carbon black, 0.1 part by weight of methyl isobutyl ketone, 1.36 parts by weight of dimethylethanolamine, 2 parts by weight of a commercial polyether (Pluriol® P900, from BASF AG) and 61.45 parts by weight of deionized water. E5 water-based coating material:
    [130] To prepare the non-inventive water-based coating material E5, a coating material was prepared analogously to the preparation of the water-based coating material 2, using BI1 instead of melanin-formaldehyde resin Resimene HM-2608, available from Ineos in the aqueous phase. E6 water-based coating material:
    [131] To prepare the non-inventive water-based coating material E6, a coating material was prepared analogously to the preparation of the water-based coating material 2, using P1 instead of melanin-formaldehyde resin Resimene HM-2608, available from Ineos in the aqueous phase. E7 water-based coating material:
    [132] To prepare the non-inventive water-based coating material E7, a coating material was prepared analogously to the preparation of the water-based coating material 2, using P2 instead of melanin-formaldehyde resin Resimene HM-2608, available from Ineos in the aqueous phase Table 3: Compositions of waterborne basecoat materials 2 and E5 to E7.

    [133] The percent by weight figures in Table 3 are based on the total weight of the water-based basecoat material.
    [134] MFR = melamine-formaldehyde resin Comparison of waterborne basecoat material 2 and waterborne basecoat materials E5-E7
    [135] In order to determine stability against blistering and swelling after storage under heat and humidity, finishes on the plastic were produced according to the following general procedure:
    [136] A plastic substrate made of PP-EPDM (Hifax EKC 112X, from Lyondell-Basell) was cleaned with a degreaser and then briefly ignited using a laboratory flaming device with a blue oxidizing flame.

    [137] Then, a 2-component (2K) primer-surfacer (slate gray, R1471, with Worwag WW60738 100:10 curing agent) was applied to the panels, which were flamed at room temperature for 10 minutes and then dried for 30 minutes in an air oven at 80 °C. The water-based base coat material was applied pneumatically. The resulting water-based basecoat film was flashed at room temperature for 2 minutes and then dried for 10 minutes in an air oven at 70 °C. Over the dry water-based basecoat film a two-component clear coat material was applied slow fired and typically at 80°C (EverGloss® 905, from BASF Coatings GmbH). The resulting clearcoat film was flashed at room temperature for 10 minutes. Then the water-based base coat film and clear coat film were cured in an air oven at 80 °C for 40 minutes. The present system represents an original system for plastic parts for installation in or on vehicles.
    [138] The panels were stored at room temperature for seven days. They were then stored under hot and humid conditions, CH test conditions according to DIN IN ISO 6270-2:2005-09 (test duration: 10 days).
    [139] 30 minutes and 24 hours after removal from the climatic chamber, the panels were inspected for blistering and swelling.
    [140] Additionally, after 24 hours, a steam jet test was performed in accordance with test method A of DIN 55662:2009-12. After exposure to the steam jet, the test sample is inspected for peeling from the paint surface and for peeling at the diagonal crossing. An assessment is made for the degree of damage according to the diagrams in Figure 4, section 9.2 of DIN 55662:2009-12. For the purposes of the evaluation, delaminations smaller than 1 mm, resulting from the adverse cut in the cross cut, are disregarded. After the steam jet test there must be no delamination of the coating films. Table 4: steam jet testing / bubbling and swelling of waterborne basecoat material 2 and waterborne basecoat materials E5 to E7.
    Key: m = number of bubbles g = size of sat bubbles. = unsatisfactory result. = unsatisfactory result BC/CC = separation plane base coat / clear coat 4a, 3a and 2 refer to the characteristic values in DIN 55662.
    [141] The results clearly show that, when using the polyesters of the invention, there are no longer any bubbles after exposure to heat and moisture and there is no longer any visible swelling. In addition, clearcoat/basecoat adhesion has been significantly improved. 3. Preparation of a silver water-based coating material
    [142] The components listed in Table C under “aqueous phase” were stirred together in the stated order to form an aqueous mixture. In the next step an organic mixture was prepared from the components listed under “organic phase”. The organic mixture was added to the aqueous mixture. The resulting mixture was then stirred for 10 minutes and adjusted using deionized water and dimethylethanolamine to a pH of 8 and a spray viscosity of 85 mPas under a shear load of 1000 s-1, measured using a rotary viscometer ( Mettler-Toledo Rheomat RM 180 instrument) at 23°C. Table C

    E8 water-based coating material:
    [143] To prepare the inventive water-based coating material E8 a coating material was prepared analogously to the preparation of the water-based coating material 3, using BI1 instead of polyester P1 in both the aqueous and in the organic phase. E9 water-based coating material:
    [144] To prepare the non-inventive water-based coating material E9 a coating material was prepared analogously to the preparation of the water-based coating material 3, using BC1 instead of polyester P1 in both the aqueous phase and in the organic phase. E10 water-based coating material:
    [145] To prepare the inventive water-based coating material E10 a coating material was prepared analogously to the preparation of the water-based coating material 3, using BI2 instead of polyester P1 in both the aqueous and in the organic phase. E11 water-based coating material:
    [146] To prepare the non-inventive water-based coating material E11 a coating material was prepared analogously to the preparation of the water-based coating material 3, using BC2 instead of polyester P1 in both the aqueous phase and in the organic phase. Table 5: Compositions of water-based coating materials 3 and E8 to E11

    [147] The weight percent figures in Table 1 are based on the total weight of the water-based basecoat material. Comparison between waterborne basecoat material 3 and waterborne basecoat materials E8 to E11.
    [148] In order to determine stability towards bubbling and swelling after storage in heat and humidity, multi-layer paint systems were produced according to the following general procedure:
    [149] A steel panel measuring 10 x 20 cm, coated with a standard cathodic electrocoat (Cathoguard® 800, from BASF Coatings GmbH), was coated with a standard medium gray surface primer (ALG 670173, from Hemmelrath). After preliminary drying of the aqueous surface primer for a period of 10 minutes at 80 °C, it was oven baked at a temperature of 190 °C for a period of 30 minutes.
    [150] Each waterborne basecoat material in Table 5 was then applied pneumatically. The resulting water-based basecoat film was flashed at room temperature for 2 minutes and then dried for 10 minutes in an air oven at 70 °C. A standard two-component clear coat material (Progloss® 345 from BASF Coatings GmbH) was applied to the dry water-based basecoat film. The resulting clearcoat film was flashed for 20 minutes at room temperature. Subsequently, the water-based base coat film and clear coat film were cured in an air oven at 160 °C for 30 minutes. The present system represents an original oven baked system and is referred to below as the original finish.
    [151] The original finish is blasted with an abrasive paper, after which each of the water-based basecoat materials from Table 5 is pneumatically applied to this blasted original finish. The resulting water-based basecoat film was flashed at room temperature for 2 minutes and then dried for 10 minutes in an air oven at 70 °C. A so-called two-component clear coat material at 80 °C (FF230500 2K stress-resistant refinish clear coat from BASF Coatings GmbH) was applied over the water-based and dried basecoat film. The resulting clearcoat film was flashed at room temperature for 20 minutes. Subsequently, the water-based base coat film and clear coat film were cured in an air oven at 80 °C for 30 minutes.
    [152] The steel panels thus treated were then stored for a period of 10 days in a climatic chamber in accordance with CH test conditions of DIN EN ISO 6270-2:2005-09. Subsequently, 24 after removing the climate chamber panels, they were inspected for bubbles and swelling.
    [153] The occurrence of bubbles was evaluated as follows, through a combination of 2 values: - the number of bubbles was evaluated through a quantity distribution from 1 to 5, with m1 meaning very few bubbles and m5 many bubbles . - the size of the bubbles was evaluated using a size distribution, again from 1 to 5, with g1 denoting very small bubbles and g5 denoting very large bubbles. - the designation m0g0 therefore denotes a bubble-free finish after storage under heat and humidity and represents a satisfactory result in terms of bubble formation. Table 6: Bubble formation and expansion of waterborne basecoat material 3 and waterborne basecoat materials E8 to E11.
    Key: m = number of bubbles g = size of sat bubbles. = unsatisfactory result. = unsatisfactory result
    [154] The results confirm that when using the polyesters of the invention, there are no longer any bubbles after exposure to heat and moisture and there is no longer any visible swelling.
    权利要求:
    Claims (14)
    [0001]
    1. A pigmented aqueous basecoat material characterized in that it comprises at least one polymer, which polymer can be prepared by reacting (a) dimer fatty acids with (b) at least one polyether of general structure (I)
    [0002]
    2. A pigmented aqueous basecoat material according to claim 1, characterized in that the dimer fatty acids consist of an extension of at least 90% by weight of dimeric molecules, less than 5% by weight of trimeric molecules and less than 5% by weight of monomeric molecules and other by-products.
    [0003]
    3. A pigmented aqueous basecoat material according to claim 1, characterized in that the dimer fatty acid is prepared from linolenic, linoleic and/or oleic acid and consists of an extension of at least 98% by weight of dimeric molecules, less than 1.5% by weight of trimeric molecules and less than 0.5% by weight of monomeric molecules and other by-products and has an iodine number of < 10 g/100 g.
    [0004]
    4. Aqueous pigmented basecoat material, according to any one of the preceding claims, characterized in that said polyether of general structural formula (I) is polypropylene glycol or polytetrahydrofuran and has, in addition, an average molecular weight of 800 to 1200 g/mol.
    [0005]
    5. A water-based pigmented basecoat material according to any one of the preceding claims, characterized in that components (a) and (b) are used in a molar ratio of 0.9/2.1 to 1.1/ 1.9.
    [0006]
    6. Aqueous pigmented basecoat material, according to any one of the preceding claims, characterized in that it has an average molecular weight of 3000 to 4000 g/mol.
    [0007]
    7. A pigmented aqueous basecoat material according to any one of the preceding claims, characterized in that it has an acid number of < 5 mg KOH/g.
    [0008]
    8. The pigmented aqueous basecoat material according to claims 1 to 7, characterized in that the sum total of the percentage fractions by weight, based on the total weight of the pigmented aqueous basecoat material, of the polymers, is 0.1% to 30% by weight.
    [0009]
    9. A water-based pigmented basecoat material, according to claims 1 to 8, characterized in that it comprises, as an additional binder, at least one polyurethane resin.
    [0010]
    10. Use of a polymer comprised of an aqueous pigmented material as defined in claim 1, characterized in that it takes place in pigmented aqueous basecoat materials to promote adhesion.
    [0011]
    11. Method for producing a multi-layer paint system by (1) applying a pigmented aqueous basecoat material to a substrate; (2) forming a polymer film from the coating material applied in stage (1); (3) apply a clearcoat material to the resulting basecoat film and subsequently (4) cure the basecoat film together with the clearcoat film, characterized in that in stage (1) a material is used pigmented aqueous basecoat as defined in any one of claims 1 to 9.
    [0012]
    12. Method according to claim 11, characterized in that said substrate from stage (1) is a multilayer paint system that has areas of imperfection.
    [0013]
    13. Multilayer paint system characterized by the fact that it can be produced by the method as defined in claim 12.
    [0014]
    14. Method according to claim 11, characterized in that said multilayer paint system that has areas of imperfection is a paint system as defined in claim 13.
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    同族专利:
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    JP2015534588A|2015-12-03|
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    EP2890728A2|2015-07-08|
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    RU2015111092A|2016-10-20|
    CA2875640A1|2014-03-06|
    BR112014031698A2|2017-06-27|
    MX2015002389A|2015-08-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    BE794946A|1972-02-04|1973-08-02|Unilever Emery|NEW ESTERS COMPOSITIONS|
    NL194372C|1987-04-13|2002-02-04|Unichema Chemie Bv|Timerized fatty acids with a high content of dicarboxylic acid.|
    DE3825278A1|1988-07-26|1990-02-01|Basf Lacke & Farben|METHOD FOR PRODUCING MULTI-LAYER, PROTECTIVE AND / OR DECORATIVE COATINGS ON SUBSTRATE SURFACES|
    DE4107136A1|1991-03-06|1992-09-10|Basf Lacke & Farben|METHOD FOR PRODUCING A MULTILAYER, PROTECTIVE AND / OR DECORATIVE PAINT|
    CA2241071A1|1995-12-21|1997-07-03|Basf Coatings Aktiengesellschaft|Process for the production of multilayered coatings|
    JPH11315195A|1998-05-07|1999-11-16|Toyobo Co Ltd|Thermoplastic polyester elastomer|
    WO2000051708A1|1999-03-01|2000-09-08|Vulcan Performance Chemicals|Polyester water-based defoamer|
    US6638616B2|1999-10-15|2003-10-28|Dsm N.V.|Radiation-curable compositions comprising oligomers having an alkyd backbone|
    JP2001335623A|2000-03-22|2001-12-04|Dainippon Ink & Chem Inc|Impact resistance-imparting agent and polyester composition containing it|
    JP4385553B2|2000-09-11|2009-12-16|凸版印刷株式会社|Adhesive for dry or non-solvent lamination and laminated packaging material and packaging bag using the same|
    GB0213818D0|2002-06-17|2002-07-24|Ici Plc|Dispersions|
    US20080138627A1|2006-12-08|2008-06-12|Ppg Industries Ohio, Inc.|Color-plus-clear composite coatings|EP2910612A1|2014-02-20|2015-08-26|BASF Coatings GmbH|Coating compositions and coatings prepared from these and their use|
    EP3164433B1|2014-07-01|2019-01-09|BASF Coatings GmbH|Carboxyfunctional polyether based reaction products and aqueous base paints containing the reaction products|
    CN106661178A|2014-07-01|2017-05-10|巴斯夫涂料有限公司|Polyether-based reaction products and aqueous base paints containing the reaction products|
    EP2963093A1|2014-07-01|2016-01-06|BASF Coatings GmbH|Carboxyfunctional dimeric fatty acid based reaction products and aqueous base paints containing the reaction products|
    RU2017131080A3|2015-02-05|2019-03-06|
    EP3291922A1|2015-05-06|2018-03-14|BASF Coatings GmbH|Method for producing a multilayered coating on plastic substrates|
    RU2695222C2|2015-05-06|2019-07-22|БАСФ Коатингс ГмбХ|Method of producing a multilayer paint system|
    JP6863983B2|2015-11-26|2021-04-21|ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ|How to generate a multi-coat paint system|
    CN108698080A|2016-02-18|2018-10-23|巴斯夫涂料有限公司|Purposes of the low molecular carboxylic acid in water colour paint|
    CN108698079A|2016-02-18|2018-10-23|巴斯夫涂料有限公司|Purposes of the low molecular carboxylic acid in water colour paint|
    JP6378709B2|2016-03-16|2018-08-22|日新製鋼株式会社|Manufacturing method of decorative building board|
    PL3484936T3|2016-07-15|2022-01-31|Basf Coatings Gmbh|Aqueous base coat and production of multilayer coatings using the base coat|
    KR20190042577A|2016-08-24|2019-04-24|바스프 코팅스 게엠베하|Method for manufacturing coating system using aqueous basecoat|
    ES2818553T3|2016-09-22|2021-04-13|Basf Coatings Gmbh|Aqueous basecoat paint with improved stability in annular pipe|
    JP2020514517A|2017-03-23|2020-05-21|ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ|Aqueous effect pigment pastes containing polymers, and base coats made therefrom|
    JP2020511582A|2017-03-23|2020-04-16|ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ|Aqueous colored pigment paste containing a polymer and a base coat produced therefrom|
    EP3700982A1|2017-10-23|2020-09-02|BASF Coatings GmbH|Primer coating agent system for plastic substrates|
    JP2021519375A|2018-03-28|2021-08-10|ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ|Aqueous base coat material and a method for manufacturing a multi-coat system using the base coat material|
    JP2021522390A|2018-04-27|2021-08-30|ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ|Surface-modified aluminum hydroxide particles as rheology aids in aqueous coating compositions|
    WO2019211473A1|2018-05-03|2019-11-07|Basf Coatings Gmbh|Colloidal dispersions for preparing coatings having a viewing-angle-dependent brightness, and use thereof|
    US20210262912A1|2018-06-25|2021-08-26|Basf Coatings Gmbh|Method for determining the average filament length during a rotational atomization, and screening method based thereon during the development of a paint|
    EP3810337A1|2018-06-25|2021-04-28|BASF Coatings GmbH|Method for producing an optimized coating, and coating which can be obtained using said method|
    JP2021529657A|2018-06-25|2021-11-04|ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ|A method for producing an optimal coating, and a coating that can be obtained using the method described above.|
    JP2021529656A|2018-06-25|2021-11-04|ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ|A method for determining the droplet size distribution during spraying and a selection method based on it in paint development|
    EP3863773A1|2018-10-12|2021-08-18|BASF Coatings GmbH|Method for producing a multi-layer lacquer finish via the post-additivation of an aqueous dispersion, containing polyamides and/or amide waxes, to at least one base lacquer|
    CA3125931A1|2019-01-23|2020-07-30|Basf Coatings Gmbh|Polycarboxylic acid-containing aqueous coating agent having an improved effect pigment alignment|
    WO2021028466A1|2019-08-12|2021-02-18|Basf Coatings Gmbh|Method for producing effect pigment pastes using a vibrator|
    WO2021032812A1|2019-08-20|2021-02-25|Basf Coatings Gmbh|Device for monitoring rotational atomization of a coating material composition|
    WO2021037792A1|2019-08-29|2021-03-04|Basf Coatings Gmbh|Coating composition curable by aceto-michael addition|
    WO2021037791A1|2019-08-29|2021-03-04|Basf Coatings Gmbh|Coating composition curable by thio-michael addition|
    WO2021074359A1|2019-10-17|2021-04-22|Basf Coatings Gmbh|Aqueous dispersions for producing high-solid coating material compositions and coatings thereof with excellent flop|
    WO2021074360A1|2019-10-17|2021-04-22|Basf Coatings Gmbh|Nir light scattering coatings and compositions for preparing them|
    WO2021224232A1|2020-05-04|2021-11-11|Basf Coatings Gmbh|Coating systems with increased jetness of black and improved color|
    WO2022038203A1|2020-08-18|2022-02-24|Basf Coatings Gmbh|2-wet coating method for preparing multilayer coating systems|
    WO2022038202A1|2020-08-18|2022-02-24|Basf Coatings Gmbh|3-wet coating method for preparing multilayer coating systems|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-01-19| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12182050.0|2012-08-28|
    EP12182050|2012-08-28|
    PCT/EP2013/067742|WO2014033135A2|2012-08-28|2013-08-27|Polymer in multi-coat colour and/or effect paint system|
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