WO2003057740A1 - Dispersions organiques de nanoparticules a surface modifiee, leur procede de production et leur utilisation - Google Patents

Dispersions organiques de nanoparticules a surface modifiee, leur procede de production et leur utilisation Download PDF

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Publication number
WO2003057740A1
WO2003057740A1 PCT/EP2002/014569 EP0214569W WO03057740A1 WO 2003057740 A1 WO2003057740 A1 WO 2003057740A1 EP 0214569 W EP0214569 W EP 0214569W WO 03057740 A1 WO03057740 A1 WO 03057740A1
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organic
modified nanoparticles
groups
dispersions
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PCT/EP2002/014569
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German (de)
English (en)
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Hubert Baumgart
Peter Hommes
Ulrike RÖCKRATH
Winfried Stübbe
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Basf Coatings Ag
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Priority to AU2002358768A priority Critical patent/AU2002358768A1/en
Publication of WO2003057740A1 publication Critical patent/WO2003057740A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • 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
    • C08G18/8093—Compounds containing active methylene groups
    • 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
    • C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds having only one group containing active hydrogen
    • 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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • Nanoparticles processes for their production and their use
  • the present invention relates to new organic dispersions of surface-modified nanoparticles.
  • the present invention also relates to a new method for producing organic dispersions of surface-modified nanoparticles.
  • the present invention relates to the use of the new organic dispersions of surface-modified nanoparticles as coating materials, adhesives and sealants or for their production and for the production of moldings, in particular optical moldings, and self-supporting films.
  • US Pat. No. 4,652,479 A discloses organic dispersions of surface-modified nanoparticles, which are produced by grinding silicon dioxide nanoparticles in monoalcohols.
  • the surface-modified nanoparticles contained in the known organic dispersions have no reactive functional groups.
  • organic dispersions of surface-modified nanoparticles are known which are produced, for example, from boehmite and 3-methacryloyloxypropyltrimethoxysilane.
  • the resulting sol is diluted with 2-isopropoxyethanol, followed by the addition of triethylene glycol dimethacrylate.
  • a grinding process is not provided.
  • the organic dispersions are used as coating materials and are radically hardened with peroxides.
  • European dispersions EP 0 832 947 A 2 disclose organic dispersions of surface-modified nanoparticles, which are produced, for example, from colloidal silicon dioxide and the reaction product of 3-isocyanatopropyltrimethoxysilane and hydroxypropyl carbamate.
  • a grinding process is not provided.
  • the dispersions are used in solvent-based, thermally curable clear coats based on carbamate group-containing binders.
  • organic dispersions of surface-modified nanoparticles which, for example, consist of colloidal metal oxides and the reaction product of hexamethylene diisocyanate partially blocked with 3,5-dimethylpyrazole and diethyl N- (3-trimethoxysilylpropyl) aspartate in isopropanol / isopropanol getting produced. Isopropanol is then removed by vacuum distillation at 40 ° C and replaced with a higher-boiling solvent. A grinding process is not provided. The dispersions are used to manufacture thermally curable coating materials based on polyesters.
  • organic dispersions of surface-modified nanoparticles consist, for example, of silicon dioxide which has been dispersed in isopropanol with stirring and ultrasound, and 3-
  • Methacryloyloxypropyltrimethoxysilane be prepared.
  • the resulting dispersion is mixed with tetraethylene glycol dimethacrylate and a photoinitiator. A grinding process is not provided.
  • the solvent is then partially distilled off in vacuo.
  • the mixture is used to produce molded articles. For this purpose they are poured into a mold and hardened with UV radiation and IR radiation. The result is a solvent-free, binder-containing shaped silicon dioxide body, which corresponds to a ceramic green body. This is completely burned at temperatures from 500 to 1,400 ° C.
  • organic dispersions of surface-modified nanoparticles are known which are produced, for example, by reacting silicon dioxide nanoparticles with 3-methacryloyloxypropyltrimethoxysilane and aluminum triisopropylate in ethoxylated pentaerythritol tetraacrylate at 80 ° C. After its preparation, the mixture is cooled as quickly as possible to room temperature for coating processing. A grinding process is not provided. The coating material is cured using electron beams.
  • coating materials curable with actinic radiation (100% systems) which contain 3-methacryloxypropyltrimethoxysilane-modified nanoparticles based on silicon dioxide in an amount of 5 to 16% by weight and polyester acrylates, oligoether acrylates, urethane acrylates, ethoxylated Contain pentaerythritol tetraacrylate or epoxy acrylate and a photoinitiator.
  • the surface-modified nanoparticles were incorporated into the olefinically unsaturated compounds by predispersing the surface-modified nanoparticles in a dissolver and grinding the resulting coating material with a bead mill, so that the grindometer value is below 10 ⁇ m.
  • the article does not indicate the conditions under which the surface of the nanoparticles was modified.
  • nanoparticles When the surface of nanoparticles is modified with, for example, 3-methacryloyloxypropyltrimethoxysilane, triethoxysilane or tri-sec-butoxysilane in the presence of higher-functionality olefinically unsaturated monomers at temperatures at which the alcohol formed distills off, the transesterification between the acrylate monomers and the alcohol occurs which causes considerable odor nuisance from methyl acrylate, ethyl acrylate or sec-butyl acrylate.
  • actinic radiation includes electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, in particular UV radiation, or
  • thermally or thermally and with actinic radiation curable coating materials which contain surface-modified nanoparticles, such as those from the VILF series of lectures by the Association of Engineers of the Paint and Paint Industry eV, Volume 3, p Frahn, V. Valter, T. Ladwig, M. Ettinger and J. Meyer, "New modified, highly disperse silicon dioxide for radiation-curing coating systems", are known.
  • These surface-modified nanoparticles are preferably added to the coating materials in the form of a paste
  • the surface-modified nanoparticles are predispersed in a binder solution and the dispersion is ground
  • the coating materials can contain even more highly functional olefinically unsaturated monomers, such as dipentaerythritol pentaacrylate, but they do not contain the organic dispersion of the surface-modified nanoparticles l, but must be entered separately.
  • the object of the present invention is to provide new organic dispersions of surface-modified nanoparticles which no longer have the disadvantages of the prior art, but which can be prepared in a simple manner without causing any unpleasant odors caused by undesired by-products.
  • the new organic dispersions of surface-modified nanoparticles are said to be suitable as coating materials, adhesives and sealants. Furthermore, the new organic dispersions of surface-modified nanoparticles are said to be suitable for the production of moldings, in particular optical moldings, and self-supporting films.
  • the new organic dispersions of surface-modified nanoparticles should be able to be distributed homogeneously without much effort in customary and known coating materials, adhesives and sealants curable thermally and / or with actinic radiation, in particular thermally and with actinic radiation, so that haze-free, highly scratch-resistant coatings, adhesive layers and Seals, especially clear coats, result.
  • R non-hydrolyzable, single-membered organic group
  • o an integer from 1 to 5;
  • + p is an integer from 2 to 6;
  • p is an integer from 1 to 6
  • n is zero or an integer from 1 to 5;
  • R non-hydrolyzable, single-membered organic group
  • o an integer from 1 to 5;
  • + p is an integer from 2 to 6;
  • p is an integer from 1 to 6
  • n and n are zero or an integer from 1 to 5;
  • the new process for the production of organic dispersions of surface-modified nanoparticles is referred to below as the “process according to the invention”.
  • the new coating materials, adhesives and sealants were found which contain at least one dispersion according to the invention and / or at least one dispersion produced according to the method according to the invention and which are hereinafter referred to as »coating materials, adhesives and
  • the dispersions according to the invention free of undesirable odors could readily be incorporated homogeneously into coating materials, adhesives and sealing compounds which are known per se and which are curable thermally and / or with active radiation, in particular thermally and with actinic radiation.
  • the coating materials, adhesives and sealants according to the invention therefore provided haze-free, highly scratch-resistant coatings, adhesives and seals, in particular clearcoats.
  • the dispersions of the invention can be prepared by the process of the invention.
  • the strong shear can be applied with conventional and known devices.
  • suitable devices are gear rim dispersers or mills. Mills, in particular agitator mills and ball mills containing grinding media, are preferably used (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 369 and 370, "grinding media").
  • Step (1) is preferably carried out at a temperature of ⁇ 40 ° C., preferably ⁇ 30 ° C. and in particular at room temperature.
  • the mixture (1) can be sheared for more or less long.
  • the duration of the shear is preferably 10 minutes to 10 hours, preferably 20 minutes to 5 hours and in particular 30 minutes to 3 hours.
  • the composition of the mixture (1) can vary widely and depends on the requirements of the individual case. Preferably, in the mixture (1), based in each case on the total amount of the mixture (1),
  • Organic and inorganic, in particular inorganic, nanoparticles (A) are suitable.
  • the nanoparticles (A) are preferably selected from the group consisting of compounds of metals from subgroups I to VIII and III. to V. main groups and selected from metals of the I., VII. and VIII. subgroup of the periodic table of the elements. Compounds of metals of IV., V. and VI are preferred. Subgroup and the III. and IV. main group used. In particular, compounds of metals of subgroup IV and III. and IV. Main group used.
  • the metal compounds (A) are preferably selected from the group consisting of oxides, oxide hydrates, sulfides, selenides, tellurides, halides, arsenides, antimonides, nitrides, phosphides, carbides, phosphates, sulfates, carbonates, silicates, titanates, tungstates, zirconates, aluminates and Stannates, preferably selected from the group of oxides and oxide hydrates.
  • suitable metals (A) and metal compounds (A) are from the German patent applications
  • Silicon dioxide, aluminum oxide and aluminum oxide hydrate are particularly preferably used.
  • Hydrophilic fumed silicon dioxides which are not porous, whose agglomerates and aggregates have a chain-like structure and which can be produced by flame hydrolysis of silicon tetrachloride in a detonating gas flame are very particularly preferably used. These are sold, for example, by Degussa under the brand Aerosil ®. Precipitated water glasses, such as nanohectorites, which are sold, for example, by Südchemie under the Optigel ® brand or by Laporte under the Laponite ® brand, are also used with particular preference.
  • the further essential component of the mixture (1) is at least one amphiphile (B).
  • Amphiphiles are known to be molecules that have both hydrophilic and lipophilic properties (cf. Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart, New York, 9th edition, 1989, volume 1, page 176, »Amphiphil «).
  • amphiphiles (B) are preferably selected from the group consisting of monoalcohols, in particular monoalcohols with 3 to 6 carbon atoms in the molecule, and aliphatic polyols, in particular diols with 3 to 12 carbon atoms in the molecule.
  • Examples of highly suitable monoalcohols (B) are propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, amyl alcohol,
  • Neopentyl alcohol or n-hexanol Neopentyl alcohol or n-hexanol.
  • Suitable diols (B) are propylene glycol, trimethylene glycol,
  • Propanol, isopropanol, butanol or isobutanol are particularly preferably used.
  • the further essential constituent of the mixture (1) is at least one, in particular one, compound (C) with at least two, preferably at least three, preferably at least four, particularly preferably at least five and in particular six reactive functional groups which have at least one, in particular one, contains bond that can be activated with actinic radiation.
  • Bonds from the group consisting of carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, Carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds.
  • Double bonds Carbon-carbon double bonds (“double bonds”) are preferably used.
  • the reactive functional groups from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or are particularly preferred butenyl; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.
  • (Meth) acrylate groups in particular acrylate groups, are very particularly preferably used.
  • the compounds (C) can have at least one, in particular one, reactive functional group which undergoes reactions with groups of their type (“with themselves”) and / or with complementary reactive functional groups.
  • groups of their type (“with themselves”) and / or with complementary reactive functional groups.
  • suitable groups of this type are the reactive functional groups (S 2) described below, in particular hydroxyl groups or blocked isocyanate groups.
  • the base body to which the double bonds and the optional reactive functional groups are bound is not critical, but low molecular weight, oligomeric and / or polymeric base bodies can be used.
  • the double bonds can be carried out in a customary and known manner by optionally polymer-analogous reactions of pendant and / or terminal hydroxyl groups with olefinically unsaturated monoisocyanates, such as vinyl isocyanate, Methacryloyl isocyanate or 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC), of pendant and / or terminal isocyanate groups with hydroxyl-containing olefinically unsaturated monomers such as hydroxyethyl acrylate or of pendant and / or terminal epoxy groups with olefinically unsaturated carboxylic acids such as acrylic acid or methacrylic acid.
  • olefinically unsaturated monoisocyanates such as vinyl iso
  • suitable constituents (C) which contain six or more double bonds in the molecule are (meth) acrylic-functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates,
  • the urethane (meth) acrylates (C) and processes for their preparation are known, for example, from patent applications and patents EP 0 204 161 A 1 DE 196 45 761 A1, WO 98/10028, EP 0 742 239 A1, EP 0 661 321 B 1, EP 0 608 021 B 1, EP 0 447 998 B 1, or EP 0 462 287 B 1.
  • the urethane (meth) acrylates (C) are commercially available products and are sold, for example, under the brand Ebecryl ® 1290 by UCB, Belgium, or sold under the brand Rahn ® 99-664 by the company Rahn.
  • Suitable constituents (C) are known from German patent application DE 198 18 735 A1, column 2, lines 24 to 36, column 3, line 16, to column 6, line 33, and column 6, lines 34 to 68 .
  • Well-suited examples are pentaerythritol triacrylate, which is sold under the trademark Sartomer ® 444 D by Cray Valley, France, and dipentaerythritol pentaacrylate, which is sold under the trademark Sartomer ® 399 by the same company.
  • At least one further stage (2) is added to the strongly sheared mixture (1) described above with at least one compound (D) of the general formula I:
  • the compound (D) serves to modify the nanoparticles (A).
  • the modification can take place by physical adsorption of the compounds (D) on the surface of the unmodified nanoparticles (A) and / or by chemical reaction of the compounds (D) with suitable reactive functional groups on the surface of the unmodified nanoparticles (A).
  • the modification is preferably carried out via chemical reactions.
  • L at least double-bonded, linking organic group; H hydrolyzable, monovalent organic group or hydrolyzable atom;
  • R non-hydrolyzable, single-membered organic group
  • o an integer from 1 to 5, in particular 1;
  • + p is an integer from 2 to 6, especially 3 or 4;
  • p is an integer from 1 to 6, preferably 1 to 4, in particular 3;
  • suitable metals M are those described above, in particular silicon and aluminum.
  • the reactive functional group S is preferably selected from the group consisting of (S1) reactive functional groups which contain at least one bond which can be activated with actinic radiation and (S2) reactive functional groups which contain groups of their type (“with themselves”) and / or enter into thermally initiated reactions with complementary reactive functional groups.
  • Suitable reactive functional groups (S 1) are the reactive functional groups described above at least one bond that can be activated with actinic radiation, in particular methacrylate groups.
  • Suitable reactive functional groups are blocked isocyanate groups, carboxyl groups, anhydride groups, hydroxyl groups, amino groups and epoxy groups, in particular epoxy groups.
  • the bonds which can be activated with actinic radiation can be formed via carbon-carbon bonds or ether, thioether, carboxylic acid ester, thiocarboxylic acid ester, carbonate, thiocarbonate, phosphoric acid ester, thiophosphoric acid ester, phosphonic acid ester, thiophosphonic acid ester, phosphite, thiophosphite, sulfonic acid ester , Amide, amine, thioamide, phosphoric acid amide, thiophosphoric acid amide, phosphonic acid amide, thiophosphonic acid amide, sulfonic acid amide, imide, urethane, hydrazide, urea, thiourea, carbonyl, thiocarbonyl, sulfone or sulfoxide groups , but especially with carbon-carbon bonds, carboxylic acid ester groups and ether groups, especially carboxylic acid ester groups, with the linking group L.
  • variable H stands for a hydrolyzable, single-bonded, organic group or for a hydrolyzable atom.
  • Suitable hydrolyzable atoms are hydrogen atoms and halogen atoms, in particular chlorine and bromine atoms.
  • the hydrolyzable, monovalent, organic groups H are preferably used.
  • Suitable groups H of this type are groups of the general formula II: -XR (II).
  • variable X represents an oxygen atom, a sulfur atom, an oxycarbonyl group and / or a group> NR 1 , where R 1 is an alkyl group having 1 to 4 carbon atoms, in particular methyl, ethyl, propyl and n-butyl, means. X preferably represents an oxygen atom.
  • R has the meaning given below, methyl and ethyl being particularly preferred here.
  • R stands for a non-hydrolyzable, single-bonded, organic group.
  • the group R can be substituted or unsubstituted; it is preferably unsubstituted. It can be aromatic, aliphatic or cycloaliphatic. A group R is considered aromatic if M and / or X is directly connected to the aromatic group. This rule applies mutatis mutandis to the aliphatic and cycloaliphatic groups.
  • alkyl radicals examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
  • Suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.
  • alkylcycloalkyl radicals examples include methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane.
  • Suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl.
  • Suitable aryl radicals are phenyl, naphthyl or biphenylyl.
  • suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene.
  • Suitable cycloalkylaryl radicals are 2-, 3-, or 4-phenylcyclohex-1-yl.
  • Suitable arylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or butylphen-1-yl.
  • Suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1 -yl.
  • the groups R described above can be substituted.
  • electron-withdrawing or electron-donating atoms or organic residues can be used.
  • Suitable substitutes are halogen atoms, in particular chlorine and fluorine, nitrile groups, nitro groups, partially or completely halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and Arylcycloalkyl radicals, including those exemplified above; Aryloxy, alkyloxy and cycloalkyloxy radicals, in particular phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy or cyclohexyloxy; Arylthio, alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio or cyclohexylthio
  • Linear or branched, in particular linear, aliphatic radicals are preferably used. Lower aliphatic radicals are preferred. Of these, the methyl groups or the ethyl groups are used with very particular preference.
  • variable L stands for an at least double-bonded, in particular double-bonded, linking, organic group.
  • suitable divalent organic linking groups L are aliphatic, aromatic, cycloaliphatic and aromatic-cycloaliphatic and heteroatoms containing aliphatic, aromatic, cycloaliphatic and aromatic-cycloaliphatic hydrocarbon radicals, such as
  • divalent polyester residues with recurring polyester portions of the formula - (- CO- (CHR 7 ) r CH2-O -) - from.
  • linear polyether residues preferably with a number average molecular weight from 400 to 5,000, in particular from 400 to
  • linear siloxane residues such as those found in silicone rubbers, hydrogenated polybutadiene or polyisoprene residues, statistical or alternating butadiene-isoprene residues
  • Graft copolymer residues which may also contain copolymerized styrene, and ethylene-propylene-diene residues;
  • Cycloalkanediyl radicals having 4 to 20 carbon atoms such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,3 or-1,4-diyl, cycloheptane-1,4-diyl , Norboman-1,4-diyl, adamantane-1,5-diyl, decalin-diyl, 3,3,5-trimethyl-cyclohexane-1,5-diyl, 1-methylcyclohexane-2,6-diyl, dicyclohexylmethane-4 , 4'-diyl, 1, 1'-dicyclohexane-4,4'-diyl or 1, 4-dicyclohexylhexane-4,4 "-diyl, in particular 3,3,5-trimethyl-cyclohexane-1, 5-diyl or
  • the linking groups L (1) are particularly preferred, very particularly preferably trimethylene, tetramethylene, pentamethylene, Hexamethylene, heptamethylene or octamethylene and especially trimethylene.
  • the compounds (D) can also be used in a complex form, as is described, for example, in international patent application WO 39/52964, page 8, lines 12 to 20.
  • the compounds (D) are customary and known and a large part of them are commercially available.
  • Well suited compounds (D) are for example from the
  • EP 0 872 500 A1 page 2, line 32, to page 3, line 12, and page 4, line 16, line 53,
  • the compounds (D) are preferably selected from the group consisting of 3- (meth) acryloyloxypropyltriethoxysilane, 3-
  • Methacryloyloxypropyltrimethoxysilane is preferably used.
  • particularly suitable compounds (D) of this type are aluminum tris (ethoxylate), tris (methoxyethylate), tripropylate, triisopropoxide, tris (n-butoxide) or tris (sec-butoxide).
  • the weight ratio of the nanoparticles (A) to the compounds (D) can also vary widely. It depends primarily on the functionality of the surface of the nanoparticles (A) on the one hand and the functionality of the compounds (D) on the other hand and the desired degree of modification, so that the person skilled in the art may consider the weight ratio of (A): (D) based on his general specialist knowledge Can set simple preliminary tests.
  • the weight ratio of (A): (D) is preferably 1:20 to 0.5: 1, preferably 1:15 to 1: 1 and in particular 1:10 to 2: 1.
  • water (E) is added in step (2). The water is used for the hydrolysis and condensation of the compounds (D) with the reactive functional groups on the surface of the nanoparticles (A).
  • the water is added in an amount just sufficient to accomplish the hydrolysis and condensation.
  • the amount of water is added so that local over-concentrations are avoided. This is achieved, for example, by entering the amount of water in the reaction mixture with the aid of moisture-laden adsorbents, for example silica gel or molecular sieves, water-containing organic solvents, for example 80% ethanol, or salt hydrates, for example CaCl 2 x 6H 2 O.
  • moisture-laden adsorbents for example silica gel or molecular sieves
  • water-containing organic solvents for example 80% ethanol
  • salt hydrates for example CaCl 2 x 6H 2 O.
  • pure water is preferably used.
  • Proton- or hydroxyl-ion-releasing compounds and amines can be used as hydrolysis and condensation catalysts.
  • organic or inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid or acetic acid as well as organic or inorganic bases such as ammonia, alkali or alkaline earth metal hydroxides, e.g. Sodium, potassium or calcium hydroxide, and amines soluble in the reaction medium, e.g. lower alkylamines or alkanolamines.
  • Volatile acids and bases in particular hydrochloric acid, acetic acid, ammonia or triethylamine, are preferred here.
  • the resulting mixture is subjected to weak shear in step (2).
  • the weak shear can be exerted with the aid of customary and known devices, such as stirrers of the most varied types, for example anchor stirrers or paddle stirrers.
  • Step (2) is preferably carried out at a temperature of ⁇ 40 ° C., preferably ⁇ 30 ° C. and in particular at room temperature.
  • the mixture (2) can be sheared for more or less long.
  • the duration of the shear is preferably 10 minutes to 10 hours, preferably 20 minutes to 5 hours and in particular 30 minutes to 3 hours.
  • the dispersions according to the invention can be used as such as coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals or for the production of optical moldings and self-supporting foils, as described, for example, in the patent applications described at the outset or in the German patent application DE 198 16 136 A 1, column 7, line 24 until column 8, line 57 is described.
  • dispersions according to the invention are preferably used for the production of coating materials, adhesives and sealants, in particular coating materials.
  • the content of the dispersions according to the invention in the dispersions according to the invention can vary widely and depends on the requirements of the individual case.
  • the content is preferably adjusted so that the coating materials, adhesives and sealants according to the invention, based in each case on their total amount, the surface-modified nanoparticles in an amount of 0.05 to 4, preferably 0.07 to 3.5, particularly preferably 0.1 to 3, very particularly preferably 0.15 to 2.5 and in particular 0.2 to 2 wt.% Contain. It is advantageous if the content of the coating materials, adhesives and
  • Sealants on the compounds (C), based in each case on their total amount, are 5 to 30, preferably 6 to 28, particularly preferably 7 to 26, very particularly preferably 8 to 24 and in particular 10 to 22% by weight. If such a share does not have the inventive Dispersions can be entered, additional amounts of compounds (C) are added.
  • the coating materials, adhesives and sealants according to the invention are used to produce coatings, adhesive layers and seals.
  • the coatings, adhesive layers and seals according to the invention are used for coating, gluing and sealing motor vehicle bodies and parts thereof, vehicles in interior and exterior areas, structures in interior and exterior areas, doors, windows, furniture and hollow glass articles and in the context of industrial painting for the coating, gluing and sealing of plastic parts, small parts, coils, containers, electrotechnical components and white goods as well as of.
  • the coatings serve to increase the scratch and abrasion resistance and the corrosion resistance, to improve the cleaning behavior, to improve the removal from the mold and to reduce the adhesion, to produce an anti-fogging effect, to produce anti-reflective properties and / or to increase the burst pressure.
  • the coating materials according to the invention are used as clear lacquers for the production of clear lacquers, in particular in color and / or effect multi-layer lacquers.
  • the dispersions of the invention are added to customary and known clearcoats. From a methodological point of view, the production of the clear lacquers according to the invention has no special features, but takes place with the help of customary and known mixing methods and devices, such as stirred kettles, Ultraturrax, dissolvers, inline dissolvers, gear rim dispersers, static mixers, kneaders or extruders.
  • Suitable clearcoats are one- or multi-component clearcoats, powder clearcoats, powder slurry clearcoats, UV-curable clearcoats or sealers, as described in patent applications, patent specifications and publications DE 4204518 A1, EP 0594068 A1, EP 0594071 A1, EP 0594142 A1, EP 0604992 A 1, EP 0596460 A 1, WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, US 5,474,811 A 1, US 5,356,669 A 1 or US 5,605,965 A 1, DE 4222194 A 1, the product information from the company BASF Lacke + Maschinen AG, "Powder Coatings", 1990, the company publication of BASF Coatings AG "Powder Coatings, Powder Coatings for Industrial Applications", January 2000, US 4,268,542 A1, DE 19540977 A 1, DE 19518392 A1, DE 19617086 A1, DE-A-19613547, DE 1965
  • Solvent-containing one-component and multi-component clearcoats are particularly preferably used. These clear coats preferably contain
  • At least one binder with a statistical average of at least one isocyanate-reactive functional group in the molecule.
  • At least one crosslinking agent containing, on average, at least one blocked or unblocked isocyanate group and at least one functional group with at least one bond which can be activated with actinic radiation in the molecule, as described above.
  • Suitable isocyanate-reactive functional groups are hydroxyl, thiol and primary and secondary amino groups, especially hydroxyl groups.
  • the binder can also contain at least one, in particular at least two, of the reactive functional groups described above with at least one bond which can be activated with actinic radiation.
  • Suitable binders are thermally or thermally and curable with actinic radiation, random, alternating and / or block-shaped linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, polyaddition resins and / or polycondensation resins.
  • Polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyester.
  • the (meth) acrylate copolymers and the polyesters have particular advantages and are therefore used with particular preference.
  • Suitable olefinically unsaturated monomers (a) for the preparation of the (meth) acrylate copolymers are
  • Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha.beta-olefinically unsaturated carboxylic acid which are derived from an alkylene glycol which is esterified with the acid, or which can be obtained by reacting the alpha.beta- olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are, in particular, hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid,
  • Fumaric acid or itaconic acid in which the Hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1, 4-
  • olefinically unsaturated alcohols such as allyl alcohol
  • Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
  • Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid or instead of the reaction product, an equivalent amount of acrylic and / or methacrylic acid, which then during or after the polymerization reaction with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, is reacted;
  • Methyliminoethylacrylat; and or Acryloxysilane-containing vinyl monomers which can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with (meth) acrylic acid and / or hydroxyalkyl and / or cycloalkyl esters of (meth) acrylic acid and / or other hydroxyl-containing monomers (a1).
  • Acrylic acid beta-carboxyethyl acrylate, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
  • Methyl vinyl benzoic acid (all isomers) or vinyl benzene sulfonic acid (all isomers).
  • acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane-1, 6-diol, octahydro- 4,7-methano-1 H-indene-dimethanol or cyclohexane-1, 2-, -1, 3- or -1, 4-diol-di (meth) acrylate;
  • higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane-1, 6-diol, octahydro- 4,7-methano-1 H-indene-dimethanol or cyclohexane-1, 2-, -1, 3- or -1, 4-d
  • Trimethylolpropane di- or tri (meth) acrylate or pentaerythritol di, tri or tetra (meth) acrylate.
  • minor amounts of higher-functional monomers (a31) are to be understood as amounts which do not lead to crosslinking or gelling of the copolymers, unless they are intended to be in the form of crosslinked microgel particles.
  • the branched Monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins. When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • vinyl esters can also be prepared from the acids in a manner known per se, e.g. by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used. Vinyl esters of this type are sold under the VeoVa® brand (see also Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598).
  • Diarylethylenes in particular those of the general formula I:
  • radicals R 2 , R 3 , R 4 and R 5 each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals the
  • R 2 , R 3 , R 4 and R 5 represent substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals.
  • suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
  • suitable cycloalkyl radicals are examples of suitable alkyl radicals.
  • Cyclobutyl, cyclopentyl or cyclohexyl examples include methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane.
  • suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl.
  • suitable aryl radicals are phenyl,
  • Naphthyl or biphenylyl preferably phenyl and naphthyl and especially phenyl.
  • suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene.
  • suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl.
  • suitable arylalkyl radicals are 2-, 3- or 4-methyl-,
  • Ethyl, propyl or butylphen-1-yl examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.
  • the aryl radicals R 2 , R 3 , R 4 and / or R 5 are preferably phenyl or naphthyl radicals, in particular phenyl radicals.
  • the substituents optionally present in the radicals R 2 , R 3 , R 4 and / or R 5 are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or completely halogenated alkyl, cycloalkyl, alkylcycloalkyl , Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl
  • Arylalkyl and arylcycloalkyl radicals Aryloxy, alkyloxy and cycloalkyloxy radicals; and / or arylthio, alkylthio and cycloalkylthio radicals.
  • Diphenylethylene, dinaphthaleneethylene, eis or trans-stilbene or vinylidene-bis (4-nitrobenzene), in particular diphenylethylene (DPE), are particularly advantageous, which is why they are preferably used.
  • the monomers (b33) are used in order to regulate the copolymerization in an advantageous manner in such a way that free-radical copolymerization in a batch mode is also possible.
  • Vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene.
  • Nitriles such as acrylonitrile and / or methacrylonitrile.
  • Vinyl compounds especially vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride,
  • Vinylidene dichloride or vinylidene difluoride N-vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam or N-vinylpyrrolidone; 1-vinylimidazole; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; and / or vinyl esters such as vinyl acetate,
  • Monomers (a37) allyl compounds, in particular allyl ethers and esters such as
  • Monomers (a38) polysiloxane macromonomers, which are number average
  • Molecular weight Mn from 1,000 to 40,000 and on average 0.5 to 2.5 have ethylenically unsaturated double bonds per molecule; in particular polysiloxane macromonomers which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated
  • Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene,
  • the (meth) acrylate copolymers have a glass transition temperature of - 50 ° C. to + 110, preferably - 30 to + 80, preferably - 15 to + 70, particularly preferably - 15 to + 50, very particularly preferably - 15 to + 5 40 and in particular - 15 to + 30 ° C.
  • the acid number is preferably 3 to 100 mg KOH / g.
  • Particular advantages result from the use of the monomers (a2) 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl and 4-hydroxybutyl acrylate and methacrylate.
  • Reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, as described, for example, in the patents and the
  • polyesters are, in particular, aliphatic polyesters based on hexahydrophthalic anhydride.
  • the polyesters are commercially available products and are sold, for example, by Bayer AG under the Desmophen ® 2089, A 575 and 670 brand.
  • polyesters are described, for example, in the standard work Ullmanns Encyklopadie der Technische Chemie, 3rd edition, volume 14, Urban & Schwarzenberg, Kunststoff, Berlin, 1963, pages 80 to 89 and pages 99 to 105, and in the books: “Resines Alkydes -Polyesters "by J. Bourry, Paris, Dunod Verlag, 1952," Alkyd Resins “by CR Martens, Reinhold Publishing Corporation, New York, 1961, and” Alkyd Resin Technology “by TC Patton, Intersience Publishers, 1962.
  • Reactive functional groups with at least one bond which can be activated by actinic radiation can be introduced, for example, by polymer-analogous reaction of the (meth) acrylate copolymers described above with suitable compounds which contain bonds which can be activated by actinic radiation.
  • any side glycidyl groups of the (meth) acrylate copolymers present can be reacted with (meth) acrylic acid.
  • some of the hydroxyl groups can be reacted with compounds which contain a free isocyanate group and at least one, in particular one, bond which can be activated with actinic radiation.
  • suitable compounds of this type are 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® from Cytec) or vinyl isocyanate.
  • the content of the binders in the clearcoat materials of the invention can vary widely and depends primarily on the functionality of the binders on the one hand and the crosslinking agents on the other.
  • the content, based on the solids content of a coating material according to the invention, is preferably 20 to 90, preferably 25 to 85, particularly preferably 30 to 80, very particularly preferably 35 to 75 and in particular 40 to 70% by weight.
  • the crosslinking agent preferably takes part in both thermal curing and curing with actinic radiation.
  • the statistical crosslinking agent contains at least one, in particular at least two unblocked or at least two blocked isocyanate groups in the molecule.
  • phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol,
  • lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam or ß-propiolactam
  • active methylenic compounds such as diethyl malonate
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol,
  • Ethylene glycol monobutyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, glycolic acid ester, lactic acid,
  • Lactic acid ester methylol urea, methylol melamine, Diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1, 3-dichloro-2-propanol, 1, 4-cyclohexyldimethanol or
  • mercaptans such as butyl mercaptan, hexyl mercaptan, t-
  • Acid amides such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or
  • imides such as succinimide, phthalimide or maleimide
  • amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
  • imidazoles such as imidazole or 2-ethylimidazole
  • ureas such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;
  • xi) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone
  • imines such as ethyleneimine
  • oximes such as acetone oxime, formal doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime,
  • Benzophenone oxime or chlorohexanone oximes xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;
  • xv) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or
  • the crosslinking agent contains on average at least one, in particular at least two, functional groups with at least one bond which can be activated with actinic radiation in the molecule, as described above.
  • the crosslinking agent can be made in any manner.
  • crosslinking agents which are produced from at least one polyisocyanate with an isocyanate functionality of at least 2.0 are particularly advantageous.
  • the polyisocyanate preferably had an isocyanate functionality of 2.0 to 6.0, preferably 2.0 to 5.0, particularly preferably 2.0 to 4.5 and in particular 2.0 to 3.5.
  • aliphatic and cycloaliphatic polyisocyanates are preferably used.
  • cycloaliphatic diisocyanate denotes a diisocyanate in which at least one isocyanate group is bonded to a cycloaliphatic radical.
  • Suitable acyclic aliphatic diisocyanates with an isocyanate functionality of 2.0 are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate,
  • hexamethylene diisocyanate is of particular advantage and is therefore used with very particular preference in accordance with the invention.
  • suitable polyisocyanates with an isocyanate functionality> 2 are polyisocyanates, in particular based on hexamethylene diisocyanate, which contain isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione groups and which are more commonly known Ways are obtainable from the diisocyanates described above.
  • the allophanate groups are advantageous and are therefore used with particular preference in accordance with the invention.
  • polyisocyanates described above are reacted with at least one compound which contains at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, bond which can be activated with actinic radiation.
  • Suitable isocyanate-reactive functional groups are hydroxyl, thiol and / or primary and / or secondary amino groups, especially hydroxyl groups.
  • Suitable compounds having at least one, in particular one, isocyanate-reactive functional group and at least one, in particular one, bond which can be activated with actinic radiation are per molecule Allyl alcohol or 4-butyl vinyl ether;
  • Esterification of aliphatic diols for example the low-molecular diols B) described above, with acrylic acid or methacrylic acid or by reaction of acrylic acid or methacrylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid or methacrylic acid, in which the
  • Hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, bis (hydroxymethyl) cyclohexane acrylate or methacrylate; Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly advantageous and are therefore used with particular preference in accordance with the invention; or
  • Reaction products from cyclic esters e.g. epsilon-caprolactone, and these hydroxyalkyl or cycloalkyl esters.
  • the higher-functionality polyisocyanates described above are used as crosslinking agents.
  • the polyisocyanates are mixed with at least one of those described above Blocking agents converted to the corresponding blocked isocyanate crosslinking agents.
  • the crosslinking agent is prepared by reacting the compounds described above with the polyisocyanates in a molar ratio such that, on statistical basis, at least one free isocyanate group remains in the resulting adduct, which is available for reaction with the blocking agents described above ,
  • the crosslinking agent is prepared by reacting the blocking agents described above with the polyisocyanates in a molar ratio such that, on statistical average, at least one free isocyanate group remains in the adduct and is available for reaction with the compounds described above.
  • the crosslinking agent is prepared by reacting the compounds described above and the blocking agents described above with the polyisocyanates in a one-pot process.
  • the content of the crosslinking agents in the clearcoat materials of the invention can vary widely and depends primarily on the functionality of the crosslinking agent (A) on the one hand and the functionality of the binder (B) on the other hand.
  • the one-component system according to the invention preferably contains 10 to 80, based on its solid, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight.
  • the clear lacquer according to the invention can also contain conventional and known additives in effective amounts, such as those from German patent application DE 199 24 171 A1, page 8, lines 5 to 46, and page 8, line 61, to page 9, line 32, are known, in particular photoinitiators, such as those of the Norrish II type, whose mechanism of action is based on an intramolecular variant of the hydrogen abstraction reactions, as they occur in a variety of ways in photochemical reactions (for example, here on Römpp Chemie Lexikon, 9th expanded and revised edition, Georg Thieme Verlag Stuttgart, Vol.
  • cationic photoinitiators for example, refer to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446, in particular benzophenones, benzoins or benzoin ether or phosphine oxides.
  • Suitable substrates are all surfaces to be painted which are not damaged by hardening of the paints thereon using heat or heat and actinic radiation.
  • Suitable substrates consist, for example, of metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials such as gypsum and cement boards or roof tiles, as well as composites of these materials.
  • the surfaces of these materials can already be pre-painted or pre-coated.
  • primers can be used which are made in a customary and known manner from electrocoat materials
  • ETL electrocoat materials
  • ATL anodic
  • KTL cathodic
  • primed or non-primed plastics such as. B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) as well as their polymer blends or the fiber-reinforced composite materials made with these plastics are coated.
  • plastics such as. B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, P
  • non-functionalized and / or non-polar substrate surfaces these can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before the coating.
  • the clear lacquers according to the invention and the clear lacquers according to the invention show particular advantages in automotive series and refinishing as clear and transparent, highly scratch-resistant, high-gloss flexible, chemical-resistant, weather-resistant, acid and water-resistant, firmly adhering, stone-chip-resistant clear lacquers in the context of coloring and / or effect-giving coating systems.
  • the multi-layer coatings according to the invention can be produced in different ways according to the invention.
  • a first preferred variant of the painting process according to the invention comprises the process steps: (I) producing a basecoat film by applying a waterborne basecoat to the substrate,
  • This variant offers particular advantages particularly when painting plastics and is therefore used with particular preference here.
  • a second preferred variant of the painting process according to the invention comprises the process steps:
  • a third preferred variant of the painting process according to the invention comprises the process steps:
  • a fourth preferred variant of the painting process according to the invention comprises the process steps:
  • Basecoat and the clearcoat according to the invention result (wet-on-wet process).
  • the last three variants offer particular advantages, particularly for the initial painting of automobile bodies, and are therefore used with particular preference here. It is a very particular advantage of the coatings produced from the clearcoats according to the invention that they also adhere excellently to already cured electro-dip coats, filler coats, basecoats or customary and known clearcoats, so that they are excellently suited for automotive refinishing or scratch-proofing of exposed areas of painted automobile bodies.
  • the clearcoats of the invention can be applied by all customary application methods, such as Spraying, knife coating, brushing, pouring, dipping, watering, trickling or rolling.
  • the substrate to be coated can rest as such, with the application device or system being moved.
  • the substrate to be coated in particular a coil, can also be moved, the application system being stationary relative to the substrate or being moved in a suitable manner.
  • Spray application methods are preferably used, such as, for example, compressed air spraying, Airiess spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as, for example, hot air hot spraying.
  • the applications can be used at temperatures of max. 70 to 80.degree. C. are carried out so that suitable application viscosities are achieved without the water-borne basecoat and its overspray, which may need to be reprocessed, being changed or damaged in the event of brief thermal exposure.
  • hot spraying can be designed in such a way that the clear lacquer is only heated very briefly in or shortly before the spray nozzle.
  • the spray booth used for the application can be operated, for example, with a circulation that can be tempered, if necessary, which is equipped with a suitable absorption medium for the overspray, e.g. B. the clearcoat of the invention itself is operated.
  • the electrophoretic coating layer, the filler coating layer, the basecoat layer and the inventive clearcoat layer are applied in a wet layer thickness so that after curing, layers with the necessary and advantageous layer thicknesses for their functions result.
  • this layer thickness is 10 to 70, preferably 10 to 60, particularly preferably 15 to 50 and in particular 15 to 45 ⁇ m; in the case of filler coating it is 10 to 150, preferably 10 to 120, particularly preferably 10 to 100 and in particular 10 to 90 ⁇ m; in the case of the basecoat, it is 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 ⁇ m; and in the case of the clearcoats according to the invention it is 10 to 100, preferably 15 to 80, particularly preferably 20 to 70 and in particular 25 to 60 ⁇ m.
  • suitable fillers in particular aqueous fillers, which are also referred to as stone chip protection primers or functional layers, for example from the patents US 4,537,926 A1, EP 0 529335 A1, EP 0595186 A1, EP 0639660 A1, DE 4438504 A1, DE 4337961 A 1, WO 89./10387, US 4,450,200 A 1, US 4,614,683 A 1 or WO 490/26827 are known.
  • Suitable basecoats in particular waterborne basecoats, and their use for producing color and / or effect multicoat paint systems, in particular by the wet-on-wet process, are known from patent applications EP 0089497 A1, EP 0256540 A1, EP 0260447 A1, EP 0297576 A.
  • the electrocoat, filler, basecoat and clearcoat of the invention can be thermally cured, and the Filler lacquer layer, base lacquer layer and clear lacquer layer according to the invention can be cured thermally or thermally and with actinic radiation (dual cure).
  • the clear lacquer layer according to the invention is cured thermally and with actinic radiation.
  • the hardening can take place after a certain rest period. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min.
  • the rest period is used, for example, for the course and degassing of the paint layers or for the evaporation of volatile components such as solvents.
  • the rest period can be supported and / or shortened by the use of elevated temperatures up to 90 ° C and / or by a reduced air humidity ⁇ 10g water / kg air, in particular ⁇ 5g / kg air, provided that no damage or changes to the paint layers occur. such as early full networking.
  • the thermal hardening has no special features in terms of method, but takes place according to the customary and known methods such as heating in a forced air oven or irradiation with IR lamps.
  • the thermal hardening can also be carried out in stages.
  • the thermal curing is advantageously carried out at a temperature of 50 to 200 ° C., particularly preferably 60 to 190 ° C. and in particular 80 to 180 ° C. for a time of 1 minute to 2 hours, particularly preferably 2 minutes to 1 hour and in particular 3 min to 45 min.
  • the curing with actinic radiation is preferably carried out with UV radiation and / or electron beams.
  • a dose of 1,000 to 3,000, preferably 1,100 to 2,900, particularly preferably 1,200 to 2,800, very particularly preferably 1,300 to 2,700 and in particular 1,400 to 2,600 mJ / cm 2 is preferably used here. If necessary this hardening with actinic radiation can be supplemented by other radiation sources.
  • electron beams work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the lacquer layers. Even in the case of curing with UV radiation, in order to avoid the formation of ozone, work can be carried out under an inert gas or in an oxygen-depleted atmosphere.
  • the usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.
  • Suitable radiation sources are flash lamps from VISIT,
  • High-pressure or low-pressure mercury vapor lamps which are optionally doped with lead in order to open a radiation window up to 405 nm, or
  • Electron beam sources The facilities and conditions of these curing methods are described, for example, in R. Holmes, U.V. and E.B.
  • German patent application DE 198 18 735 A1 column 10, lines 31 to 61.
  • the areas (shadow areas) which are not directly accessible to radiation, such as cavities, folds and other undercuts due to construction, can be combined with automatic, point, small area or all-round emitters
  • Movement device for irradiating cavities or edges (partially) are cured.
  • the curing can take place in stages, ie by multiple exposure or irradiation with actinic radiation. This can also be the case take place alternately, that is, alternately curing with UV radiation and electron radiation.
  • thermal curing and curing with actinic radiation are used together, these methods can be used simultaneously or alternately. If the two curing methods are used alternately, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start and end the curing with actinic radiation.
  • the multicoat paint systems of the invention have an excellent profile of properties, which is very well balanced in terms of mechanics, optics, corrosion resistance and adhesion.
  • the multi-layer coatings according to the invention have the high optical quality and interlayer adhesion required by the market and do not pose any problems, such as a lack of condensation resistance, cracking (mud cracking) or flow disturbances or
  • the multi-layer coatings according to the invention have an excellent metallic effect, an excellent D.O.I. (distinctiveness of the reflected image) and excellent surface smoothness. They are weather-resistant, resistant to chemicals and bird droppings and highly scratch-resistant.
  • the primed or unprimed substrates according to the invention have at least one substrate according to the invention
  • Coating are coated, with a particularly advantageous profile of application properties a particularly long Service life on what makes them economically, aesthetically and technically particularly valuable.
  • dispersions 1 to 3 For the preparation of the dispersions 1 to 3 according to the invention, 40.9 parts by weight of dipentaerythritol pentaacrylate, 35.2 parts by weight of n-propanol and 4.4 parts by weight of silicon dioxide nanoparticles were mixed together.
  • Aerosil ® 200 in example 2 Aerosil ® 130 and in example 3 Aerosil ® OX 50 from Degussa were used.
  • the resulting mixtures were ground in the first stage for one hour in a bead mill (Vollrath VSME). The temperatures did not rise above 30 ° C. The grinding media were then separated.
  • Methacryloyloxypropyltrimethoxysilane 6.3 parts by weight of aluminum tris (sec-butoxide) and 3 parts by weight of water are mixed.
  • the resulting mixture from step (2) was stirred for one hour at room temperature with a paddle stirrer.
  • Production Example 1 The production of a binder
  • the solvent was heated to 140 ° C, at which temperature a mixture of 652 parts by weight of ethylhexyl acrylate, 383 parts by weight of hydroxyethyl methacrylate, 143 parts by weight of styrene, 213 parts by weight of 4-hydroxybutyl acrylate and 49 parts by weight of acrylic acid was added for four hours and an initiator solution of 113 parts by weight was stirred at this temperature.
  • - Butyl perethylhexanoate and 113 parts by weight of the aromatic solvent were metered in uniformly over the course of four and a half hours. The inlets were started at the same time. After the end of the initiator feed, the editorial mixture was kept at 140 ° C. for two hours and then cooled.
  • the reaction mixture was diluted with a mixture of 1-methoxypropylacetate-2, butylglycol acetate and butyl acetate.
  • the resulting binder solution had a solids content of 65% by weight (1 h / 130 ° C.).
  • the acid number was 15 mg KOH / g solid resin.
  • a base coat of 35.9 parts by weight was first used the binder solution of Preparation 1, 1, 0 parts by weight of a substituted hydroxyphenyltriazine (65% in toluene), 1, 0 parts by weight of N-methyl-2,2,6,6-tetramethyl-piperidinyl ester (Tinuvin® 123 from Ciba Specialty Chemicals ), 0.4 part by weight of a leveling agent (BYK® 306 from Byk Chemie), 0.5 part by weight of Lucirin® TPO (photoinitiator from BASF Aktiengesellschaft), 1.0 part by weight of Genocure® MBF (photoinitiator from Rahn), 2.0 Parts by weight of Irgacure® 184 (photoinitiator from Specialty Chemicals, Inc.), 10.8 parts by weight of solvent naphtha and 27.4 parts by weight of butyl diglycol acetate.
  • a leveling agent BYK® 306 from Byk Chemie
  • the base lacquer was then mixed in each case with the dispersion according to the invention from Example 1 and the isocyanatoacrylate Roskydal® UA VPLS 2337 from Bayer AG (based on: trimers hexamethylene diisocyanate; content of isocyanate groups: 12% by weight).
  • isocyanatoacrylate Roskydal® UA VPLS 2337 from Bayer AG (based on: trimers hexamethylene diisocyanate; content of isocyanate groups: 12% by weight).
  • dipentaerythritol pentaacrylate was additionally added. Table 1 gives an overview of the material composition of the clearcoats according to the invention.
  • Table 1 The material composition of the clearcoats of Examples 4 to 8 according to the invention
  • dipentaerythritol pentaacrylate 15.5 13.0 10.2 7.2 3.8 parts by weight of Aerosil® 200: 1, 7 1, 4 1.1 0.8 0.4 Additional dipentaerythritol pentaacrylate: 0.0 3.2 6.8 10.8 15.1
  • the clearcoats of Examples 4 to 8 were applied with the aid of a box doctor to degreased glass plates in a wet layer thickness of 100 ⁇ m.
  • the resulting clear lacquer layers were peeled off and dried at room temperature for 5 minutes and at 80 ° C. for 10 minutes. Then they were first cured with UV radiation at a dose of 1,500 mJ / cm2 and then for 20 minutes at 140 ° C.
  • the scratch resistance was determined using the steel wool test. For this purpose, the flat side of a locksmith hammer according to DIN 1041 was covered with a layer of steel wool. Then the hammer was carefully placed on the clearcoats at a right angle and passed over the clearcoats in a trace without tilting and without additional physical strength. In each test, 10 double strokes had to be carried out over 15 seconds.
  • the damage pattern was graded as follows:
  • the damage pattern was determined after 200 double strokes and the depth of the scratches was determined qualitatively.
  • the clearcoats were adjusted to a spray viscosity of 18s in a DIN 4 flow cup with butyl acetate and sieved (mesh size 31 ⁇ m).
  • test panels made of steel which were coated with electro-dip coatings with a dry film thickness of 18 to 22 ⁇ m, were coated with a water filler.
  • the resulting water filler layers were baked at 165 ° C. for 20 minutes, so that filler coatings with a dry layer thickness of 35 to 40 ⁇ m resulted.
  • the filler coatings were then coated with a black water-based lacquer in a layer thickness of 12 to 15 ⁇ m, and the resulting water-based lacquer layers were flashed off at 80 ° C. for 10 minutes.
  • the clearcoats of Examples 4 and 5 were then applied wet-on-wet pneumatically in a cloister with a gravity cup gun.
  • the clear lacquer layers were flashed off at room temperature for 5 minutes and at 80 ° C. for 10 minutes and dried. Then they were first cured with UV radiation at a dose of 1,500 mJ / cm2 and then for 20 minutes at 140 ° C.
  • the gloss and haze of the multi-layer coatings were determined in accordance with DIN 67530.
  • the micro penetration hardness was measured as universal hardness at 25.6 mN with a Fischersope 100 V with diamond pyramid according to Vickers.
  • the scratch resistance of the multi-layer paintwork was determined after the sand test.
  • the paint surface was loaded with sand
  • the scratch resistance was determined according to the Amtec-Kistler test known in the art (cf. T. Klimmasch, T. Engbert, Technologietage, Cologne, DFO, Report Volume 32, pages 59 to 66, 1997).
  • the scratch resistance was also determined using the steel wool test.
  • Example 1 The dispersion of Example 1 according to the invention was used to produce the clearcoat of Example 11 according to the invention.
  • Example 2 The inventive dispersion of Example 2 was used to produce the clearcoat material of Example 12 according to the invention.
  • Trimeric hexamethylene diisocyanate which was blocked with diethyl malonate and ethyl acetoacetate (cf. European patent application EP 0 626 888 A1, component C), was used as the crosslinking agent.
  • Table 4 gives an overview of the material composition.
  • Table 4 the material composition of the clearcoats according to the invention from Examples 4 to 8
  • Aerosil ® 130 1, 7
  • Aerosil ® OX50 - 1, 7

Abstract

L'invention concerne des dispersions organiques de nanoparticules à surface modifiée, que l'on produit (1) en soumettant à un cisaillement important un mélange contenant (A) des nanoparticules, (B) un amphiphile et (C) un composé comprenant au moins deux groupes à liaison activable par rayonnement actinique, (2) puis en soumettant à un cisaillement faible le mélange (1) conjointement avec un mélange contenant (D) un composé de formule générale (SoL-)mM(R)n(H)p (I) et (E) de l'eau. Dans la formule générale (I), S représente un groupe fonctionnel réactif, L représente un groupe de liaison au moins bivalent, H représente un groupe ou un atome hydrolysable, M représente un métal d'un groupe principal ou secondaire bivalent à hexavalent, R représente un groupe organique, o est un nombre entier compris entre 1 et 5, m + n + p est un nombre entier compris entre 2 et 6, p est un nombre entier compris entre 1 et 6, et m et n sont nuls ou sont un nombre entier compris entre 1 et 5. L'invention concerne également un procédé pour la production de ces dispersions organiques et leur utilisation.
PCT/EP2002/014569 2002-01-12 2002-12-19 Dispersions organiques de nanoparticules a surface modifiee, leur procede de production et leur utilisation WO2003057740A1 (fr)

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US8448885B2 (en) 2008-06-12 2013-05-28 3M Innovative Properties Company Methods of compounding nanoparticles with a resin
US9221970B2 (en) 2008-12-19 2015-12-29 3M Innovative Properties Company Nanocalcite composites
US9783681B2 (en) 2009-10-21 2017-10-10 3M Innovative Properties Company Solventless functionalization, milling, and compounding process with reactive diluents
US10023726B2 (en) 2009-12-17 2018-07-17 3M Innovative Properties Company Nanocalcite and vinyl ester composites
US10035909B2 (en) 2009-12-17 2018-07-31 3M Innovative Properties Company High magnesium surface concentration nanocalcite composites

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DE102004028764A1 (de) 2004-06-16 2006-01-12 Henkel Kgaa Strahlungshärtbares elektrisch leitfähiges Beschichtungsgemisch
DE102006044718A1 (de) * 2006-09-20 2008-04-03 Tesa Ag Klebemasse
DE102021003568A1 (de) 2021-07-12 2021-09-23 Daimler Ag Sitzanlage

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8448885B2 (en) 2008-06-12 2013-05-28 3M Innovative Properties Company Methods of compounding nanoparticles with a resin
US9221970B2 (en) 2008-12-19 2015-12-29 3M Innovative Properties Company Nanocalcite composites
US9783681B2 (en) 2009-10-21 2017-10-10 3M Innovative Properties Company Solventless functionalization, milling, and compounding process with reactive diluents
US10023726B2 (en) 2009-12-17 2018-07-17 3M Innovative Properties Company Nanocalcite and vinyl ester composites
US10035909B2 (en) 2009-12-17 2018-07-31 3M Innovative Properties Company High magnesium surface concentration nanocalcite composites

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