Classifications

• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/005—Repairing damaged coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/53—Base coat plus clear coat type
  • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
  • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts

Definitions

• the invention relates to an innovative reaction product containing dimer fatty acid. It further relates to a pigmented aqueous basecoat material which comprises this reaction product, and also to the use of said reaction product in pigmented aqueous basecoat materials. It also relates to a method for producing multicoat paint systems, using the pigmented aqueous basecoat material, and also to the multicoat paint systems producible by means of said method. The present invention relates, furthermore, to the refinishing of defects on multicoat paint systems.
• This method is widely employed, for example, for the OEM finishing of automobiles and also for the painting of metal and plastic ancillary components. Under certain conditions, adhesion problems arise here, particularly between basecoat film and clearcoat film.
• the method is also used, furthermore, for the refinishing of automobile bodies. This refers both to OEM automobile refinishing and also to the automotive refinishing which takes place, for example, in a workshop. Particularly problematic in this context is the adhesion between the original finish and the basecoat used in the finishing, or the coating film produced from it.
• the properties of a basecoat material and of the coating films produced from it are determined in particular by the binders and additives present in the basecoat material, examples being specific reaction products.
• the problem addressed by the present invention was that of providing a reaction product which can be used to produce coatings which no longer have the above-identified disadvantages of the prior art.
• the adhesion of coatings, especially basecoat films ought therefore to be improved significantly both when painting metallic and plastic substrates and when carrying out automotive refinishing.
• the foreground was occupied, as well as by the adhesion of the basecoat to the substrate, by the adhesion between basecoat and clearcoat.
• the foreground was occupied, as well as by the adhesion between basecoat and clearcoat, by the adhesion between basecoat and original finish. This ought to be improved in particular for use in OEM automobile refinishing.
• the intention through the provision of a new reaction product and the use thereof in coating compositions, especially pigmented basecoat materials, was to improve the adhesion of these basecoat materials to the respective interfaces within the nexus of coats in multicoat paint systems.
• adhesion problems affecting the systems known from the prior art may in particular be especially pronounced when the coated substrates are exposed to weathering. It is a further object of the present invention, therefore, to provide coatings which even after having been exposed to weathering still possess outstanding adhesion properties.
• a central problem addressed by the present invention was that of reducing, or even entirely preventing, the incidence of blisters and swelling after weathering exposures.
• R is a C 3 to C 6 alkylene radical and n correspondingly is selected such that the compound (b) possesses a number-average molecular weight of 120 to 445 g/mol, components (a) and (b) are used in a molar ratio of 0.7/2.3 to 1.6/1.7, and the resulting reaction product possesses a number-average molecular weight of 600 to 4000 g/mol and an acid number of less than 10 mg KOH/g.
• n is selected such that said compound (b) possesses a number-average molecular weight of 120 to 445 g/mol
• R is a hexamethylene radical and the number-average molecular weight is to be 400 g/mol
• n is on average between 3 and 4. From the provisos given, the skilled person is perfectly well aware of how to prepare or select a corresponding reaction product. Apart from this, the description which follows on below, and especially the examples, provide additional information as well.
• the parameter n then, just like the number-average molecular weight, is to be understood as a statistical average value.
• reaction product of the invention is also referred to below as reaction product of the invention.
• Preferred embodiments of the reaction product of the invention are apparent from the description which follows and also from the dependent claims.
• a pigmented aqueous basecoat material comprising the reaction product of the invention, and the use of the reaction product in aqueous basecoat materials for improving adhesion.
• the present invention relates not least to a method for producing a multicoat paint system on a substrate, and also to a multicoat paint system produced by said method.
• the present invention also relates to a method for refinishing defects on multicoat paint systems, wherein the basecoat of the invention is used.
• the reaction product of the invention produces outstanding adhesion between basecoat materials or basecoat films which comprise the reaction product, and the underlying substrate, and also the clearcoat situated above.
• Particularly effective is the minimization of typical phenomena which indicate deficient adhesion, especially blisters and swelling in the respective paint system.
• the reaction product of the invention and also the basecoat material of the invention can therefore be used to particularly good effect in the sector of automotive refinish.
• the reaction product of the invention is prepared using at least one dimer fatty acid (a).
• Dimer fatty acids are generally, and especially in the context of the present invention, mixtures prepared by oligomerization of unsaturated fatty acids. They are preparable, for example, by catalytic dimerization of unsaturated plant fatty acids, with starting materials used more particularly being unsaturated C 12 to C 22 fatty acids. Linkage is primarily in accordance with the Diels-Alder type, and the result, depending on the number and position of the double bonds in the fatty acids used for preparing the dimer fatty acids, are mixtures of principally dimeric products, which have cycloaliphatic, linear aliphatic, branched aliphatic, and also C 6 aromatic hydrocarbon groups between the carboxyl groups.
• the aliphatic radicals may be saturated or unsaturated and the fraction of aromatic groups as well may vary.
• the radicals between the carboxylic acid groups then contain, for example, 24 to 44 carbon atoms.
• fatty acids having 18 carbon atoms are preferably used, and so the dimeric product has 36 carbon atoms.
• the radicals which join the carboxyl groups of the dimer fatty acids preferably have no unsaturated bonds and no aromatic hydrocarbon radicals.
• C 18 fatty acids are used preferably in the preparation. Particular preference is given to the use of linolenic, linoleic and/or oleic acid.
• dimer fatty acids generally contain at least 80 wt % of dimeric molecules, up to 19 wt % of trimeric molecules, and not more than 1 wt % of monomeric molecules and of other byproducts.
• dimer fatty acids which consist of at least 90 wt %, preferably at least 95 wt %, very preferably at least 98 wt % of dimeric fatty acid molecules.
• dimer fatty acids which consist of at least 90 wt % of dimeric molecules, less than 5 wt % of trimeric molecules, and less than 5 wt % of monomeric molecules and other byproducts.
• dimer fatty acids which consist of 95 to 98 wt % of dimeric molecules, less than 5 wt % of trimeric molecules, and less than 1 wt % of monomeric molecules and of other byproducts.
• dimer fatty acids consisting of at least 98 wt % of dimeric molecules, less than 1.5 wt % of trimeric molecules, and less than 0.5 wt % of monomeric molecules and other byproducts.
• Determining the fractions of monomeric, dimeric, and trimeric molecules and of other byproducts in the dimer fatty acids may be done for example by means of gas chromatography (GC).
• GC gas chromatography
• the dimer fatty acids are converted to the corresponding methyl esters via the boron trifluoride method (compare DIN EN ISO 5509) and then analyzed by means of GC.
• a fundamental identifier of “dimer fatty acids” in the context of the present invention is that their preparation involves the oligomerization of unsaturated fatty acids.
• the principal products of this oligomerization in other words to an extent preferably of at least 80 wt %, more preferably of at least 90 wt %, very preferably of at least 95 wt %, and more particularly of at least 98 wt %, are dimeric products.
• the fact that the oligomerization produces predominantly dimeric products, which therefore contain precisely two fatty acid molecules, justifies this designation, which is in any case commonplace.
• the dimer fatty acids to be used can be obtained as commercial products. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976, and Radiacid 0977 from Oleon, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 from Croda, Empol 1008, Empol 1061, and Empol 1062 from Cognis, and Unidyme 10 and Unidyme TI from Arizona Chemical.
• reaction products of the invention are prepared using at least one compound (b) of the general structural formula (I)
• R is a C 3 to C 6 alkyl radical.
• the index n is to be selected in each case such that the compound (b) possesses a number-average molecular weight of 120 to 445 g/mol. It preferably possesses a number-average molecular weight of 130 to 435 g/mol, more preferably of 140 to 425 g/mol, more particularly 150 to 400 g/mol, preferably in turn 170 to 350 g/mol, and, in one particular embodiment, 200 to 300 g/mol. Unless specifically indicated otherwise, the number-average molecular weight for the purposes of the present invention is determined by means of vapor pressure osmosis.
• a compound (b) comprises mixtures of molecules with different sizes. At least a portion, or all, of these molecules are distinguished by a sequence of identical or different monomer units (as a reacted form of monomers).
• a compound (b) or the corresponding molecule mixture therefore in principle comprises molecules which comprise a plurality of (that is, at least two) identical or different monomer units. It will be appreciated that in the mixture there may also, proportionally, be the monomers themselves, in other words in their unreacted form.
• a compound (b) is a mixture of molecules which differ in their molecular weights.
• a compound (b) therefore cannot be described by a discrete molecular weight, but instead, therefore, is always assigned average molecular weights, such as the number-average molecular weight specified above, for example.
• This principle is known to the skilled person from, for example, the polymers. Polymers too are always mixtures of different molecules.
• Compound (b) is therefore understood in the context of the present invention to comprise a mixture of molecules, the mixture including molecules which are distinguished by a sequence of identical or different monomer units.
• the parameter n is in every case greater than 1.0.
• n is at least 1.5, more particularly at least 2.0, more preferably at least 3.0.
• Preferred in turn are the ranges 1.5 to 9.0, preferably 2.0 to 7.0, very preferably 3.0 to 5.0.
• the compound (b) is therefore preferably an oligoether or a polyether.
• n being at least 3, for example)
• n radicals R are identical. It is likewise also possible, however, for different kinds of radicals R to be present. Preferably all the radicals R are identical.
• R preferably is a C 3 or C 4 alkylene radical. With particular preference it is an isopropylene radical or a tetramethylene radical.
• the compound (b) for use in accordance with the invention is polypropylene glycol or polytetrahydrofuran.
• component (a) and (b) are linked to one another via common-knowledge esterification. Accordingly, the carboxyl groups of component (a) are reacted with the hydroxyl groups of component (b).
• the reaction may take place, for example, in bulk or in solution with typical organic solvents at temperatures of, for example, 50° C. to 300° C.
• catalysts such as sulfuric acid, sulfonic acids and/or tetraalkyl titanates, zinc alkoxylates and/or tin alkoxylates, dialkyltin oxides such as di-n-butyltin oxide, for example, or organic salts of the dialkyltin oxides.
• a water separator is used as well, to collect the water produced during the condensation reaction.
• the components (a) and (b) here are used in a molar ratio of 0.7/2.3 to 1.6/1.7, preferably of 0.8/2.2 to 1.6/1.8, and very preferably of 0.9/2.1 to 1.5/1.8.
• the reaction is discontinued when the reaction product of the invention possesses an acid number of less than 10 mg KOH/g. Preferably it possesses an acid number of less than 7.5 mg KOH/g, and very preferably of less than 5 mg KOH/g.
• the acid number is determined in accordance with DIN 53402.
• the resulting reaction product possesses a number-average molecular weight of 600 to 4000 g/mol, preferably 800 to 3500 g/mol, and very preferably 900 to 3000 g/mol.
• reaction products of the invention generally possess a low water-solubility. If used in aqueous systems, they generally accumulate at the interfaces, owing to their incompatibility, for example, and are therefore able to contribute to improving the adhesion with respect to adjoining films.
• the reaction product of the invention is generally hydroxy-functional, preferably dihydroxy-functional.
• the present invention further relates to a pigmented aqueous basecoat material which comprises at least one reaction product of the invention.
• a basecoat material is a color-imparting intermediate coating material that is used in automotive finishing and general industrial painting.
• This basecoat material is generally applied to a metallic or plastics substrate which has been pretreated with surfacer or primer-surfacer, or else, occasionally, directly to the plastics substrate.
• Substrates used may also include existing paint systems, which may optionally require pretreatment as well (by abrading, for example). It is presently entirely customary to apply more than one basecoat film. Accordingly, in such a case, a first basecoat film represents the substrate for a second such film. To protect a basecoat film from environmental effects in particular, at least one additional clearcoat film is applied over it.
• the sum total of the weight-percentage fractions, based on the total weight of the pigmented aqueous basecoat material, of all reaction products of the invention is preferably 0.1 to 30 wt %, more preferably 1 to 20 wt %, and very preferably 1.5 to 15 wt % or even 2 to 12 wt %.
• reaction product of the invention is below 0.1 wt %, it may be possible that no improvement in adhesion is obtained any longer.
• amount is more than 30 wt %, there may in certain circumstances be disadvantages, such as incompatibility of said reaction product in the basecoat material, for example. Such incompatibility may be manifested, for example, in uneven leveling and also in floating or settling.
• the reaction product of the invention is generally of poor solubility in aqueous systems. It is therefore preferably used directly during the production of the pigmented aqueous basecoat material, and not only added to the otherwise complete basecoat material after production has taken place.
• the sum total of the weight-percentage fractions of all reaction products of the invention is 0.1 to 30 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the sum total of the weight-percentage fractions of all preferred embodiments of the reaction products of the invention is preferably likewise 0.1 to 30 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the pigmented aqueous basecoat material comprises, as reaction products of the invention, exclusively preferred embodiments of the reaction products of the invention.
• the sum total of the weight-percentage fractions of all reaction products of the invention is 1 to 20 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the sum total of the weight-percentage fractions of all preferred embodiments of the reaction products of the invention is preferably likewise 1 to 20 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the pigmented aqueous basecoat material comprises, as reaction products of the invention, exclusively preferred embodiments of the reaction products of the invention.
• the sum total of the weight-percentage fractions of all reaction products of the invention is 1.5 to 15 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the sum total of the weight-percentage fractions of all preferred embodiments of the reaction products of the invention is preferably likewise 1.5 to 15 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the pigmented aqueous basecoat material comprises, as reaction products of the invention, exclusively preferred embodiments of the reaction products of the invention.
• the sum total of the weight-percentage fractions of all reaction products of the invention is 2 to 12 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the sum total of the weight-percentage fractions of all preferred embodiments of the reaction products of the invention is preferably likewise 2 to 12 wt %, based on the total weight of the pigmented aqueous basecoat material.
• the pigmented aqueous basecoat material comprises, as reaction products of the invention, exclusively preferred embodiments of the reaction products of the invention.
• the basecoat materials used in accordance with the invention comprise color and/or effect pigments.
• color pigments and effect pigments are known to the skilled person and are described for example in ⁇ umlaut over (R) ⁇ ompp-Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 176 and 451.
• the fraction of the pigments may be situated for example in the range from 1 to 40 wt %, preferably 2 to 30 wt %, more preferably 3 to 25 wt %, based on the total weight of the pigmented aqueous basecoat material.
• Preferred basecoat materials in the context of the present invention are those which comprise, as binders, polymers curable physically, thermally, or both thermally and with actinic radiation.
• Binder for the purposes of the present invention and in accordance with relevant DIN EN ISO 4618 is the nonvolatile fraction of a coating composition, without pigments and fillers.
• Specific binders accordingly, include, for example, typical coatings additives, the reaction product of the invention, or typical crosslinking agents described later on below, even if the expression is used primarily below in relation to particular polymers curable physically, thermally, or both thermally and with actinic radiation, as for example particular polyurethane resins.
• the pigmented aqueous basecoat materials of the invention more preferably comprise at least one polyurethane resin as binder. Coating materials of this kind comprising polyurethane resins may likewise customarily be cured physically, thermally, or both thermally and with actinic radiation.
• the term “physical curing” denotes the formation of a film by loss of solvent from polymer solutions or polymer dispersions. Typically no crosslinking agents are necessary for this curing.
• thermal curing denotes the heat-initiated crosslinking of a coating film, with either a separate crosslinking agent or else self-crosslinking binders being employed in the parent coating material.
• the crosslinking agent comprises reactive functional groups which are complementary to the reactive functional groups present in the binders. This is commonly referred to by those in the art as external crosslinking.
• the complementary reactive functional groups or autoreactive functional groups that is, groups which react with groups of the same kind—are already present in the binder molecules
• the binders present are self-crosslinking. Examples of suitable complementary reactive functional groups and autoreactive functional groups are known from German patent application DE 199 30 665 A1, page 7, line 28 to page 9, line 24.
• actinic radiation means electromagnetic radiation such as near infrared (NIR), UV radiation, more particularly UV radiation, and particulate radiation such as electron radiation. Curing by UV radiation is commonly initiated by radical or cationic photoinitiators.
• NIR near infrared
• UV radiation more particularly UV radiation
• particulate radiation such as electron radiation. Curing by UV radiation is commonly initiated by radical or cationic photoinitiators.
• Preferred thermally curing basecoat materials are those which comprise as binder a polyurethane resin, preferably a hydroxyl-containing polyurethane resin, and as crosslinking agent an aminoplast resin or a blocked or nonblocked polyisocyanate, preferably an aminoplast resin.
• a polyurethane resin preferably a hydroxyl-containing polyurethane resin
• crosslinking agent an aminoplast resin or a blocked or nonblocked polyisocyanate, preferably an aminoplast resin.
• aminoplast resins melamine resins are preferred.
• the sum total of the weight-percentage fractions, based on the total weight of the pigmented aqueous basecoat material, of all crosslinking agents, preferably aminoplast resins and/or blocked and/or nonblocked polyisocyanates, more particularly preferably melamine resins, is preferably 1 to 20 wt %, more preferably 1.5 to 17.5 wt %, and very preferably 2 to 15 wt % or even 2.5 to 10 wt %.
• the polyurethane resin preferably present may be ionically and/or nonionically hydrophilically stabilized. In preferred embodiments of the present invention the polyurethane resin is ionically hydrophilically stabilized.
• the preferred polyurethane resins are linear or contain instances of branching.
• the polyurethane resin is more preferably one in whose presence olefinically unsaturated monomers have been polymerized. This polyurethane resin may be present alongside the polymer originating from the polymerization of the olefinically unsaturated monomers, without these polymers being bonded covalently to one another.
• the polyurethane resin may also be bonded covalently to the polymer originating from the polymerization of the olefinically unsaturated monomers.
• the olefinically unsaturated monomers are preferably monomers containing acrylate groups and/or methacrylate groups. It is likewise preferred for the monomers containing acrylate and/or methacrylate groups to be used in combination with other olefinically unsaturated compounds which contain no acrylate or methacrylate groups.
• Olefinically unsaturated monomers attached to the polyurethane resin are more preferably monomers containing acrylate groups or methacrylate groups, thereby producing polyurethane (meth)acrylates.
• the polyurethane resin is a polyurethane (meth)acrylate.
• the polyurethane resin present with preference is curable physically, thermally, or both thermally and with actinic radiation. More particularly it is curable either thermally or both thermally and with actinic radiation.
• the polyurethane resin comprises reactive functional groups through which external crosslinking is possible.
• the polyurethane resin is prepared using preferably the aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and/or cycloaliphatic-aromatic polyisocyanates that are known to the skilled person.
• the saturated and unsaturated polyols of relatively high molecular mass and of low molecular mass preference is given to using the saturated and unsaturated polyols of relatively high molecular mass and of low molecular mass, and also, optionally, monoalcohols, in minor amounts, that are known to the skilled person.
• Low molecular mass polyols used are more particularly diols and, in minor amounts, triols, for introducing instances of branching.
• suitable polyols of high molecular mass are saturated or olefinically unsaturated polyester polyols and/or polyether polyols.
• High molecular mass polyols are more particularly polyester polyols, especially those having a number-average molecular weight of 400 to 5000 g/mol.
• the polyurethane resin preferably present may contain particular ionic groups and/or groups which can be converted into ionic groups (potentially ionic groups).
• Polyurethane resins of this kind are referred to for the purposes of the present invention as ionically hydrophilically stabilized polyurethane resins.
• the modifying groups are alternatively
• the functional groups for cationic modification are, for example, primary, secondary and/or tertiary amino groups, secondary sulfide groups and/or tertiary phosphine groups, more particularly tertiary amino groups and secondary sulfide groups (functional groups which, by neutralizing agents and/or quaternizing agents, can be converted into cationic groups).
• cationic groups groups prepared from the aforementioned functional groups using neutralizing agents and/or quaternizing agents that are known to the skilled person—such as primary, secondary, tertiary and/or quaternary ammonium groups, tertiary sulfonium groups and/or quaternary phosphonium groups, more particularly quaternary ammonium groups and tertiary sulfonium groups.
• the functional groups for anionic modification are, as is known, for example, carboxylic acid, sulfonic acid and/or phosphonic acid groups, more particularly carboxylic acid groups (functional groups which, by neutralizing agents, can be converted into anionic groups), and also anionic groups—groups prepared from the aforementioned functional groups using neutralizing agents known to the skilled person—such as carboxylate, sulfonate and/or phosphonate groups.
• the functional groups for nonionic hydrophilic modification are preferably poly(oxyalkylene) groups, more particularly poly(oxyethylene) groups.
• the polyurethane resin may preferably be a graft polymer. More particularly it is a polyurethane resin grafted with olefinically unsaturated compounds, preferably olefinically unsaturated monomers. In this case, then, the polyurethane is grafted, for example, with side groups and/or side chains that are based on olefinically unsaturated monomers. These are more particularly side chains based on poly(meth)acrylates.
• Poly(meth)acrylates for the purposes of the present invention are polymers or polymeric radicals which comprise monomers containing acrylate and/or methacrylate groups, and preferably consist of monomers containing acrylate groups and/or methacrylate groups.
• Side chains based on poly(meth)acrylates are understood to be side chains which are constructed during the graft polymerization, using monomers containing (meth)acrylate groups.
• preference here is given to using more than 50 mol %, more particularly more than 75 mol %, especially 100 mol %, based on the total amount of the monomers used in the graft polymerization, of monomers containing (meth)acrylate groups.
• the side chains described are introduced into the polymer preferably after the preparation of a primary polyurethane resin dispersion.
• the polyurethane resin present in the primary dispersion may contain lateral and/or terminal olefinically unsaturated groups via which, then, the graft polymerization with the olefinically unsaturated compounds proceeds.
• the polyurethane resin for grafting may therefore be an unsaturated polyurethane resin (A).
• the graft polymerization is in that case a radical polymerization of olefinically unsaturated reactants. Also possible, for example, is for the olefinically unsaturated compounds used for the graft polymerization to contain at least one hydroxyl group.
• olefinically unsaturated compounds with which the polyurethane resin (A) is preferably grafted it is possible to use virtually all radically polymerizable, olefinically unsaturated, and organic monomers which are available to the skilled person for these purposes.
• a number of preferred monomer classes may be specified by way of example:
• the lateral and/or terminal olefinically unsaturated groups in the polyurethane resin, via which the graft polymerization with the olefinically unsaturated compounds can proceed, are introduced into the polyurethane resin preferably via particular monomers.
• These particular monomers, in additional to an olefinically unsaturated group, also include, for example, at least one group that is reactive toward isocyanate groups.
• Preferred are hydroxyl groups and also primary and secondary amino groups. Especially preferred are hydroxyl groups.
• the monomers described through which the lateral and/or terminal olefinically unsaturated groups may be introduced into the polyurethane resin may also, of course, be employed without the polyurethane resin being additionally grafted thereafter with olefinically unsaturated compounds. It is preferred, however, for the polyurethane resin to be grafted with olefinically unsaturated compounds.
• the polyurethane resin preferably present may be a self-crosslinking and/or externally crosslinking binder.
• the polyurethane resin preferably comprises reactive functional groups through which external crosslinking is possible. In that case there is preferably at least one crosslinking agent in the pigmented aqueous basecoat material.
• the reactive functional groups through which external crosslinking is possible are more particularly hydroxyl groups.
• the polyurethane resin is prepared by the customary methods of polymer chemistry. This means, for example, the polymerization of polyisocyanates and polyols to polyurethanes, and the graft polymerization that preferably then follows with olefinically unsaturated compounds.
• the methods are known to the skilled person and can be adapted individually. Exemplary preparation processes and reaction conditions can be found in European patent EP 0521 928 B1, page 2, line 57 to page 8, line 16.
• the polyurethane resin preferably present preferably possesses a number-average molecular weight of 200 to 30 000 g/mol, more preferably of 2000 to 20 000 g/mol. It further possesses, for example, a hydroxyl number of 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 5 to 200 mg KOH/g, more particularly 10 to 40 mg KOH/g. The hydroxyl number is determined in accordance with DIN 53240, the acid number in accordance with DIN 53402.
• the polyurethane resin content is preferably between 5 and 80 wt %, more preferably between 8 and 70 wt %, and very preferably between 10 and 60 wt %, based in each case on the film-forming solids of the basecoat material.
• film-forming solids corresponding ultimately to the binder fraction, is meant the nonvolatile weight fraction of the basecoat material, without pigment and, where appropriate, fillers.
• the film-forming solids can be determined as follows: A sample of the pigmented aqueous basecoat material (approximately 1 g) is admixed with 50 to 100 times the amount of tetrahydrofuran and then stirred for around 10 minutes. The insoluble pigments and any fillers are then removed by filtration and the residue is rinsed with a little THF, the THF being removed from the resulting filtrate on a rotary evaporator. The residue of the filtrate is dried at 120° C. for two hours and the resulting film-forming solids is obtained by weighing.
• the sum total of the weight-percentage fractions, based on the total weight of the pigmented aqueous basecoat material, of all polyurethane resins is preferably 2 to 40 wt %, more preferably 2.5 to 30 wt %, and very preferably 3 to 20 wt %.
• the pigmented aqueous basecoat material to be used may further comprise at least one polyester different from the reaction products of the invention, more particularly a polyester having a number-average molecular weight of 400 to 5000 g/mol, as binder.
• polyesters are described for example in DE 4009858 in column 6, line 53 to column 7, line 61 and column 10, line 24 to column 13, line 3.
• Suitable thickeners are inorganic thickeners from the group of the phyllosilicates. Besides the inorganic thickeners, however, there may also be one or more organic thickeners used. These are preferably selected from the group consisting of (meth)acrylic acid-(meth)acrylate copolymer thickeners, such as the commercial product Rheovis AS S130 (BASF), and of polyurethane thickeners, such as the commercial product Rheovis PU 1250 (BASF), for example. The thickeners used are different from the binders used.
• the pigmented aqueous basecoat material may further comprise at least one adjuvant.
• adjuvants are salts which can be decomposed thermally without residue or substantially without residue, binder resins different from polyurethane resins and curable physically, thermally and/or with actinic radiation, further crosslinking agents, organic solvents, reactive diluents, transparent pigments, fillers, molecularly dispersely soluble dyes, nanoparticles, light stabilizers, antioxidants, deaerating agents, emulsifiers, slip additives, polymerization inhibitors, radical polymerization initiators, adhesion promoters, leveling agents, film-forming assistants, sag control agents (SCAs), flame retardants, corrosion inhibitors, waxes, siccatives, biocides, and flatting agents.
• SCAs sag control agents
• Suitable adjuvants of the aforementioned kind are known for example from
• the solids content of the basecoat materials of the invention may vary according to the requirements of the case in hand.
• the solids content is guided primarily by the viscosity required for application, more particularly for spray application, and so may be adjusted by the skilled person on the basis of his or her general art knowledge, optionally with assistance from a few rangefinding tests.
• the solids content of the basecoat materials is preferably 5 to 70 wt %, more preferably 8 to 60 wt %, and very preferably 12 to 55 wt %.
• solids content is meant that weight fraction which remains as a residue on evaporation under specified conditions.
• the solids are determined in accordance with DIN EN ISO 3251. This is done by evaporating the basecoat material at 130° C. for 60 minutes.
• this test method is likewise employed in order to determine, for example, the fraction of various components of the basecoat material as a proportion of the total weight of the basecoat material.
• the solids of a dispersion of a polyurethane resin which is to be added to the basecoat material may be determined correspondingly in order to ascertain the fraction of this polyurethane resin as a proportion of the overall composition.
• the basecoat material of the invention is aqueous.
• aqueous is known in this context to the skilled person. The phrase refers in principle to a basecoat material which is not based exclusively on organic solvents, i.e., does not contain exclusively organic-based solvents as its solvents instead, in contrast, including a significant fraction of water as solvent.
• “Aqueous” for the purposes of the present invention should preferably be understood to mean that the coating material in question, more particularly the basecoat material, has a water fraction of at least 40 wt %, preferably at least 50 wt %, very preferably at least 60 wt %, based in each case on the total amount of the solvents present (i.e., water and organic solvents).
• the water fraction is 40 to 90 wt %, more particularly 50 to 80 wt %, very preferably 60 to 75 wt %, based in each case on the total amount of solvents present.
• the basecoat materials employed in accordance with the invention may be produced using the mixing assemblies and mixing techniques that are customary and known for producing basecoat materials.
• a further aspect of the present invention is a method for producing a multicoat paint system, where
• Said method is employed preferably for producing multicoat color paint systems, effect paint systems, and color and effect paint systems.
• the pigmented aqueous basecoat material used in accordance with the invention is commonly applied to metallic or plastics substrates that have been pretreated with surfacer or primer-surfacer. Said basecoat material may also be applied, optionally, directly to the plastics substrate.
• a metallic substrate is to be coated, it is preferably further coated with an electrocoat system before the surfacer or primer-surfacer is applied.
• a plastic substrate is being coated, it is preferably also pretreated before the surfacer or primer-surfacer is applied.
• the techniques most frequently employed for such pretreatment are those of flaming, plasma treatment, and corona discharge. Flaming is used with preference.
• the pigmented aqueous basecoat material of the invention may be applied to a metallic substrate, at the film thicknesses customary within the automobile industry, in the range, for example, of 5 to 100 micrometers, preferably 5 to 60 micrometers. This is done using spray application methods, such as, for example, compressed air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), alone or in conjunction with hot spray application such as hot air spraying, for example.
• spray application methods such as, for example, compressed air spraying, airless spraying, high-speed rotation, electrostatic spray application (ESTA), alone or in conjunction with hot spray application such as hot air spraying, for example.
• 1K (1-component) basecoat materials which are preferred, can be flashed at room temperature for 1 to 60 minutes and subsequently dried, preferably at optionally slightly elevated temperatures of 30 to 90° C. Flashing and drying for the purposes of the present invention mean the evaporation of organic solvents and/or water, as a result of which the paint becomes dryer but has not yet cured or not yet formed a fully crosslinked coating film.
• the clearcoat material After the clearcoat material has been applied, it can be flashed at room temperature for 1 to 60 minutes, for example, and optionally dried. The clearcoat is then cured together with the applied pigmented basecoat. In the course of these procedures, crosslinking reactions occur, for example, to produce on a substrate a multiple-coat color and/or effect paint system of the invention. Curing takes place preferably thermally at temperatures from 60 to 200° C.
• Thermally curing basecoat materials are preferably those which comprise as additional binder a polyurethane resin and as crosslinking agent an aminoplast resin or a blocked or nonblocked polyisocyanate, preferably an aminoplast resin. Among the aminoplast resins, melamine resins are preferred.
• plastics substrates takes place basically in the same way as that of metallic substrates. Here, however, in general, curing takes place at significantly lower temperatures, of 30 to 90° C. Preference is therefore given to the use of two-component clearcoat materials. Preference is further given to use of basecoat materials which comprise a polyurethane resin as binder, but no crosslinker.
• the method of the invention can be used to paint metallic and nonmetallic substrates, more particularly plastics substrates, preferably automobile bodies or components thereof.
• the method of the invention can be used further for dual finishing in OEM finishing. This means that a substrate which has been coated by means of the method of the invention is painted a second time, likewise by means of the method of the invention.
• the invention relates further to multicoat paint systems which are producible by the method described above. These multicoat paint systems are to be referred to below as multicoat paint systems of the invention.
• the multicoat paint systems of the invention are preferably multicoat color paint systems, effect paint systems, and color and effect paint systems.
• a further aspect of the invention relates to the method of the invention, said substrate from stage (1) comprising a multicoat paint system which possesses defects.
• This substrate/multicoat paint system, which possesses defects, is therefore an original finish, which is to be repaired or completely recoated.
• the method of the invention is suitable accordingly for repairing defects on multicoat paint systems.
• Defects or film defects are, generally speaking, disturbances on and in the coating, named usually according to their shape or their appearance.
• the skilled person is aware of a host of possible kinds of such film defects. They are described for example in Römpp-Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 235, “Film defects”.
• the multicoat paint systems produced by means of the method of the invention may likewise have such defects.
• the substrate from stage (1) is a multicoat paint system of the invention which exhibits defects.
• These multicoat paint systems are produced preferably on automobile bodies or parts thereof, by means of the method of the invention, identified above, in the context of automotive OEM finishing. Where such defects occur directly after OEM finishing has taken place, they are repaired immediately.
• OEM automotive refinishing is therefore also used. Where only small defects require repair, only the “spot” is repaired, and the entire body is not completely recoated (dual coating). The latter process is called “spot repair”.
• spot repair The use of the method of the invention for remedying defects on multicoat paint systems (original finishes) of the invention in OEM automobile refinishing, therefore, is particularly preferred.
• this of course means that this substrate/multicoat paint system with defects (original finish) is generally located on a plastic substrate or on a metallic substrate as described above.
• the aqueous basecoat material used in stage (1) of the method of the invention for repairing defects to be the same as that which was used to produce the substrate/multicoat paint system with defects (original finish).
• the above-described defects on the multicoat paint system of the invention can be repaired by means of the above-described method of the invention.
• the surface to be repaired on the multicoat paint system may initially be abraded.
• the abrading is preferably performed by partially sanding, or sanding off, only the basecoat and the clearcoat from the original finish, but not sanding off the primer layer and surfacer layer that are generally situated beneath them. In this way, during the refinish, there is no need in particular for renewed application of specialty primers and primer-surfacers.
• the pigmented aqueous basecoat material is applied to the defect site in the original finish by pneumatic atomization.
• the pigmented aqueous basecoat material can be dried by known methods.
• the basecoat material may be dried at room temperature for 1 to 60 minutes and subsequently dried at optionally slightly elevated temperatures of 30 to 80° C. Flashing and drying for the purposes of the present invention means evaporation of organic solvents and/or water, whereby the coating material is as yet not fully cured.
• the basecoat material it is preferred for the basecoat material to comprise a polyurethane resin as binder and an aminoplast resin, preferably a melamine resin, as crosslinking agent.
• a commercial clearcoat material is subsequently applied, by techniques that are likewise commonplace. Following application of the clearcoat material, it may be flashed at room temperature for 1 to 60 minutes, for example, and optionally dried. The clearcoat is then cured together with the applied pigmented basecoat.
• low-temperature baking curing takes place preferably at temperatures of 20 to 90° C.
• two-component clearcoat materials Preference here is given to using two-component clearcoat materials.
• a polyurethane resin is used as further binder and an aminoplast resin is used as crosslinking agent, there is only slight crosslinking by the aminoplast resin in the basecoat film at these temperatures.
• the aminoplast resin in addition to its function as a curing agent, also serves for plasticizing and may assist pigment wetting.
• nonblocked isocyanates may also be used. Depending on the nature of the isocyanate used, they crosslink at temperatures from as low as 20° C.
• the low-temperature baking is preferably employed.
• a further aspect of the present invention is the use of the reaction product of the invention in pigmented aqueous basecoat materials for improving adhesion. This should be understood as improving adhesion relative to pigmented aqueous basecoat materials which do not comprise a reaction product of the invention.
• the reaction product of the invention can be used for improving adhesion in the coating of metallic and plastic substrates. It can also be used in automotive refinishing.
• automotive refinishing is meant not only OEM automotive refinishing but also the automotive refinishing which takes place, for example, in a workshop.
• the use of the reaction product of the invention leads in particular to an improvement in the adhesion between the basecoat film and the clearcoat film directly adjoining it.
• the reaction product of the invention is therefore used preferably for improving adhesion between basecoat film and clearcoat film in the coating of metallic substrates and plastic substrates.
• the use of the reaction product of the invention leads in particular to an improvement in adhesion between basecoat and original finish.
• the reaction product of the invention is therefore likewise used preferably for improving the adhesion between basecoat film and original finish in automotive refinish, more preferably in OEM automotive refinish.
• condensation-water storage denotes the storage of coated substrates in a climate chamber in accordance with CH test conditions according to DIN EN ISO 6270 2:2005-09.
• reaction products of the invention are therefore also used in particular in order to improve the adhesion following condensation-water storage.
• the adhesion is investigated preferably by means of a steam jet test according to test method A of DIN 55662:2009-12.
• reaction products of the invention are therefore also used in particular to prevent or reduce the incidence of blisters and swelling in multicoat paint systems. The presence of blisters and swelling in this context may be appraised visually.
• the dimer fatty acid used contains less than 1.5 wt % trimeric molecules, 98 wt % dimeric molecules, and less than 0.3 wt % fatty acid (monomer). It is prepared on the basis of linolenic, linoleic, and oleic acids (PripolTM 1012-LQ-(GD) (from Croda)).
• polyester solution has a solids content of 60 wt %, the solvent used being butyl glycol rather than butanol, so the solvents present are primarily butyl glycol and water.
• the number-average molecular weight was determined by means of vapor pressure osmosis. Measurement took place using a vapor pressure osmometer (model 10.00 from Knauer) on concentration series of the component under investigation in toluene at 50° C., with benzophenone as calibration substance for the determination of the experimental calibration constant of the instrument employed (in accordance with E. Schröder, G. Müller, K.-F. Arndt, “Leitfaden der Polymer charactertician”, Akademie-Verlag, Berlin, pp. 47-54, 1982, in which benzil was used as calibration substance).
• Amount of condensate (water): 58.2 g Acid number: 0.6 mg KOH/g Solids content (GC): 100.0% Number-average molecular weight (vapor pressure osmosis): 990 g/mol Viscosity (resin:xylene 2:1): 92 mPas, (measured at 23° C. using a rotational viscometer from Brookfield, model CAP 2000+, spindle 3, shear rate: 10 000 s ⁇ 1 )
• Amount of condensate (water): 77.0 g Acid number: 0.4 mg KOH/g Solids content (GC): 100.0% Number-average molecular weight (vapor pressure osmosis): 2630 g/mol Viscosity (resin:xylene 2:1): 221 mPas, (measured at 23° C. using a rotational viscometer from Brookfield, model CAP 2000+, spindle 3, shear rate: 10 000 s ⁇ 1 )
• aqueous phase in table A were stirred together in the order stated to give an aqueous mixture.
• organic mixture was prepared from the components listed under “organic phase”. The organic mixture was added to the aqueous mixture. The combined mixtures was then stirred for 10 minutes and adjusted using deionized water and dimethylethanolamine to a pH of 8 and to a spray viscosity of 58 mPas under a shearing load of 1000 s ⁇ 1 , as measured using a rotational viscometer (Rheomat RM 180 instrument from Mettler-Toledo) at 23° C.
• a paint was produced as for the production of the comparative waterborne basecoat 1 (C1), using IR1, instead of the polyester P1, both in the aqueous phase and in the organic phase.
• IR1 was used here as an 80% strength solution in butyl glycol. Based on the solids fraction (nonvolatile fraction), the amount of IR1 used in I1 was the same as that of the polyester P1 used in C1. The different amounts of butyl glycol resulting from the different solids of dispersions P1 and IR1 were compensated in the formulation I1 by corresponding addition of butyl glycol.
• a paint was produced as for the production of the comparative waterborne basecoat 1 (C1) using IR2, instead of the polyester P1, both in the aqueous phase and in the organic phase.
• IR2 was used here as an 80% strength solution in butyl glycol. Based on the solids fraction (nonvolatile fraction), the amount of IR2 used in I2 was the same as that of the polyester P1 used in C1. The different amounts of butyl glycol resulting from the different solids of dispersions P1 and IR2 were compensated in the formulation I2 by corresponding addition of butyl glycol.
• Table 1 shows again the polyesters and reaction products, and their proportions (based on the total amount of the waterborne basecoat materials), used in waterborne basecoat materials C1, I1, and I2, as an overview.
• multicoat paint systems were produced in accordance with the following general instructions.
• the respective waterborne basecoat material from table 1 was then applied pneumatically.
• the resulting waterborne basecoat film was flashed at room temperature for 2 minutes and subsequently dried in a forced-air oven at 70° C. for 10 minutes.
• a customary two-component clearcoat material (Progloss® 345 from BASF Coatings GmbH) was applied to the dried waterborne basecoat film.
• the resulting clearcoat film was flashed at room temperature for 20 minutes.
• the waterborne basecoat film and the clearcoat film were then cured in a forced-air oven at 160° C. for 30 minutes.
• the present system represents an overbaked original system and will be referred to below as the original finish.
• This original finish is abraded with abrasive paper and then the respective waterborne basecoat material from table 1 is applied pneumatically to this abraded original finish.
• the resulting waterborne basecoat film was flashed at room temperature for 2 minutes and subsequently dried in a forced-air oven at 70° C. for 10 minutes.
• a so-called 80° C. two-component clearcoat material (FF230500 2K refinish clearcoat, scratchproof, from BASF Coatings GmbH) was applied to the dried waterborne basecoat film.
• the resulting clearcoat film was flashed at room temperature for 20 minutes.
• the waterborne basecoat film and the clearcoat film were then cured in a forced-air oven at 80° C. for 30 minutes.
• the steel panels thus treated were then stored over a period of 10 days in a conditioning chamber under CH test conditions according to DIN EN ISO 6270 2:2005-09. 24 hours after removal from the conditioning chamber, the panels were then inspected for blistering and swelling.
• Table 2 shows the corresponding results for waterborne basecoat materials C1, I1, and I2.
• aqueous phase in table B were stirred together in the order stated to form an aqueous mixture.
• organic mixture was prepared from the components listed under “organic phase”. The organic mixture was added to the aqueous mixture. The combined mixtures was then stirred for 10 minutes and adjusted using deionized water and dimethylethanolamine to a pH of 8 and to a spray viscosity of 58 mPas under a shearing load of 1000 s ⁇ 1 , as measured using a rotational viscometer (Rheomat RM 180 instrument from Mettler-Toledo) at 23° C.
• a paint was produced as for the production of the comparative waterborne basecoat 2 (C2), using IR1, instead of the polyester P1, both in the aqueous phase and in the organic phase.
• IR1 was used here as an 80% strength solution in butyl glycol. Based on the solids fraction (nonvolatile fraction), the amount of IR1 used in I3 was the same as that of the polyester P1 used in C2. The different amounts of butyl glycol resulting from the different solids of dispersions P1 and IR1 were compensated in the formulation I3 by corresponding addition of butyl glycol.
• a paint was produced as for the production of the comparative waterborne basecoat 2 (C2) using IR2, instead of the polyester P1, both in the aqueous phase and in the organic phase.
• IR2 was used here as an 80% strength solution in butyl glycol. Based on the solids fraction (nonvolatile fraction), the amount of IR2 used in I4 was the same as that of the polyester P1 used in C2. The different amounts of butyl glycol resulting from the different solids of dispersions P1 and IR2 were compensated in the formulation I4 by corresponding addition of butyl glycol.
• Table 3 shows again the polyesters and reaction products, and their proportions (based on the total amount of the waterborne basecoat materials), used in waterborne basecoat materials C2, I3, and I4, as an overview.

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• 2013
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