WO2020089019A1 - Procédé de fabrication d'une structure de peinture multicouche à couche de recouvrement en prépolymères contenant des groupes silane - Google Patents

Procédé de fabrication d'une structure de peinture multicouche à couche de recouvrement en prépolymères contenant des groupes silane Download PDF

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Publication number
WO2020089019A1
WO2020089019A1 PCT/EP2019/078965 EP2019078965W WO2020089019A1 WO 2020089019 A1 WO2020089019 A1 WO 2020089019A1 EP 2019078965 W EP2019078965 W EP 2019078965W WO 2020089019 A1 WO2020089019 A1 WO 2020089019A1
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WO
WIPO (PCT)
Prior art keywords
equal
layer
basecoat
acid
silane
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PCT/EP2019/078965
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German (de)
English (en)
Inventor
Florian Golling
Andreas Hecking
Raul Pires
Hans-Josef Laas
Jan Weikard
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Covestro Deutschland Ag
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Publication of WO2020089019A1 publication Critical patent/WO2020089019A1/fr

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    • 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
    • B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • 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
    • B05D2503/00—Polyurethanes
    • 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
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment

Definitions

  • the present invention relates to a method for producing an at least two-layer lacquer structure from a lower basecoat and an upper topcoat layer arranged above it on a substrate, the method comprising the steps of: a) applying a basecoat layer comprising polymers selected from the group consisting of polyacrylates , Polyurethanes, polyether polyols, polycarbonate polyols, polyester polyols, melamine resins, alkyd resins or mixtures thereof on a substrate; b) at least partial curing of the basecoat film; c) applying a topcoat to the basecoat layer applied in step b), the topcoat being the structuring component containing prepolymers containing silane groups with a content of greater than or equal to 20% by weight and less than or equal to 100% by weight based on the cured topcoat layer and comprises a catalyst with a content of greater than or equal to 0.01% by weight and less than or equal to 5% by weight, based on the cured topcoat layer, and the catalyst is selected from the group
  • a primer is first applied to multilayer automotive paint structures, which, depending on the substrate, is intended to improve the adhesion between the substrate and the subsequent layer or layers.
  • This coating can also serve to protect the substrate from corrosion if it is susceptible to corrosion.
  • the primer improves the surface quality by covering any roughness and structure of the surface.
  • a filler is often applied to the primer, particularly in the case of metal substrates, the purpose of which is to further improve the Surface quality and the improvement of the risk of falling rocks.
  • One or more coloring and / or effect layers which are referred to as basecoat, are usually applied to the filler.
  • a highly cross-linked top coat is applied to the basecoat, which ensures the desired glossy look and protects the paint structure from environmental influences.
  • silane-functional prepolymers in particular silane-functional polyurethane prepolymers, can be used to build up topcoat layers.
  • the preparation of polyurethanes containing silane groups can be carried out in various ways, for example by reaction of polyisocyanates or isocyanate-functional prepolymers with silane compounds which are reactive toward isocyanate groups, such as, for. B. secondary aminoalkylsilanes or mercaptoalkylsilanes.
  • Adducts of isocyanatoalkylalkoxysilanes such as. B. isocyanatopropyltrimethoxysilane, and low molecular weight, up to 20 carbon atoms containing, branched diols or polyols are the subject of EP-A 2 641 925.
  • low molecular weight branched diols or polyols up to a proportion of 40 wt .-% further diols and / or polyols, including, for example hydroxyl-containing polyesters or polyacrylates can also be used.
  • WO 2013/189882 describes adducts of isocyanatotrialkyoxysilanes and polyhydric alcohols as additional crosslinking agents in non-aqueous two-component polyurethane coatings (2K-PUR).
  • WO 2014/180623 describes moisture-crosslinking coating compositions which contain at least one adduct of an isocyanatosilane with a hydroxy-functional compound, a tin-containing catalyst and an aminosilane.
  • Monohydric or polyhydric alcohols and polyols are mentioned as suitable hydroxy-functional compounds for the preparation of the adducts, including, in a long list of suitable polymeric polyols, also hydroxy-functional polyacrylates.
  • Vestanat M 95 only uses a low molecular weight 2: 1 adduct (molar) of isocyanatopropytrimethoxysilane and 1,9-nonanediol.
  • WO 2008/034409 describes, by way of example, the partial conversion of a commercially available polyester polyol Desmophen 1145 (Covestro GmbH AG) with a deficit of isocyanatopropyltriethoxysilane. Because of the selected equivalent ratio, less than 15% of the hydroxyl groups originally present in the polyol are urethanized. Furthermore, WO 2014/037265 discloses the production of silane-functional binders with a thiourethane structure by reacting polyols with low-monomer diisocyanate mercaptosilane adducts.
  • silane-functional polymers as an additional crosslinking component in paint structures. These layers use "usual" paint build-up polymers and modify their properties by adding this additional component.
  • the build-up of lacquer layers mainly based on silane-functional polymers is much less common. This is partly due to the fact that top layers with silane-functional polymers as main components on the different base layers show significantly more complex drying properties than the varnishes commonly used. The coating properties vary significantly more and the drying kinetics are significantly worse than those of the known paints.
  • the layer composite being intended to have comparable functional and drying properties to the known paint coatings. It is therefore the object of the present invention to provide a method for producing functional layer composites with silane-functional topcoat layers, the layer composite showing good mechanical properties and excellent drying kinetics. It is also the object of the present invention to provide a laminate with these good mechanical properties and a body part coated with the laminate.
  • the object is achieved for the method by the features of claim 1 and for a layer composite according to the invention by the features of claim 11.
  • Advantageous further developments are specified in the subclaims. They can be combined as required, unless the context clearly indicates the opposite.
  • the references to “comprising”, “containing” etc. preferably mean “essentially consisting of” and very particularly preferably “consisting of”.
  • a method for producing an at least two-layer lacquer structure from a lower basecoat and an upper topcoat layer arranged above it on one Substrate comprising the steps of: a) applying a basecoat layer comprising polymers selected from the group consisting of polyacrylates, polyurethanes, polyether polyols, polycarbonate polyols, polyester polyols, melamine resins, alkyd resins or mixtures thereof on a substrate; b) at least partial curing of the basecoat film; c) applying a topcoat to the basecoat layer applied in step b), the topcoat being the structuring component containing prepolymers containing silane groups with a content of greater than or equal to 20% by weight and less than or equal to 100% by weight based on the cured topcoat layer and comprises a catalyst with a content of greater than or equal to 0.01% by weight and less than or equal to 5% by weight, based on the cured topcoat layer, and the catalyst is selected from the group consisting of polyacrylates, poly
  • the above two-layer paint structure has excellent mechanical properties.
  • the resulting lacquer composite is highly elastic and both layers show very good adhesion. This is highly surprising, since normally prepolymers containing silane groups have property profiles that depend strongly on the substrate and actually only adhere poorly to the above-mentioned basecoats. This is in contrast to other substrates such as glass, on which the silane group-containing
  • Prepolymers have reasonable adhesion.
  • drying behavior of the topcoat layer is also surprising, since normally topcoat layers composed of prepolymers containing silane groups on base coat layers of the abovementioned polymers have only insufficient drying properties. In contrast to drying on glass, drying takes place only very slowly, which prevents economical use.
  • mechanically stable layer composites can be obtained from at least two layers. Without being bound by theory, the stability of the composite with a topcoat layer of silane group-containing prepolymers seems to be achievable over the specially selected catalysts, which apparently do not only lead to a mechanical one
  • the catalyst is selected from the group consisting of protonic acids or mixtures thereof.
  • protonic acids such as, for example, aluminum compounds, in particular aluminum triisopropylate, aluminum tri-sec-butoxide and other alcoholates and aluminum acetylacetonate, are not catalysts according to the invention.
  • an at least two-layer lacquer structure is produced.
  • the two-layer structure according to the invention can be used as the sole structure for modifying a substrate or in combination with further layers.
  • the lacquer layer structure according to the invention is thus characterized by a physical contact between the base lacquer layer according to the invention and the top lacquer layer according to the invention. Additional layers can also be arranged above the topcoat layer, which can be applied independently of the topcoat layer according to the invention after it has hardened. It is also a sandwich from the composite according to the invention, which has the combination of both layers on the inside.
  • the layer composite has at least a lower basecoat and an upper topcoat layer arranged above it. This means that from the substrate to the air side, the basecoat is closer to the substrate and the topcoat layer is closer to the air.
  • the upper topcoat layer can be a clearcoat layer, this means that the topcoat layer is transparent and the optical properties of the layer composite are determined via the optical properties of the basecoat film.
  • the transparency of a pigmented or unpigmented system means its property of scattering the light as little as possible. Accordingly, the color change of the black background should be as small as possible when applied to a black background. The transparency of the pigmented or unpigmented system is higher, the smaller the color difference from the black background.
  • the transparency of a top coat is determined based on DIN 55988: 2013-04.
  • the two-layer composite is arranged on a substrate.
  • Suitable substrates are known to the person skilled in the art.
  • the layered composite can be applied to solid substrates such as glass or metal.
  • polymeric carrier materials for example printed circuit boards.
  • Suitable metal surfaces are for example iron, steel, aluminum or the like.
  • the substrates can be uncoated or coated.
  • primers and / or fillers may already have been applied to the substrate before it is used in the method according to the invention.
  • primers are, in particular, cathodic dip coatings, such as those used in automotive painting, solvent-based or aqueous primers for plastics, in particular for plastics with low surface tension, such as PP or PP-EPDM.
  • the substrates to be provided can be a body or parts thereof, which comprises one or more of the aforementioned materials.
  • the body or parts thereof preferably comprise one or more materials selected from metal, plastic or mixtures thereof.
  • the substrate can comprise metal, in particular the substrate can contain 80% by weight, 70% by weight, 60% by weight, 50% by weight, 25% by weight, 10% by weight, 5% by weight. -%, 1 wt .-% consist of metal.
  • the substrate can at least partially consist of a composite material, in particular a composite material comprising metal, glass, carbon fiber and / or plastic.
  • a basecoat layer comprising polymers selected from the group consisting of polyacrylates, polyurethanes, polyether polyols, polycarbonate polyols, polyester polyols, melamine resins, alkyd resins or mixtures thereof is applied to a substrate.
  • This first step together with the next step leads to the formation of the basecoat layer.
  • the substrate can of course also be pretreated by further steps above, for example by smoothing, roughening or cleaning the surface.
  • the basecoat can be a one-component (IC) system, a two-component (2K) or multi-component (3K, 4K) system.
  • IC one-component
  • 2K two-component
  • 3K, 4K multi-component
  • a one-component (IC) system is to be understood as a thermally curing coating material in which the binder and the crosslinking agent are side by side, i.e. in one component.
  • the first constituent of the coating material of the basecoat can comprise at least one, in particular one, saturated, unsaturated and / or grafted with olefinically unsaturated compounds, ionically and / or non-ionically stabilized polyurethane (A), preferably based on aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, araliphatic, aliphatic-aromatic and / or cycloaliphatic-aromatic polyisocyanates.
  • the polyurethane (A) can either contain (A) either contain
  • the coating material is physically, thermally self-crosslinking or thermally self-crosslinking and curable with actinic radiation
  • its polyurethane content (A) is preferably 50 to 100% by weight, preferably 50 to 90% by weight and in particular 50 to 80% by weight .-%, each based on the film-forming solid of the coating material.
  • the coating material is thermally crosslinking or thermally crosslinking and curable with actinic radiation
  • its polyurethane content (A) is preferably 10 to 80, preferably 15 to 75 and in particular 20 to 70% by weight, in each case based on the film-forming solid of the coating material.
  • the film-forming solid is to be understood as the sum of all constituents of the coating material which build up the solid of the thermoplastic or thermosetting materials produced therefrom, preferably the thermoplastic or thermosetting coatings, adhesive layers, seals, foils and moldings, in particular the thermosetting coatings.
  • the second constituent of the coating material can be a wetting or dispersing agent (B) which is selected from the group consisting of hyperbranched polymers, polyether-modified polydimethylsiloxanes, ionic and non-ionic (meth) acrylate copolymers, high-molecular block copolymers with pigment-affine groups and dialkyl sulfosuccinates.
  • B wetting or dispersing agent
  • hyperbranched polymers polyether-modified polydimethylsiloxanes, ionic and non-ionic (meth) acrylate copolymers, high-molecular block copolymers with pigment-affine groups and dialkyl sulfosuccinates.
  • hyperbranched polymers are used.
  • the wetting or dispersing agents (B) are known, commercially available materials and are, for example, from BASF under the brands Starfactant 20 and Hydropalat 875, from Byk Chemie under the brands Disperbyk 162, 163 and 182 and Byk 348 , 355, 381 and 390, distributed by Coatex under the Coatex P90 and BP3 brands and Efka under the Efka 4580 brand.
  • Starfactant 20 is used in particular.
  • the wetting or dispersing agents (B) are used in the customary and known, effective amounts. They are preferably used in an amount of 0.01 to 5, preferably 0.05 to 2.5 and in particular 0.1 to 1.5% by weight, in each case based on the coating material.
  • the third component of the coating material can be at least one organic solvent (C).
  • Suitable solvents are described, for example, in German patent application DE 102 005 060 A1, page 5 to page 6, paragraphs [0038] to [0040].
  • the solvent can preferably be triethylene glycol.
  • organic solvent (C) can vary widely and can thus be optimally adapted to the requirements of the individual case.
  • organic solvent (C) content in view of the aqueous nature of the coating material, efforts are made to keep its organic solvent (C) content as low as possible. It is a particular advantage here that an organic solvent (C) content of the coating material of 0.1 to 10, preferably 0.5 to 7 and in particular 0.5 to 5% by weight, based in each case on the coating material, is sufficient to achieve beneficial technical effects.
  • the coating material can also contain an additive (D). It preferably contains at least two additives (D).
  • the additive (D) is preferably selected from the group of additives usually used in the field of coating materials.
  • the additive (D) from the group consisting of residue-free or essentially residue-free thermally decomposable salts is particularly preferred; binders which are different from the polyurethanes (A) and are curable physically, thermally and / or with actinic radiation; Crosslinking agents; organic solvents other than organic solvents (C); thermally curable reactive thinners; reactive diluents curable with actinic radiation; coloring and / or effect pigments; transparent pigments; Fillers; molecularly dispersible luminescent materials; Nanoparticles; Light stabilizers; Antioxidants; Deaerators; Emulsifiers; Slip additives; Polymerization inhibitors; Radical polymerization initiators; thermolabile free radical initiators; Adhesion promoters; Leveling agents; film-forming aids, such as
  • Suitable additives (D) of the type mentioned above are, for example, from German patent application DE 199 48 004 A1, page 14, line 4, to page 17, line 5, and German patent application DE 199 14 98 Al, column 11, line 9, to Column 15, line 63, or the German patent DE 100 43 405 CI, column 5, paragraphs [0031] to [0033]. They are used in the usual and known, effective amounts.
  • the solids content of the coating material can vary very widely and can therefore be optimally adapted to the requirements of the individual case.
  • the solids content primarily depends on the viscosity required for the application, in particular spray application, so that it can be adjusted by the person skilled in the art on the basis of his general specialist knowledge, possibly with the aid of less orienting experiments.
  • the solids content is preferably 5 to 70, preferably 10 to 65 and in particular 15 to 60% by weight, in each case based on the coating material.
  • the coating material is preferably produced using a coating process.
  • the constituents (A), (B) and (C) and optionally (D) described above are dispersed in an aqueous medium, in particular in water, after which the resulting mixture is homogenized. From a methodological point of view, the method has no special features in terms of method, but can be carried out using the customary and known mixing processes and mixing units, such as stirred kettles, dissolvers, agitator mills, kneaders, static mixers, extruders, or in a continuous process. Because of the advantages of the coating material and the coating material produced by means of the method, numerous purposes can be fulfilled. They are preferably used for the production of the thermoplastic and thermosetting, in particular thermosetting, materials. They are preferably used as coating materials for the production of thermoplastic and thermosetting, in particular thermosetting, coatings, which can be bonded to primed and unprimed substrates of all kinds in a adhesively bonded or detachable manner.
  • suitable substrates are known from German patent application DE 199 48 004 A1, page 17, lines 12 to 36, or German patent DE 100 43 405 CI, column 2, paragraph [0008], to column 3, paragraph [0017] .
  • the coating materials are particularly preferably used as topcoats for the production of topcoats or as water-based lacquers for the production of color and / or effect multi-layer coatings. They are very particularly preferred as water-based basecoats for the production of color and / or effect basecoats of multi- layer coatings, preferably multi-layer coatings for automobile bodies, used.
  • Multilayer coatings can very particularly preferably be produced using a wet-on-wet method, with at least one water-based lacquer being applied to a primed or unprimed substrate, resulting in at least one water-based lacquer layer.
  • thermoplastic and thermoset materials produced from it also have an outstandingly balanced physico-chemical, optical and mechanical property profile. Therefore, the films and molded parts as well as the substrates coated with the coatings have a particularly high utility value and a long service life.
  • Additional basecoat layers can be basecoat layers for low stoving temperatures.
  • An exemplary embodiment includes a curable coating composition for a low bake temperature basecoat: a crosslinkable component comprising an acid functional acrylic copolymer polymerized from a monomer mixture comprising 2% to 12% by weight of one or more Monomers containing carboxylic acid group (s), the percentages based on the total weight of the acid-functional acrylic copolymer, a crosslinking component; and a low baking temperature control agent comprising a rheology component selected from an amorphous silica gel, a clay, or a combination thereof, the rheology component being present in an amount of about 0.1 to about 10% by weight and about 0.1% to about 10% by weight polyurea, the percentages being based on the total weight of the crosslinkable and crosslinking components.
  • a crosslinkable component comprising an acid functional acrylic copolymer polymerized from a monomer mixture comprising 2% to 12% by weight of one or more Monomers containing carboxylic acid group (s), the percentages based on the total weight of the acid
  • the multi-layer coating system includes: a curable basecoat coating for a low baking temperature comprising: a crosslinkable component comprising an acid functional acrylic copolymer polymerized from a monomer mixture comprising 2% by weight to 12% by weight of monomers containing one or more carboxylic acid groups, the percentages being based on the total weight of the acid functional acrylic copolymer, a crosslinking component; and a low baking temperature control agent comprising a rheology component selected from an amorphous silica gel, a clay, or a combination thereof, the rheology component being present in an amount from about 0.1 to about 10 percent by weight and about 0.1 % By weight to about 10% by weight of polyurea, the percentages being based on the total weight of the crosslinkable and crosslinking components.
  • a curable basecoat coating for a low baking temperature comprising: a crosslinkable component comprising an acid functional acrylic copolymer polymerized from a monomer mixture comprising 2% by weight to 12% by weight
  • the present coating composition includes a crosslinkable and crosslinking component.
  • the crosslinkable component includes from about 2% to about 25%, preferably from about 3% to about 20%, more preferably from about 5% to about 15% by weight of one or more acid-functional acrylic Copolymers, all percentages based on the total weight of the crosslinkable component. If the composition contains more than the upper limit of the acid functional acrylic copolymer, the resulting composition will typically have more than the required application viscosity. If the composition contains less than the lower limit of the acid-functional copolymer, the coating obtained would have insignificant strike-in (or mixing) properties for a multilayer structure or system or scale or flake orientation.
  • the crosslinkable component contains an acid functional acrylic copolymer polymerized from a monomer mixture comprising about 2% to about 12%, preferably about 3% to about 10%, more preferably about 4% by weight Wt .-% to about 6 wt .-% of one or more carboxylic acid containing monomers, all percentages on the
  • Total weight of the acid-functional acrylic copolymer is based. If the amount of carboxylic acid group-containing monomer in the monomer mixture exceeds the upper limit, the coatings resulting from such a coating composition would have unacceptable water sensitivity, and if the amount was less than the lower limit, the coating obtained would become insignificant " Strike-in "properties for a multilayer structure or system or scale orientation control in general.
  • the acid-functional acrylic copolymer preferably has a weight average molecular weight according to GPC (in g / mol), determined in accordance with DIN 55672: 2016-03, in the range from about 8000 to about 100000, preferably from about 10,000 to about 50,000 and more preferably from about 12,000 to about 30,000.
  • the copolymer preferably has a polydispersity in the range from about 1.05 to about 10.0, preferably in the range from about 1.2 to about 8, and more preferably in the range from about 1.5 to about 5.
  • the copolymer preferably has a T g ranging from about -5 ° C to about +100 ° C, preferably from about 0 ° C to about 80 ° C, and more preferably from about 10 ° C to about 60 ° C.
  • the monomers containing carboxylic acid group (s) suitable for use in the present invention include (meth) acrylic acid, crotonic acid, oleic acid, cinnamic acid, glutaconic acid, muconic acid, undecylenic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or a combination thereof.
  • (Meth) acrylic acid is preferred. It is understood that users can also provide the acid functional acrylic copolymer having carboxylic acid groups by producing a copolymer polymerized from a monomer mixture containing anhydrides of the above-mentioned carboxylic acids and then hydrolyzing such copolymers to provide the obtained copolymer with carboxylic acid groups.
  • Maleic and itaconic anhydrides are preferred. Users may also consider hydrolyzing such anhydrides in their monomer mixture prior to polymerizing the monomer mixture to the acid functional acrylic copolymer.
  • the monomer mixture suitable for use in the present invention includes about 5 percent to about 40 percent, preferably about 10 percent to about 30 percent, of one or more functional (meth) acrylate monomers, all based on the total weight of the acid-functional acrylic Copolymers based. It should be noted that if the amount of functional (meth) acrylate monomers in the monomer mixture exceeds the upper limit, the pot life of the coating composition obtained is reduced, and if less than the lower limit is used, it will affect the coating properties obtained, such as durability, negatively influenced.
  • the functional (meth) acrylate monomer can be provided with one or more crosslinkable groups selected from a primary hydroxyl, secondary hydroxyl, or a combination thereof.
  • Suitable hydroxyl-containing (meth) acrylate monomers may have the following structure: wherein RH is methyl and X is a divalent unit which can be substituted or unsubstituted Ci to Ci8 linear aliphatic unit or substituted or unsubstituted C3 to Cis branched or cyclic aliphatic unit.
  • X is a divalent unit which can be substituted or unsubstituted Ci to Ci8 linear aliphatic unit or substituted or unsubstituted C3 to Cis branched or cyclic aliphatic unit.
  • substituents include nitrile, amide, halide such as chloride, bromide, fluoride, acetyl, acetoacetyl, hydroxyl, benzyl and aryl.
  • Some specific hydroxyl-containing (meth) acrylate monomers in the monomer mixture include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate a.
  • the monomer mixture can also include one or more non-functional (meth) acrylate monomers.
  • non-functional groups are those that do not crosslink with a crosslinking component.
  • suitable non-functional CI to C20 alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, isodecyl (meth) acrylate and lauryl (meth) acrylate; branched alkyl monomers such as isobutyl (meth) acrylate, t-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; and cyclic alkyl monomers such as cyclo
  • the monomer mixture can also include one or more of other monomers for the purpose of achieving the desired properties, such as hardness, appearance, and damage resistance.
  • Some of the other such monomers include, for example, styrene, alpha-methylstyrene, acrylonitrile and methacrylonitrile. If included, the monomer mixture preferably includes such monomers in the range of about 5 percent to about 30 percent, all percentages being in weight percent based on the total weight of the polymer solids. Styrene is preferred.
  • Any conventional bulk or solution polymerization process can be used to make the acid functional acrylic copolymer of the present invention.
  • One of the suitable methods for making the copolymer of the present invention includes free radical solution polymerization of the monomer mixture described above.
  • the polymerization of the monomer mixture can be carried out by adding conventional heat initiators, such as Azos, exemplified by Vazo 64, obtained from DuPont Company, Wilmington, Delaware; and peroxides such as t-butyl peroxyacetate are started.
  • the molecular weight of the copolymer obtained can be controlled by adjusting the reaction temperature, the selection and the amount of the initiator used, as carried out by a person skilled in the art.
  • the crosslinking component of the present invention can include one or more polyisocyanates, melamines, or a combination thereof. Polyisocyanates are preferred.
  • the polyisocyanate is provided in the range of about 2 to about 10, preferably about 2.5 to about 8, more preferably about 3 to about 5 isocyanate functionalities.
  • the ratio of equivalents of isocyanate functionalities to the polyisocyanate per equivalent of all of the functional groups present in the crosslinking components ranges from about 0.5 / 1 to about 3.0 / 1, preferably from about 0 .7 / 1 to about 1.8 / 1, more preferably from about 0.8 / 1 to about 1.3 / 1.
  • Some suitable polyisocyanates include aromatic, aliphatic or cycloaliphatic polyisocyanates, trifunctional polyisocyanates, and isocyanate-functional adducts of a polyol and difunctional isocyanates.
  • polyisocyanates include diisocyanates such as 1,6-hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, 4,4'-biphenylene diisocyanate, toluene diisocyanate, 4,4-methylene dicyclohexyl diisocyanate,
  • trifunctional polyisocyanates include triphenylmethane triisocyanate, 1,3,5-benzene triisocyanate and 2,4,6-toluene triisocyanate.
  • Trimers of diisocyanate such as the trimer of hexamethylene diisocyanate, sold under the trademark Desmodur N-3390 by Covestro AG, Leverkusen, North Rhine-Westphalia, and the trimer of isophorone diisocyanate are also suitable.
  • Trifunctional adducts of triols and diisocyanates are also suitable. Trimers of diisocyanates are preferred and trimers of isophorone, pentamethylene and hexamethylene diisocyanates are more preferred.
  • the coating composition may contain from about 0.1% to about 40%, preferably from about 15% to about 35%, and more preferably from about 20% to about 30% by weight of the Include melamines, the percentages based on the total weight of composition solids.
  • the suitable melamines include monomeric melamine, polymeric melamine-formaldehyde resin, or a combination thereof.
  • the monomeric melamines close Low molecular weight melamines containing an average of three or more methylol groups etherified with a monohydric CI to C5 alcohol, such as methanol, n-butanol or isobutanol, per triazine nucleus and an average degree of condensation of up to about 2 and preferably im Range from about 1.1 to about 1.8, and have a mononuclear species content of not less than about 50% by weight.
  • the polymeric melamines have an average degree of condensation of more than about 1.9.
  • Suitable monomeric melamines include alkylated melamines, such as methylated, butylated, isobutylated melamines, and mixtures thereof. Many of these suitable monomeric melamines are supplied commercially. For example, Cytec Industries Ine., West Patterson, New Jersey, Cymel 301 (degree of polymerization of 1.5, 95% methyl and 5% methylol), Cymel 350 (degree of polymerization of 1.6, 84% methyl and 16% methylol), 303, 325, 327, 370 and XW3106, all of which are monomeric melamines.
  • Suitable polymeric melamines include high amino content melamine (partially alkylated, -N, -H) known as Resimene BMP5503
  • Cytec Industries Inc. also supply Cymel 1130 with 80 percent solids (degree of polymerization 2.5), Cymel 1133 (48% methyl, 4% methylol and 48% butyl), both of which are polymeric melamines.
  • suitable catalysts contained in the crosslinkable component can accelerate the curing process of a pot mix of the coating composition.
  • the crosslinkable component of the coating composition preferably includes a catalytically active amount of one or more catalysts to accelerate the curing process.
  • a catalytically active amount of the catalyst in the coating composition ranges from about 0.001 percent to about 5 percent, preferably ranges from about 0.005 percent to about 2 percent, more preferably ranges from about 0.01 percent to about 1 percent, all in % By weight, based on the total weight of crosslinkable and crosslinking component solids, are present.
  • catalysts can be used, such as tin compounds, including dibutyltin dilaurate and dibutyltin diacetate; tertiary amines such as triethylene diamine.
  • catalysts can be used individually or in combination with carboxylic acids such as acetic acid or benzoic acid.
  • carboxylic acids such as acetic acid or benzoic acid.
  • the crosslinking component includes melamine, it also preferably includes a catalytically active amount of one or more acidic catalysts to further increase the crosslinking of the components upon curing.
  • the catalytically active amount of the acidic catalyst in the coating composition ranges from about 0.1 percent to about 5 percent, preferably in the range from about 0.1 percent to about 2 percent, more preferably in the range from about 0.5 percent to about 1.2 percent, all in weight percent based on the total weight of crosslinkable and crosslinking component solids.
  • Some suitable acidic catalysts contain aromatic sulfonic acids such as dodecylbenzenesulfonic acid, para-toluenesulfonic acid and dinonylnaphthalenesulfonic acid, all of which are either unblocked or with an amine such as dimethyloxazolidine and 2-amino-2-methyl-1-propanol, N, N-dimethylethanolamine or a combination thereof are blocked.
  • Other acidic catalysts that can be used are strong acids, such as phosphoric acids, especially phenylic acid phosphate, which can be unblocked or blocked with an amine.
  • the crosslinkable component of the coating composition may further range from about 0.1 percent to about 95 percent, preferably from about 10 percent to about 90 percent, more preferably from about 20 percent to about 80 percent, and most preferably from about Include 30 percent to about 70 percent of an acrylic polymer, polyester, or a combination thereof, all based on the total weight of the crosslinkable component.
  • the acrylic polymer suitable for use in the present invention may have a weight average molecular weight (in g / mol) according to GPC that exceeds 2000, preferably in the range of about 3000 to about 20,000, and more preferably in the range of about 4,000 to about 10,000.
  • the T g of the acrylic polymer varies in the range from 0 ° C. to approximately 100 ° C., preferably in the range from approximately 10 ° C. to approximately 80 ° C.
  • the acrylic polymer suitable for use in the present invention can conventionally be made from typical monomers such as alkyl (meth) acrylates having alkyl carbon atoms in the range of 1 to 18, preferably in the range of 1 to 12, and styrene and functional monomers such as Hydroxyethyl acrylate and hydroxyethyl methacrylate can be polymerized.
  • typical monomers such as alkyl (meth) acrylates having alkyl carbon atoms in the range of 1 to 18, preferably in the range of 1 to 12, and styrene and functional monomers such as Hydroxyethyl acrylate and hydroxyethyl methacrylate can be polymerized.
  • the polyester suitable for use in the present invention may have a GPC weight average molecular weight exceeding 1500, preferably in the range of about 1500 to about 100000, more preferably in the range of about 2000 to about 50,000, more preferably in the range of about 2000 to about 8000 and particularly preferably in the range from about 2000 to about 5000.
  • the T g of the polyester varies in the range from about -50 ° C to about +100 ° C, preferably in the range from about -20 ° C to about +50 ° C.
  • polyester suitable for use can be polymerized in a conventional manner from suitable polyacids, including cycloaliphatic polycarboxylic acids, and suitable polyols, including polyhydric alcohols.
  • suitable polyacids including cycloaliphatic polycarboxylic acids
  • suitable polyols including polyhydric alcohols.
  • Polycarboxylic acids are tetrahydrophthalic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-
  • the cycloaliphatic polycarboxylic acids can be used not only in their cis but also in their trans form and as a mixture of both forms.
  • suitable polycarboxylic acids which, if desired, can be used together with the cycloaliphatic polycarboxylic acids are aromatic and aliphatic polycarboxylic acids, such as, for example, phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids, such as tetrachloro- or tetrabromophthalic acid, adipic acid, glutaric acid, sebaric acid, sebacic acid, azine acid, sebacic acid, azine acid, sebacic acid, azine acid, sebacic acid, azine acid, sebacic acid, azine acid, sebacic acid, azine acid, sebacic acid, azide Fumaric acid, maleic acid, trimellitic acid and pyromellitic acid.
  • aromatic and aliphatic polycarboxylic acids such as, for example, phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids,
  • Suitable polyhydric alcohols include ethylene glycol, propanediols, butanediols, hexanediols, neopentyl glycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol, ethylbutylpropanediol, ditrimethylolpropane, trimethylolethane, trimethylolpropane, triethylglycol, tritylthryglycol, pentrylytyl glycol, pentrylytyl glycol, pentrylyl glycol, pentrylyl glycol, tritylthryglycol, pentrylyl glycol, pentrylyl glycol, pentrylyl glycol, pentrylyl glycol, tritylthryglycol, pentrylyl glycol, pentrylyl glycol, pentrylyl glycol, pentry
  • the crosslinkable component can further include one or more reactive oligomers, such as non-alicyclic (linear or aromatic) oligomers, disclosed in US 6,221,494 B4, page 3, column 4, line 1 to line 48, which are incorporated herein by reference .
  • Such non-alicyclic oligomers can be prepared using non-alicyclic anhydrides such as succinic or phthalic anhydrides or mixtures thereof.
  • the crosslinkable component of the coating composition may further include one or more modifying resins, which are also known as non-aqueous dispersions (NADs). Such resins are sometimes used to adjust the viscosity of the coating composition obtained.
  • the amount of modifying resin that can be used is typically in the range of about 10% to about 50% by weight, with all products percentages are based on the total weight of crosslinkable component solids.
  • the weight average molecular weight of the modifying resin, determined according to DIN 55672: 2016-03, is generally in the range (in g / mol) from about 20,000 to about 100,000, preferably in the range from about 25,000 to about 80,000 and more preferably in the range of about 30,000 to about 50,000.
  • the crosslinkable or crosslinking component of the coating composition of the present invention typically contains at least one organic solvent, typically from the group consisting of aromatic hydrocarbons such as petroleum naphtha or xylenes; Ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone; Esters such as butyl acetate or hexyl acetate; and glycol ether esters such as propylene glycol monomethyl ether acetate.
  • the amount of organic solvent added depends on the desired solids content and the desired amount of VOC of the composition. If desired, the organic solvent can be added to both components of the binder. A high solids, low VOC coating composition is preferred.
  • baking temperature control means with either the crosslinkable component, the crosslinking component, or both of the
  • the low bake temperature control agent of the present invention includes a rheology component.
  • the rheology component includes an amorphous silica gel, a clay, or a combination of both.
  • the low bake temperature control means includes from about 0.1% to about 10%, preferably from about 0.3% to about 5%, more preferably from about 0.5% % By weight to about 2% by weight of the rheology component, and in the range from approximately 0.1% by weight to approximately 10% by weight, preferably in the range from approximately 0.3% by weight to approximately 5 weight percent, and more preferably in the range of about 0.5 weight percent to about 2 weight percent of polyurea, the weight percentages being based on the total weight of the crosslinkable and crosslinking components of the curable, low bake coating composition of the present invention.
  • Suitable amorphous silica gels include colloidal silica gels, which are characterized by the Silanization of hydroxyl groups on the silica gel particles has been partially or completely surface modified, making some or all of the silica gel particle surface hydrophobic.
  • suitable hydrophobic silica gel include ⁇ ROSIL R972, ⁇ ROSIL R812, ⁇ ROSIL OK412, ⁇ ROSIL TS-100 and ⁇ ROSIL R805, all of which are commercially available from Evonik Industries AG, Essen, Germany.
  • Pyrogenic silica gel is particularly preferably available from Evonik Industries AG, Essen, Germany, as ⁇ ROSIL R 812.
  • Other commercially available silica gel includes SIBELITE M3000 (Cristobalite), SIL-CO-SIL, ground silica gel, MIN-U-SIL, micronized silica gel, all of which are obtained from US Silica Gel Company, Berkeley Springs, West Virginia.
  • the silica gel can be dispersed in the copolymer by a grinding process using conventional equipment such as high speed blade mixers, ball mills or sand mills.
  • the silica gel is separately dispersed in the previously described acrylic polymer and then the dispersion can be added to the crosslinkable component of the coating composition.
  • the clay suitable for use herein may include clay, dispersed clay, or a combination thereof.
  • examples of commercially available clay products include bentonite clay, available as BENTONE from Elementis Specialties, London, UK, and GARAMITE clay, available from Southern Ton Products, Gonzales, TX, USA, under registered trademarks.
  • BENTONE 34 dispersion described in U.S. Patent No. 8,357,456, and GARAMITE dispersion, described in U.S. Patent No. 8,227,544, and a combination of the two are suitable.
  • a combination of the silica gel and the clay such as the aforementioned BENTONE, GARAMITE or dispersions thereof can also be used.
  • the polyurea suitable for use in the low bake temperature control agent is obtained from the polymerization of a monomer mixture comprising about 0.5 to about 3 percent by weight of the amine monomers, about 0.5 to about 3 percent by weight of the isocyanate Monomers, and from about 94 to about 99 weight percent of a moderating polymer.
  • the amine monomer is selected from the group consisting of a primary amine, secondary amine, ketimine, aldimine, or a combination thereof. Benzylamine is preferred.
  • the isocyanate monomer is selected from the group consisting of an aliphatic polyisocyanate, cycloaliphatic polyisocyanate, aromatic polyisocyanate, and a combination thereof.
  • the preferred isocyanate monomer is 1,6-hexamethylene diisocyanate or 1,5-pentamethylene diisocyanate.
  • the moderating polymer can be one or more of the polymers described above.
  • the acrylic polymers or polyesters are preferred.
  • the polyurea is obtained by mixing one or more of the Moderating polymers made with the amine monomers and then isocyanate monomers are added over time under ambient conditions.
  • the run-off resistance of a layer of a pot mix or mixing mixture which results from mixing the crosslinkable and crosslinking components of the present coating composition when applied to a substrate, is in the range from about 5 (127 micrometers) to about 20 mils (508 microns) when measured by ASTM D4400-99. The higher the number, the higher the desired resistance to running.
  • the coating composition is preferably used as a two-component
  • the coating composition is preferably used as an automotive OEM
  • compositions or formulated as an automotive repair composition can be applied as a basecoat or as a pigmented single-coat topcoat to a substrate. These compositions require the presence of pigments. Typically a pigment to binder ratio of from about 1.0 / 100 to about 200/100 is used depending on the color and type of pigment used.
  • the pigments are formulated into regrinds by conventional methods such as milling, sand milling, and high speed mixing. Generally, the millbase comprises pigment and a dispersant in an organic solvent. The millbase is added to the coating composition in an appropriate amount with mixing to form a pigmented coating composition.
  • any of the commonly used organic and inorganic pigments such as white pigments, for example titanium dioxide, color pigments, metallic flakes, for example aluminum flakes, special effect pigments, for example coated mica flakes and coated aluminum flakes, and extender pigments, can be used.
  • the coating composition can also include other conventional formulation additives such as wetting agents, leveling agents and flow control agents, for example Resiflow S
  • composition to help stabilize include composition to help stabilize.
  • Other additives that typically improve damage resistance can be added, such as silsesquioxane and other silicate-based microparticles.
  • an ultraviolet light stabilizer or a combination of ultraviolet light stabilizers and absorbent may be added.
  • These stabilizers include ultraviolet light absorbers, screeners, quenchers and special hindered amine light stabilizers.
  • an antioxidant can also be added.
  • the coating composition is preferably formulated in the form of a two-component coating composition.
  • the present invention is particularly useful as a basecoat for outdoor objects such as vehicles and other vehicle body parts.
  • the vehicle or the other vehicle body part can be constructed from one or more materials. Suitable materials are, for example, metal, plastic or their mixtures.
  • the vehicle can be any vehicle known to those skilled in the art.
  • the vehicle can be a motor vehicle, fast motor vehicle, motorcycle, scooter, bicycle or the like.
  • the vehicle is preferably a motor vehicle and / or fast motor vehicle (FKW vehicle), particularly preferably it is a motor vehicle.
  • a typical motor vehicle or PKW body is made from a steel sheet or a plastic or a composite substrate.
  • the fenders can be made of plastic or a composite material and the main body of the body can be made of steel.
  • steel When steel is used, it is first treated with an inorganic anti-rust compound, such as zinc or iron phosphate, called an E-coating, and then a primer coating is generally applied by electrodeposition.
  • these electrodeposition primers are epoxy modified resins crosslinked with a polyisocyanate and are applied by a cathodic electrodeposition process.
  • a primer can be applied over the electrodeposited primer, usually by spraying, to provide better appearance and / or improved adhesion of a base coat or mono-coating to the primer.
  • the basecoat can also be built up without melamine.
  • the known basecoat formulations can be used both solvent-based and aqueous.
  • the basecoat layer can be essentially free of melamine and its derivatives.
  • essentially free means in particular that melamine and its derivatives in the basecoat layer in amounts of less than 5% by weight, preferably less than 3% by weight, particularly preferably less than 1% by weight, based on the Total weight of the non-volatile components of the basecoat layer are present. Melamine or its derivatives present in these quantities in the basecoat layer undercut when hardened Heat supply makes no significant contribution to the crosslinking of the basecoat layer.
  • the basecoat layer is free of melamine and its derivatives.
  • the basecoat film according to the invention comprises at least one NCO-reactive compound.
  • Suitable NCO-reactive compounds for the basecoat layer are polyether polyols, polycarbonate polyols, polyester polyols, polyacrylate polyols, polyurethane polyols, polyacrylate polyols, as have already been described above for the clear lacquer layer.
  • Preferred as the NCO-reactive compound in the basecoat layer is one or more selected from polyester polyols, polyacrylate polyols and / or
  • the basecoat layer can comprise at least one NCO-reactive compound.
  • the basecoat can be a one-component paint and have no pot life.
  • no pot life means that the ready-to-apply basecoat is stable in storage for more than 7 days, preferably more than 2 weeks, particularly preferably more than 4 weeks, i.e. even after 7 days, 2 weeks or 4 weeks with the same properties as fresh manufactured, can be used.
  • step b) the basecoat film is at least partially cured.
  • the basecoat can be applied, for example, using the following procedure.
  • the process includes the following process steps:
  • the crosslinkable component of the above described coating composition of the present invention is mixed with the crosslinking component of the coating composition to form a pot mix.
  • the crosslinkable component and the crosslinking component are mixed shortly before application to form a pot mix or a mixing batch. Mixing can take place via a conventional mixing nozzle or separately in a container.
  • a layer of the pot mix is generally applied with a thickness in the range of about 15 microns to about 200 microns on a substrate, such as an automobile body or an automobile body, which has been precoated with an E-coating, followed by one Primer.
  • the preceding application step can be carried out by spraying, electrostatic spraying, commercially available robot spraying systems, roller coating, dipping, flooding or brushing the pot mix or Mixed approach can be applied over the substrate.
  • the layer is allowed to evaporate, ie exposed to the air, in order to reduce the solvent content of the pot-mix or mixing batch layer, so that a "strike-in" -resistant or mix-resistant layer is produced.
  • the period of evaporation Steps are in the range of about 5 to about 15 minutes.
  • a layer of a clear lacquer composition with a thickness in the range of about 15 micrometers to about 200 micrometers can be applied by the previously described application agent via the “strike-in” resistant or mixture-resistant Layer are applied to form a multi-layer system on the substrate.
  • a layer of the pot mix is generally applied with a thickness in the range from approximately 15 micrometers to approximately 200 micrometers onto a substrate, such as a motor vehicle body or a motor vehicle body, with an E-coating followed by a Primer, or a primer has been pre-coated.
  • the preceding application step can be applied over the substrate by spraying, electrostatic spraying, commercially available robot spraying systems, roller coating, dipping, flooding or brushing the pot mix or mixing batch.
  • the layer is allowed to evaporate after application, i.e. H. exposed to the air to reduce the solvent content of the pot-mix layer so that a strike-in-resistant layer is produced.
  • the period of the evaporation step ranges from about 5 to about 15 minutes.
  • a topcoat is applied to the basecoat layer applied in step b), the topcoat being used as a structuring component and containing prepolymers containing silane groups with a content of greater than or equal to 20% by weight and less than or equal to 100% by weight on the cured top coat layer.
  • the prepolymers used can have one or more silane groups per prepolymer.
  • the prepolymers thus have at least one functional group consisting of a silicon backbone and hydrogen. This functional group can be, for example, -S1H 3 .
  • the hydrogens can also be substituted by further groups, for example alkyl or alkoxy groups.
  • a silane-functionalized, polymeric polyisocyanate with at least one alkoxysilane group can be provided as a silane-functional prepolymer preferred according to the invention in the context of a further embodiment.
  • Said silane-functionalized, polymeric polyisocyanates can be synthesized by the direct reaction of polymeric polyisocyanates with alkoxysilanes which carry an isocyanate-reactive group such as amino, mercapto or hydroxy.
  • Aromatic, araliphatic, aliphatic or cyclo aliphatic polymeric polyisocyanates with an NCO functionality> 2 are used as suitable polymeric polyisocyanates.
  • Suitable diisocyanates for the preparation of the polymeric polyisocyanates are any of the suitable and preferred diisocyanates mentioned above or any mixtures of these diisocyanates. Dimers from the aforementioned diisocyanates, trimers from the aforementioned diisocyanates or combinations thereof are very particularly preferably suitable as the inventive polymeric polyisocyanate for the preparation of the silane-functional polymeric polyisocyanates.
  • the silane-functional prepolymer is a silane-functional prepolymer, obtainable by reacting an isocyanatosilane with a polymer which has functional end groups which are reactive toward isocyanate groups, in particular hydroxyl groups, mercapto groups and / or amino groups.
  • the alkoxysilane-functional isocyanates are any compounds in which at least one, preferably exactly one, isocyanate group and at least one, preferably exactly one, silane group with at least one alkoxy substituent are present simultaneously.
  • the alkoxysilane-functional isocyanate is also referred to below as isocyanatoalkoxysilane.
  • Suitable isocyanatoalkoxy silanes are, for example, isocyanatoalkylalkoxy silanes, as described, for. B. by the methods described in US 3,494,951, EP-A 0 649 850, WO 2014/063895 and WO 2016/010900 in a phosgene-free manner by thermal cleavage of the corresponding carbamates or ureas.
  • Preferred polymers which contain functional end groups which are reactive toward isocyanate groups are the abovementioned polymeric polyols, very particularly polyether, polyester, polycarbonate and polyacrylate polyols, and also polyurethane polyols prepared from polyisocyanates and the polyols mentioned. Mixtures of all the polyols mentioned can also be used.
  • At least one compound of the general formula comes as the alkoxysilane-functional isocyanate
  • R 1 , R 2 and R 3 independently of one another for identical or different saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 18 carbon atoms, which may contain up to 3 heteroatoms from the series oxygen, sulfur , Can contain nitrogen, preferably each alkyl radicals having up to 6 carbon atoms and / or alkoxy radicals having up to 6 carbon atoms, which can contain up to 3 oxygen atoms, particularly preferably each denote methyl, methoxy and / or ethoxy, with the proviso that at least one the radicals R 1 , R 2 and R 3 are connected to the silicon atom via an oxygen atom, and
  • X represents a linear or branched organic radical having up to 6, preferably 1 to 4 carbon atoms, particularly preferably a propylene radical (-CH2-CH2-CH2-).
  • isocyanatoalkoxysilanes are isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyltriisopropoxysilane, 2-isocyanatoethyltrimethoxysilane, 2-isocyanatoethyltriethoxysilane, 2-isocyanatoethyltriisopropoxysilane, 3-
  • Suitable isocyanatoalkoxysilanes are, for example, isocyanatosilanes with a thiourethane structure, such as those obtained by the process of WO 2014/037279 by reacting any aliphatic, cycloaliphatic, araliphatic or aromatic diisocyanates with any mercaptosilanes in an NCO: SH ratio of 6: 1 to 40: 1 and subsequent Removal of excess, unreacted monomeric diisocyanates can be obtained by thin film distillation.
  • At least as isocyanatoalkoxysilane a compound according to the general formula for use
  • R 1 , R 2 and R 3 independently of one another for identical or different saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 18 carbon atoms, which may contain up to 3 heteroatoms from the series oxygen, Can contain sulfur, nitrogen, preferably each alkyl radicals with up to 6 carbon atoms and / or alkoxy radicals with up to 6 carbon atoms, which can contain up to 3 oxygen atoms, particularly preferably each denote methyl, methoxy and / or ethoxy, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is connected to the silicon atom via an oxygen atom, X for a linear or branched organic radical having up to 6, preferably 1 to 4 carbon atoms, particularly preferably for a propylene radical (-CH2-CH2- CH2-) stands and
  • Y represents a linear, branched, or cyclic organic radical. This can be an aromatic or aliphatic radical, preferably a unit or a mixture selected from the group consisting of isophoronyl, pentamethylene, hexamethylene, biscylohexylmethylene, toluidenyl or methylene diphenylene.
  • the isocyanatosilanes of the formula (III) can preferably be mixed with polyols to form prepolymers containing silane groups according to the general formula
  • R 1 , R 2 and R 3 independently of one another for identical or different saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 18 carbon atoms, which may contain up to 3 heteroatoms from the series oxygen, sulfur , Can contain nitrogen, preferably each alkyl radicals having up to 6 carbon atoms and / or alkoxy radicals having up to 6 carbon atoms, which can contain up to 3 oxygen atoms, particularly preferably each denote methyl, methoxy and / or ethoxy, with the proviso that at least one the radicals R 1 , R 2 and R 3 are connected to the silicon atom via an oxygen atom,
  • X represents a linear or branched organic radical having up to 6, preferably 1 to 4 carbon atoms, particularly preferably a propylene radical (-CH2-CH2-CH2-) and
  • Y represents a linear, branched, or cyclic organic radical. This can be an aromatic or aliphatic radical, preferably a unit or a mixture selected from the group consisting of isophoronyl, pentamethylene, hexamethylene, biscylohexylmethylene, toluidenyl or methylene diphenylene,
  • Z stands for a structural unit which is derived from an at least difunctional polyol which has a number average molecular weight M n of 270 to 22000 g / mol, preferably 500 to 18000 g / mol and particularly preferably 800 to 12000 g / mol.
  • the polyol preferably additionally has an acid number, determined according to DIN EN ISO 2114: 2002-06, of 0.01 to 30.0 mg KOH / g, preferably 0.1 to 25.0 mg KOH / g, particularly preferably 0.2 to 20 .0 mg KOH / g, based in each case on the solids content of the polyol.
  • the polyol is particularly preferably a polyester polyol, polycarbonate polyol and / or polyacrylate polyol, preferably with an average OH functionality of 2 to 6 and particularly preferably 2 to 4.
  • Suitable and preferred polyols from which the structural unit Z in the formula (IV) is derived are the (polymeric) polyols already described above, whereby the same preferences apply.
  • Such suitable and preferred polyols and silane-functional prepolymers obtained therefrom are the compounds disclosed in WO 2018/029197, which can preferably be prepared by the processes described there.
  • Z represents a structural unit which is derived from a polyhydric alcohol and / or ether or ester alcohol as polyol, which has 2 to 14 carbon atoms , preferably contains 4 to 10 carbon atoms.
  • suitable polyols also referred to as low molecular weight, polyhydric alcohols and / or ethers or ester alcohols, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol
  • polyhydric alcohols and / or ethers or ester alcohols such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol
  • B diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol or dibutylene glycol or low molecular weight ester alcohols, such as.
  • Preferred examples of such isocyanatosilanes with a thiourethane structure are the reaction products of 2-mercaptoethyltrimethoxylsilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysaptopylane, 3
  • alkoxysilane-functional isocyanates for the process according to the invention are isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, which are prepared by the process of WO 2014/037279 by reacting 3-mercaptopropyltrimethoxysiloxiloxysiloxiloxysiloxysilane with 1-mercapto-tranethoxysiloxysilane / 1-mercapto-tranethoxysiloxysilane / 3-mercapto-tranethoxysiloxysilane / 3-mercapto-tranethoxysiloxysilane and / or 3-mercaptopropyltrimethoxysiloxysilane , 5-diisocyanatopentane, 1,6-diisocyanatohexane, l-isocyanato-3
  • silane-functional prepolymers suitable for the present invention as in the process described in WO 2018/029197, after the reaction, preferably after the reaction of the at least one polymeric polyol or low molecular weight polyol described above, or a mixture of both, with the at least one above, reacted the reaction product obtained in a further process step with at least one alkoxysilane-functional isocyanate.
  • the reaction product obtained can optionally be subjected to any further intermediate steps before the reaction with the alkoxysilane-functional isocyanate, provided that a sufficient amount of hydroxyl groups is still present in the reaction product during the reaction with the at least one alkoxysilane-functional isocyanate.
  • the reaction product with the alkoxysilane-functional isocyanate is particularly preferably reacted without intermediate steps.
  • isocyanatoalkoxysilanes are, for example, those with a formylurea structure, such as can be obtained by the process of WO 2015/113923 by reacting silanes containing formamide groups with molar excess amounts of any aliphatic, cycloaliphatic, araliphatic or aromatic diisocyanates and subsequent removal of unreacted monomeric diisocyanates by distillation.
  • At least one compound of the general formula (V) is used as the isocyanatoalkoxysilane which are mixed with minor amounts of silane-functional compounds of the general formula (VI) are present, in the formulas (V) and (VI) R 1 , R 2 and R 3 independently of one another for identical or different saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 18 carbon atoms which can optionally contain up to 3 heteroatoms from the series oxygen, sulfur, nitrogen, preferably each Alkyl radicals with up to 6 carbon atoms and / or alkoxy radicals with up to 6 carbon atoms, which can contain up to 3 oxygen atoms, particularly preferably each denote methyl, methoxy and / or ethoxy, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is connected to the silicon atom via an oxygen atom, X represents a
  • Y represents a linear or branched, aliphatic or cycloaliphatic radical having 4 to 18 carbon atoms or an optionally substituted aromatic or araliphatic radical having 6 to 18 carbon atoms, preferably a linear or branched, aliphatic or cycloaliphatic radical having 6 to 13 carbon atoms, and
  • G can be mono-, di-, tri- or tetrafunctional and stands for a linear or branched, aliphatic or cycloaliphatic radical or a connecting unit derived therefrom having 4 to 18 carbon atoms or an optionally substituted aromatic or araliphatic radical or a derivative thereof connecting unit with 6 to 18 carbon atoms, preferably for a linear or branched, aliphatic or cyclolaliphatic radical with 6 to 13 carbon atoms.
  • the radical W can optionally contain one or more heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen.
  • Examples of such isocyanatosilanes with a formylurea structure are the reaction products of formamide silanes, as are obtained, for example, by the process disclosed in WO 2015/113923 by reacting amino silanes carrying primary amino groups, in particular 3-aminopropyltrimethoxysilane and / or 3-aminopropyltriethoxysilane, with methyl formate and preferably with methyl formates / or ethyl formate, obtained with elimination of alcohol, with aliphatic and / or cycloaliphatic diisocyanates, preferably 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4 ' - And / or 4,4'-diisocyanatodicyclohexylmethane or any mixtures of these diisocyanates.
  • At least one N-formylaminoalkylsilane of the formula (IX) as an isocyanate-reactive alkoxysilane component for the synthesis of prepolymers containing alkoxysilyl groups in which R 1 denotes an at least divalent, optionally substituted, linear or branched, aliphatic, alicyclic, araliphatic and / or aromatic structural unit having 1 to 12 carbon atoms, in which one or more non-adjacent methylene groups can be replaced by O or S,
  • R 2 and R 3 each independently represent a linear or branched, aliphatic
  • Triethoxysilylpropyl) formamide N- (3-methyldiethoxysilylpropyl) formamide, N- (3-trimethoxysilylpropyl) formamide, N- (3-methyldiethoxymethylsilylpropyl) formamide, or mixtures thereof.
  • Corresponding compounds and resulting prepolymers containing alkoxysilyl groups are disclosed in US 2016/340372 A1, to which reference is made expressly and in full.
  • isocyanatoalkoxysilanes are, for example, the 1: 1 monoadducts of diisocyanates and special secondary aminoalkylalkoxysilanes prepared by the process of EP-A 1 136 495, the aspartic acid esters obtainable from EP-A 0 596 360 and obtainable by reacting maleic dialkyl esters with aminosilanes, in which the reactants are reacted with one another using a large molar excess of isocyanate and the unconverted monomeric diisocyanates are subsequently separated off by distillation.
  • aspartic acid esters as described in EP-A-0 596 360 are preferably used as isocyanate-reactive compounds.
  • X means identical or different alkoxy or alkyl radicals, which can also be bridged, but at least one alkoxy radical must be present on each Si atom, Q is a difunctional linear or branched aliphatic radical and Z represents an alkoxy radical with 1 to 10 carbon atoms.
  • the use of such aspartic acid esters is preferred.
  • Examples of particularly preferred aspartic acid esters are diethyl N- (3-triethoxysilylpropyljaspartate, diethyl N- (3-tri-methoxysilylpropyl) diethyl and N- (3-dimethoxymethylsilylpropyl) -diethyl aspartate (3- preferred is the use of diethyl diester).
  • Triethoxysilylpropyl) aspartic acid diethyl ester Corresponding prepolymers A) prepared from compounds of the formula (VIII) are those as described and prepared in EP-A-0 994 117.
  • the alkoxysilyl-functionalized prepolymers of the publication EP 2 641 925 A and the publication DE 10 2012 204290 A are also preferably suitable in the context of this invention.
  • the silane-functionalized thioallophanates of publication WO 2015/189164 are particularly preferably usable isocyanate-functional silanes of the formula (VII)
  • R 1 , R 2 and R 3 independently of one another represent identical or different radicals and each represent a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted aromatic or araliphatic radical with up to 18 carbon atoms, which can optionally contain up to 3 heteroatoms from the series oxygen, sulfur, nitrogen,
  • X represents a linear or branched organic radical with at least 2 carbon atoms
  • Y is a linear or branched, aliphatic or cycloaliphatic, an araliphatic or aromatic radical having up to 18 carbon atoms and n is an integer from 1 to 20.
  • the reaction of the isocyanatosilanes, as exemplified in formulas (II), (III), (V) and (VII), with the isocyanate-reactive groups, with the polyols preferably used, is carried out in the same manner as above for the preparation of the isocyanate -containing prepolymer from the polyisocyanate component with the polyol component described.
  • Suitable and preferred polyols from which the structural unit Z in the formula (IV) is derived, are the (polymeric) polyols already described above, the same preferences apply.
  • Such suitable and preferred polyols and silane-functional prepolymers obtained therefrom are the compounds disclosed in WO 2018/029197, which can preferably be prepared by the processes described there.
  • Z represents a structural unit which is derived from a polyhydric alcohol and / or ether or ester alcohol as polyol, which has 2 to 14 carbon atoms , preferably contains 4 to 10 carbon atoms.
  • suitable polyols also referred to as low molecular weight, polyhydric alcohols and / or ether or ester alcohols such as, for example, 1,2-ethanediol, 1,2- and 1,3- Propanediol, the isomeric butanediols, pentanediols, hexanediols, heptanediols and octanediols, 1,10-decanediol, 1,12-dodecanediol, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-bis (2nd -hydroxyethoxy) - benzene, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxycyclohexyl) propane (perhydrobisphenol), 1,2,3-propanet
  • B diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol or dibutylene glycol or low molecular weight ester alcohols, such as.
  • the reaction of the isocyanatosilane of the formula (V) is preferred first with a monofunctional alcohol such as methanol, ethanol, propan-1-ol, propan-2-ol, 1-butanol, 2-butanol, 1-pentanol, 1-hexanol, 1 -Heptanol, ethyl-2-hexanol, 1-octanol, 1-nonanol and 1-decanol.
  • the reaction takes place to at least 50% by weight of the NCO groups of the isocyanatosilane (V), particularly preferably with up to 60% by weight and very particularly preferably with up to 70% of the monofunctional alcohol.
  • the ratio of the NCO groups of the isocyanatosilane to the isocyanate-reactive groups, preferably the hydroxyl groups of the polyols, is between 0.5: 1 and 1: 1, preferably between 0.75: 1 and 1: 1, very particularly preferably between 0.9: 1 and 1: 1.
  • silane group-containing monoisocyanates can also be obtained by reacting isocyantosilanes with amino, hydroxyl and mercapto-functional units and then allophanating them with an excess of the diisocyanates described above being represented.
  • Suitable isocyanatosilanes or isocyanate-functional alkoxysilane compounds are in principle any monoisocyanates containing alkoxysilane groups with a molecular weight of 145 g / mol to 800 g / mol.
  • Examples of such compounds are isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, (isocyanatomethyl) methyldimethoxysilane, (isocyanatomethyl) - methyldiethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilanopropyloxysilane, 3-isiethoxysiloxaneyl 3-isocyanyloxysilane.
  • 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane is preferred here, and the use of 3-isocyanatopropyltrimethoxysilane is very particularly preferred.
  • isocyanate-functional alkoxysilane compounds with a higher molecular weight can also be used. It is possible according to the invention to use isocyanate-functional silanes which have been prepared by reacting a diisocyanate with an amino or thiosilane, as are described in US Pat. No. 4,146,585 or EP-A 1 136 495.
  • Suitable solvents are in particular those which are inert towards the reactive groups of the isocyanatosilanes, for example the known customary aprotic paint solvents, such as. B. ethyl acetate, butyl acetate, ethylene glycol monomethyl or ethyl ether acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, Xylene, chlorobenzene, white spirit, more highly substituted aromatics, such as those sold under the names Solventnaphtha, Solvesso, Isopar, Nappar (Deutsche EXXON CHEMICAL GmbH, Cologne, DE) and Shellsol (Deutsche Shell Chemie GmbH, Eschborn, DE), for example, but also solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, dipropy
  • the silane-functional polymer is a silane-functional polymer which can be obtained by a hydrosilylation reaction of polymers with terminal double bonds, for example poly (meth) acrylate polymers and polyether polymers, in particular of allyl-terminated polyoxyalkylene polymers, described for example in US Pat. No. 3,071,751 and US Pat. No. 6,207,766.
  • the methoxy derivatives and ethoxysilane derivatives are preferred for use in corrosion protection and in the automotive refinish sector.
  • the prepolymers containing alkoxysilyl groups which can be used according to the invention are prepared using isocyanate-reactive alkoxysilane compounds by reacting isocyanate-functional prepolymer (preferably isocyanate-functional polyurethane or polymeric polyisocyanates) by reaction with an isocyanate-reactive alkoxysilane compound (in particular the aforementioned preferred isocyanate-reactive alkoxysilane compounds) to give the silane-terminated prepolymer.
  • Said reaction with isocyanate-reactive alkoxysilanes takes place within a temperature range from 0 ° C. to 150 ° C., preferably from 20 ° C. to 120 ° C., the proportions generally being chosen such that 0.8 to 1 per mole of NCO groups used , 3 moles of the isocyanate-reactive alkoxysilane compound are used, preferably 1.0 mole of isocyanate-reactive alkoxysilane compound per mole of NCO groups used.
  • the at least one topcoat layer can be applied to the substrate from solution, dispersion in a liquid dispersant such as water or from the melt and, in the case of powder coatings, in solid form. Application from solution is preferred.
  • Suitable methods of application are, for example, printing, brushing, rolling, pouring, dipping, fluidized bed processes and / or preferably spraying such as, for example, compressed air spraying, airless Spraying, high rotation, electrostatic spray application (ESTA), possibly combined with hot spray application such as hot air hot spraying.
  • spraying such as, for example, compressed air spraying, airless Spraying, high rotation, electrostatic spray application (ESTA), possibly combined with hot spray application such as hot air hot spraying.
  • the number of basecoat and topcoat layers to be applied is not limited to one layer. It is also possible to apply two, three, four or more layers of basecoat. It is also possible to apply two, three, four or more clear and / or topcoat layers, as long as at least one basecoat layer according to the invention is in contact with a topcoat layer according to the invention.
  • the NCO-reactive compound and / or the polyisocyanate can be present in a suitable solvent, for example.
  • suitable solvents are those which have sufficient solubility of the NCO-reactive compound and / or the polyisocyanate and are free from groups which are reactive toward isocyanates.
  • solvents examples include acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, ethyl acetate, n-butyl acetate, ethylene glycol diacetate, butyrolactone, diethyl carbonate, propylene carbonate, ethylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, and -Ethylpyrrolidone, methylal, ethylal, butylal, 1,3-dioxolane, glycerol formal, benzene, toluene, n-hexane, cyclohexane, solvent naphtha, 2-methoxypropyl acetate (MPA).
  • MPA 2-methoxypropyl acetate
  • the NCO-reactive compound can also be present in solvents which carry groups which are reactive toward isocyanates.
  • reactive solvents are those which have an average functionality of isocyanate-reactive groups of at least 1.8.
  • These can be, for example, low-molecular diols (for example 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (for example glycerol, trimethylolpropane), but also low-molecular diamines, for example polyaspartic acid esters, be.
  • the optimal waiting time can be determined in simple tests.
  • the film formation and leaving the film of solvent and / or water should have progressed to such an extent that the applied clearcoat or topcoat no longer leads to genuine dissolving and a change in the appearance of the basecoat.
  • the alignment of the metallic effect pigments can be disturbed by the application of a clear coat too early and therefore can lead to a reduction in the flip-flop effect and / or to graying.
  • the topcoat layer has a catalyst with a content of greater than or equal to 0.01% by weight and less than or equal to 5% by weight, based on the cured topcoat layer, and the catalyst is selected from the group consisting of protonic acids or mixtures thereof.
  • the content of the catalyst in the composition of the topcoat layer can be determined using quantitative FTIR.
  • Suitable protonic acids are organic and inorganic protonic acids, the acid having one or more acidic H atoms.
  • Suitable protonic acids can generally be selected from the group consisting of acetic acid, trifluoroacetic acid, sulfuric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, 1,3-propanedisulfonic acid, methylamidosulfonic acid, sulfoacetic acid, 4-bromobenzenesulfonic acid, 4-
  • Chlorobenzenesulfonic acid Chlorobenzenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, 4-hydroxybenzene sulfonic acid, 4-ethylbenzene sulfonic acid, 2-Mesithylensulfonklare, 1-naphthalenesulfonic acid, 1,5- naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, 2-hydroxy-2-naphthalenesulfonic acid, trifluoromethanesulfonic acid, substituted phosphonic diesters and diphosphonic diesters , preferably from the group consisting of acyclic phosphonic diesters, cyclic phosphonic diesters, acyclic diphosphonic diesters and cyclic diphosphonic diesters.
  • Phosphoric acid types e.g. Nacure types from King Industries, e.g. Nacure 4000
  • Diphenyl phosphite and mixtures thereof Diphenyl phosphite and mixtures thereof.
  • amine-blocked and amine-neutralized derivatives of substituted or unsubstituted phosphoric acid are not catalysts according to the invention.
  • step d) the layer applied in step c) is reacted to obtain the top coat layer.
  • the reaction takes place in the top coat layer while increasing the molecular weight of the prepolymers used containing silane groups. This can be done, for example, by removing the solvent within a wet process or by inducing chemical crosslinking of the prepolymers with one another by means of further substances or compounds.
  • the presence of the catalysts according to the invention can usually be used for crosslinking be enough. Special conditions for obtaining the top coat layer according to the invention were discussed above, for example, in connection with the usable prepolymers containing silane groups.
  • the prepolymers containing silane groups in step c) can be silane-terminated prepolymers.
  • the use of silane-terminated propolymers can contribute to preferred drying and curing kinetics of the top coat layer.
  • these connections in particular also show preferred mechanical properties, such as, for example, particularly elastic behavior and good pendulum hardness. Without being bound by theory, this can probably be attributed to the preferred end-to-end orientation of the prepolymers in the crosslinking process, with the formation of particularly long intermediate chains.
  • the prepolymers containing silane groups in step c) can be silane-terminated polyurethanes.
  • the silane-terminated polyurethanes in particular have proven suitable for use as prepolymers containing silane groups.
  • This group of prepolymers is characterized by particularly fast and efficient drying kinetics and provides visually appealing top coats.
  • the topcoat layers made from these prepolymers can in particular also be clearcoat layers which only negligibly impair the color properties of the basecoat layer.
  • Silane-terminated polyurethanes are distinguished by the fact that they are a reaction product of an isocyanatosilane with a short-chain alcohol, polyester polyol, polycarbonate polyol, polyacrylate polyol or a mixture.
  • Suitable silane-terminated prepolymers have already been described above, but particularly suitable compounds can be the reaction products of an isocyanatosilane containing a thiourethane structure with a short-chain alcohol, polyacrylate polyol or a mixture thereof.
  • the prepolymers containing silane groups and / or their crosslinking products, for the production of which isocyanate functionalities are used have an NCO residual content determined according to DIN EN ISO 11909: 2007-05 of greater than or equal to 0.0005% and less than or equal to 1%.
  • the catalyst can be a polybasic protonic acid.
  • the polybasic protonic acids in particular have proven to be very suitable for the formation of very stable and solvent-resistant layer composites.
  • Polybasic protonic acids are acids with more than one acidic group, in particular more than one acidic hydrogen atom, which can react as part of an acid-base reaction.
  • the polybasic inorganic protonic acids such as sulfuric or phosphoric acid
  • the high tendency of the free protons to diffuse can cause some of the protons to diffuse / migrate into the boundary layer between the base and topcoat layers and lead to an increased adhesion of the two layers to one another.
  • Such a diffusion process cannot take place to such an extent in the case of larger catalysts, such as Lewis acids, for example, that the polybasic protonic acids can be used with preference.
  • the polybasic protonic acids can be selected from the group consisting of phosphoric acids, phosphonic acids, phosphinic acids or their derivatives, sulfuric acid, sulfurous acid and mixtures thereof.
  • the catalyst can be a polybasic protonic acid with a pKa value of greater than or equal to -14.0 and less than or equal to 4.0.
  • the pKs value given in the context of the present invention relates to the first pKs value.
  • Protonic acids of the acid strength given above have proven to be particularly suitable for achieving particularly rapid drying kinetics of the entire paint composite. The equilibrium and thus the catalytic effect is established very quickly and very uniform topcoat layers can be obtained as a result.
  • Suitable catalysts from the range given above are, for example, dibutyl phosphate, diphenyl phosphate, bis (2-ethylhexyl phosphate), benzene phosphonic acid and benzene phosphinic acid.
  • the catalyst can be a substituted or unsubstituted phosphoric acid.
  • Phosphoric acid in particular has proven to be suitable for obtaining very fast drying kinetics and stable layer structures, which are particularly very solvent-resistant. Without being bound by theory, this is attributed to special interactions of the phosphates obtainable after the proton has been split off with the silane groups of the prepolymer.
  • a substituted phosphoric acid can generally be a phosphoric acid in which one or more OH groups have been replaced by C1-C30 organic radicals or H atoms or mixtures thereof. These organic radicals can also carry further functional groups, such as, for example, -OH or -NCO groups.
  • the catalyst can be selected from the group consisting of phosphoric acid and C 1 -C 5 alkyl, aryl, cycloalkyl-substituted phosphoric acid or mixtures thereof.
  • the pure hydrocarbon-substituted phosphoric acids in particular have proven to be suitable catalysts. By using these acids, particularly homogeneous layers with suitable optical properties, such as transparency and turbidity, can be obtained.
  • the catalyst in step c) can be used in a concentration of greater than or equal to 0.03% by weight and less than or equal to 3% by weight. This catalyst concentration is, as defined above, indicated on the entire top coat layer available.
  • concentrations can contribute to economically justifiable curing speeds and a very homogeneous layer structure. Smaller concentrations can be disadvantageous since the layers then harden very slowly and / or the required layer hardness is not achieved. Higher concentrations can be disadvantageous because the layer does not harden in an equilibrium but inhomogeneously due to a too high reaction rate.
  • Preferred catalyst concentrations also have a concentration of greater than or equal to 0.1% by weight and less than or equal to 2.5% by weight, furthermore preferably at concentrations of greater than or equal to 0.5% by weight and less than or equal to 2% by weight.
  • the silane-terminated polyurethanes can have a residual NCO content, determined in accordance with DIN EN ISO 11909: 2007-05, of greater than or equal to 0.0005% and less than or equal to 1%.
  • a residual NCO content determined in accordance with DIN EN ISO 11909: 2007-05, of greater than or equal to 0.0005% and less than or equal to 1%.
  • Prepolymers and in particular silane-terminated polyurethanes with a low proportion of NCO groups can lead to particularly well-adhering and uniform layer composites. Without being bound by theory, this can mean that the proportion of NCO side reactions with the catalyst and / or the other prepolymers is so small that they are no longer reflected in the end result of the cured layer. In this way, visually particularly appealing layer composites can be obtained.
  • the silane-terminated polyurethanes can have a viscosity, determined in accordance with DIN EN ISO 3219: 1994-08, of greater than or equal to 50 mPas and less than or equal to 5000 mPas.
  • the concentration of silane-terminated polyurethanes for determining the viscosity value can be 60% by weight. These viscosities have proven to be suitable for obtaining stable topcoat layers. Higher viscosities can lead to inhomogeneous layer build-up, while lower viscosities can only contribute to insufficient mechanical properties.
  • Preferred viscosity ranges can also be greater than or equal to 200 mPas and less than or equal to 3000 mPas and greater than or equal to 500 mPas and less than or equal to 2000 mPas.
  • a layer composite of a lower basecoat and a topcoat layer arranged above it is selected from the group consisting of polyacrylates, polyurethanes, polyether polyols, polycarbonate polyols, polyester polyols, melamine resins, alkyd resins or mixtures thereof, and the upper topcoat layer contains crosslinked silane groups. containing polymers and protonic acids or Contains mixtures thereof.
  • the layer composite of the base coat layer which can be replaced according to the invention and the top coat layer which can be used according to the invention can be distinguished by improved solvent resistance, higher mechanical hardness and improved layer adhesion.
  • the polybasic protonic acids can be selected from the group consisting of phosphoric acid, C1-C15 alkyl, aryl, cycloalkyl-substituted phosphoric acids or mixtures thereof.
  • the upper topcoat layer with a layer thickness of 50 pm on a white basecoat can have a Delta Lab value in relation to the white basecoat of AL greater than or equal to 0.2 and less than or equal to 20, of Aa greater than or equal - 0.01 and less than or equal to -20, and Ab greater than or equal to -0.01 and less than or equal to -13, which was determined in accordance with DIN EN ISO 1166-4: 2012-06.
  • clear topcoats that is to say clearcoats, which have little or no impairment of the optical properties, in particular the color, of basecoat layers can be obtained by means of the process according to the invention. Very homogeneous and transparent topcoat layers can thus be obtained.
  • the top coat layer at a layer thickness of 50 pm can have a total transmission according to ISO 14782: 1999-08 / ASTM D1003: 2013-11 of greater than or equal to 85% and less than or equal to 99.5% and a turbidity of greater or equal to 0.5 and less than or equal to 15.
  • This layer may further preferably have an image sharpness of greater than or equal to 90 and less than or equal to 99.8.
  • the structure according to the invention enables optically high-quality layer composites to be obtained, in particular the topcoat layer being highly transparent and not very light-scattering. This can contribute to a color impression of the lower lacquer layer that is as pristine as possible.
  • the upper topcoat layer with a layer thickness of 50 pm has a glossy haze measured according to DIN EN ISO 13803: 2015-02 of greater than or equal to 2 and less than or equal to 30.
  • the structure according to the invention can also be used to achieve, in particular, very shiny layer composites which have a brilliant appearance. These coatings are very suitable for the automotive sector, for example.
  • the upper topcoat layer can have a pendulum hardness, determined in accordance with DIN EN ISO 1522: 2000-09, of greater than or equal to 50 s and less than or equal to 180 s.
  • Layer composites with special viscoelastic properties can be obtained by means of the method according to the invention.
  • the top coat layer according to the invention can contribute to providing highly elastic layer composites which are suitable for the entire layer
  • the improved elasticity can, for example, help to reduce the proportion of lacquer chips due to mechanical loads, such as stone chips.
  • the catalysts used in the topcoat layer can form a concentration gradient in the basecoat. This means that the catalyst of the top coat layer can diffuse into the basecoat and the concentration of these components in the basecoat layer is not constant, but that the concentration of this component is lower at the lower limit of the basecoat layer and then rises over the basecoat layer to the topcoat layer. This training can contribute to a particularly firm adhesion of both layers.
  • the use of the layer composite according to the invention for coating a substrate is according to the invention.
  • the advantages of the use according to the invention reference is made explicitly to the advantages of the method according to the invention and the advantages of the layer composite according to the invention.
  • a vehicle or a vehicle body part has a layer composite according to the invention.
  • the vehicle or the vehicle body part can be constructed from one or more materials. Suitable materials are, for example, metal, plastic or their mixtures.
  • the vehicle can be any vehicle known to those skilled in the art.
  • the vehicle can be a motor vehicle, fast motor vehicle, motorcycle, scooter, bicycle or the like.
  • the layered composite according to the invention is particularly suitable in the field of the production of automotive coatings, since here the elastic properties and improved weather resistance are particularly in demand.
  • the high optical transparency of the top coat layer allows the color impression of a basecoat layer to be obtained particularly well.
  • the vehicle is preferably a motor vehicle and / or fast motor vehicle (FKW vehicle), particularly preferably it is a motor vehicle. Examples
  • the tests were carried out at 23 ° C and 50% relative humidity.
  • the NCO contents were determined titrimetrically in accordance with DIN EN ISO 11909: 2007-05.
  • the drying times were determined in accordance with DIN EN ISO 9117-5: 2010-07 (drying test part 5: modified Bandow-Wolff method).
  • the solvent and water resistance were determined according to DIN EN ISO 4628-1: 2016-07.
  • the solvents xylene hereinafter also abbreviated as "Xy”, methoxypropylacetate (MPA), ethyl acetate (EA) and acetone (Ac) were used.
  • the contact time was 5 minutes in each case.
  • For the measurement of water resistance the contact time was 24 hours in each case. The sampling was carried out according to the listed standard.
  • the pendulum damping was measured according to DIN EN ISO 1522: 2000-09 on a glass plate and was determined according to König.
  • the STP films were applied to glass plates with a squeegee. The film thickness was 30-35 pm for all films.
  • Setalux DA 870 BA is a commercially available polyacrylate polyol, which was obtained from Allnex. It has an OH content of 4.2% by weight (based on the solid) and is supplied in butyl acetate (70%). The viscosity (23 ° C) is 7500 mPas.
  • the raw materials were either manufactured by Covestro AG itself or were obtained from Sigma-Aldrich and used without further purification. Phosphoric acid was used at 85% by weight (water) and 100%.
  • the catalyst X-Add KR 9006 contains a metal complex based on aluminum oxide, which was obtained in solution in n-butanol from Nano-X.
  • the Nacure 4167 catalyst is an amine-neutralized phosphate catalyst.
  • the weak acid catalyst was obtained from King Industries.
  • the Nacure 4575 catalyst is an amine-neutralized phosphate catalyst.
  • the acid catalyst was purchased from King Industries.
  • the Nacure 4000 catalyst is a catalyst based on alkyl phosphates (methyl) of various functions.
  • the acid catalyst was purchased from King Industries.
  • the catalyst K-Kat XK 678 is a catalyst based on alkyl phosphates with various functions.
  • the acid catalyst was purchased from King Industries.
  • IPDI isophorone diisocyanate
  • TEOF tetraethyl orthoformate
  • BuAc butyl acetate
  • Example 1 15.02 g of TEOF and 10 drops of DBTL are mixed at 80 ° C. under dry nitrogen with 764.91 g of polymeric polyol Al and 38.83 g of Stabaxol 1 and the reaction is stirred until a remainder -NCO of ⁇ 0.3% is reached.
  • the crude product is mixed with 203.21 BuAc.
  • Basecoat Spies Hecker Permahyd basecoat 280 super deep black. Dilution with demineralized water (95%). Baking conditions: 80 ° C, 10 min or approx. 30 min air drying.
  • Example 3 a mixture of Example 3, Example 4 and Example 5 was used in a ratio of 7: 3: 1 based on the solids content for the topcoat.
  • the molar amount of catalyst used agrees in the experiments, the different amounts (% by weight) result from the different catalyst molecular weights. Curing was carried out on the specified surface for 30 min at 60 ° C. The results are summarized in Table 1 below:
  • Protonic acid catalysts are also reflected in the solvent resistance of the STP films, which is independent of the substrate. Resistance to 0 0 4 4 for example no. 13 and 0 0 4 5 to basecoat were found on glass. This is not a significant difference. The results shown here illustrate that with protonic acid catalysts, STPs are independent of the substrate - glass vs. Basecoat - can be cured.
  • Table 3 shows the formulations of the individual coatings:
  • the properties of the STP topcoats catalyzed according to the invention correspond to those of a 2-component PU coating system. For example, for example no. 14 it results that the drying times are 20 26 34 minutes. For the 2K PU reference, however, drying times T of 20 20 25 minutes are obtained on the basecoat. This finding proves that the drying times for the two coating systems do not differ significantly.
  • the solvent resistance for the 2-component PU reference is - 1 2 4 5 - after 7 days and for the inventive structure no. 14 - 2 2 4 4. This shows that the example according to the invention is analogous to a 2-component in terms of drying time and solvent resistance PU coating material is.
  • Example 3 Example 4 and Example 5 were mixed together in a ratio of 7: 3: 1. 45 g of this mixture were mixed with 0.69 g dibutyl phosphate, 0.18 g BYK 315 N, 2.12 g Tinuvin 5100 and 23 g methoxypropyl acetate (MPA). This formulation was then applied to a basecoat using a spray gun and dried for 30 min, 60 ° C. to form a hardened multilayer structure.
  • MPA methoxypropyl acetate
  • the glossy haze and the gloss measurements showed that high-gloss laminates are available.
  • the weathering tests also showed that the gloss is very weather-resistant and the values obtained change only insignificantly.
  • the cross-cut test also shows very clearly that there is an excellent overall adhesion of the layer composite and also a good adhesion of the composite to the substrate.

Abstract

La présente invention concerne un procédé de fabrication d'une structure de peinture à au moins deux couches, composée d'une couche de peinture de base inférieure et d'une couche de peinture de recouvrement supérieure disposée dessus sur un substrat, ledit procédé comprenant les étapes suivantes: a) appliquer une couche de peinture de base comprenant des polymères sélectionnés dans le groupe comprenant polyacrylates, polyuréthanes, polyéther polyols, polycarbonate polyols, polyester polyols, résines de mélanine, résines alkyde ou leurs mélanges sur un substrat; b) faire durcir au moins en partie la couche de peinture de base; c) appliquer une peinture de recouvrement sur la couche de peinture de base appliquée à l'étape b), la peinture de recouvrement comprenant comme composant structurant des prépolymères contenant des groupes silane, lesdits prépolymères ayant une teneur supérieur ou égale à 20% en poids et inférieure ou égale à 100% en poids sur la couche de peinture de recouvrement durcie et un catalyseur ayant une teneur supérieure ou égale à 0,01% en poids et inférieure ou égale à 5% en poids, rapporté à la couche de peinture de recouvrement durcie, et le catalyseur étant sélectionné dans le groupe comprenant des acides protoniques ou leurs mélanges et d) faire réagir la couche appliquée à l'étape c) de manière à obtenir la couche de peinture de recouvrement. L'invention concerne en outre un composite stratifié composé des deux couches selon l'invention, l'utilisation du composite stratifié selon l'invention pour munir un substrat d'un revêtement ainsi qu'un élément de carrosserie muni du revêtement selon l'invention.
PCT/EP2019/078965 2018-10-30 2019-10-24 Procédé de fabrication d'une structure de peinture multicouche à couche de recouvrement en prépolymères contenant des groupes silane WO2020089019A1 (fr)

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DE102012204290A1 (de) 2012-03-19 2013-09-19 Evonik Degussa Gmbh Addukte aus Isocyanatoalkyl-trialkoxysilanen und aliphatischen, alkyl-verzweigten Diolen oder Polyolen
EP2641925A1 (fr) 2012-03-19 2013-09-25 Evonik Degussa GmbH Additifs à base d'isocyanatoalkyl-trialcoxysilanes et de dioles ou de polyols aliphatiques alkyle-ramifiés
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WO2014037279A1 (fr) 2012-09-04 2014-03-13 Bayer Materialscience Ag Isocyanatosilanes avec une structure de thio-uréthannes
WO2014037265A1 (fr) 2012-09-04 2014-03-13 Bayer Materialscience Ag Liants silanofonctionnels à structure de thio-uréthanne
WO2014063895A1 (fr) 2012-10-23 2014-05-01 Evonik Industries Ag Compositions à base d'isocyanates contenant des alcoxysilanes et des stabilisateurs acides
WO2014180623A1 (fr) 2013-05-07 2014-11-13 Evonik Industries Ag Réticulation d'adduits d'ipms avec des aminosilanes
WO2015113923A1 (fr) 2014-01-31 2015-08-06 Bayer Materialscience Ag Formamides modifiés silane
US20160340372A1 (en) 2014-01-31 2016-11-24 Covestro Deutschland Ag Silane-modified formamides
WO2015189164A1 (fr) 2014-06-13 2015-12-17 Covestro Deutschland Ag Polyisocyanates de thioallophanate contenant des groupes silane
WO2016010900A1 (fr) 2014-07-14 2016-01-21 Momentive Performance Materials Inc. Procédé de production d'isocyanato-organosilanes peu colorés et de couleur stable et produits dérivés de ces derniers
US20170369626A1 (en) 2016-06-27 2017-12-28 Evonik Degussa Gmbh Alkoxysilane-functionalized allophanates
US20170369627A1 (en) 2016-06-27 2017-12-28 Evonik Degussa Gmbh Alkoxysilane-functionalized and allophanate-functionalized urethanes
US20170369631A1 (en) 2016-06-27 2017-12-28 Evonik Degussa Gmbh Alkoxysilane- and allophanate-functionalized coating materials
WO2018029197A1 (fr) 2016-08-09 2018-02-15 Covestro Deutschland Ag Polyuréthanes polymères à fonction silane

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