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WO2008145634A1 - Matières de revêtement peu visqueuses, contenant des silicates et durcissables par exposition à un rayonnement - Google Patents

Matières de revêtement peu visqueuses, contenant des silicates et durcissables par exposition à un rayonnement Download PDF

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Publication number
WO2008145634A1
WO2008145634A1 PCT/EP2008/056418 EP2008056418W WO2008145634A1 WO 2008145634 A1 WO2008145634 A1 WO 2008145634A1 EP 2008056418 W EP2008056418 W EP 2008056418W WO 2008145634 A1 WO2008145634 A1 WO 2008145634A1
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meth
coating composition
methacryloxy
radiation
silicate
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German (de)
English (en)
Inventor
Alexander Traut
Reinhold Rieger
Erich Beck
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BASF SE
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BASF SE
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    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention describes low-viscosity, silicate-containing, radiation-curable coating compositions and a process for the homogeneous dispersion of inorganic nanoparticles in radiation-curable coating compositions with the aim of reducing the viscosity.
  • Radiation-curable coating compositions comprising nanoscale silicate particles are known, for example, from EP 460560 A2, EP 565403 A1 and EP 220026 A2.
  • a disadvantage of silicate-containing radiation-curable coating compositions is that the incorporation of the silicate particles leads to a marked increase in viscosity, which must be counteracted, for example, by adding solvent or reactive diluent to the finished coating composition in order to bring the coating composition to the desired application viscosity.
  • solvents is undesirable because it must be removed from the coating and thus increases the content of volatile organic compounds (VOC).
  • VOC volatile organic compounds
  • the requirement of adding reactive diluents restricts the user's freedom of formulation.
  • This method is limited to polar compounds such as alkanol acrylates and is limited to unmodified silica sols.
  • EP 460560 A2 describes starting from alcoholic dispersions of silica sols the surface modification with double bond-containing silanes for use in free-radically polymerizable coating compositions.
  • silica sols which are present in alcohols.
  • Such silica sols are less commercially available than aqueous silica sols.
  • it is not disclosed at which pH the surface modification is carried out.
  • it is disadvantageous in this reaction procedure that only free silanol groups on the surface of the particles can react with the silanes in anhydrous alcoholic sols.
  • a condensation reaction and thus the tendency to aggregate, in alcoholic suspension can be prevented much easier than in aqueous suspension.
  • EP 1236765 A describes a process in which an alkali metal silicate solution is acidified with an acidic ion exchanger and converted to a silica sol and treated with a silicic acid. lan is surface-modified and this is then mixed with isopropanol and water is distilled off. The resulting silicates having a particle size of 3 to 50 nm can then be taken up in organic coating compositions.
  • the silica sols prepared are made alkaline after their preparation by acidic polycondensation to protect against agglomeration (paragraph [0042], see also example 1 of EP 13661 12 B1). Subsequently, ie in the alkaline pH range, the surface of the silica sol is optionally modified by reaction with functional silanes.
  • a disadvantage of this production process is that the products thus obtained have a relatively high viscosity.
  • a further disadvantage is that commercially available silicic acid sols which are modified in the alkaline pH range show a marked agglomeration and gelation tendency on addition of alcohols and / or silanes.
  • WO 2006/044376 describes the preparation of inorganic oxides, in particular silicates in an aqueous medium and subsequent distribution in organic radiation-curable coating compositions.
  • a process disclosed therein comprises, starting from a silica sol, an ion exchange with liberation of the acid, mixing with an organic solubilizer, addition of base and addition of a surface-modification silane. Again, the complete surface modification with the silane takes place in the alkaline pH range. Subsequently, the solvent is removed until dry and taken up in an organic solvent.
  • a disadvantage of this method is that the resulting solutions of silica sols using commercial silica sols have a high viscosity and also the surface of the particles must be completely reacted with silane to give a free-flowing powder. It is noted that surface treatment with silanes may be under acidic or basic conditions, but only alkaline reaction conditions are explicitly disclosed.
  • the aqueous nanosilicate sol is mixed directly with a solubilizer, which can simultaneously act as a reactive diluent, and the organic coating composition and the water is separated off by distillation and then taken up in an organic solvent.
  • the surface modification with a silane also takes place here in the alkaline.
  • the solubilizer remains in the coating composition and this method is applicable only to those solubilizers that can react simultaneously as reactive diluents.
  • another silica sol is functionalized with a functionalized alkoxysilane using a catalyst in the alkaline state. The product is taken up in a large amount of solvent and the catalyst removed by washing. The functionalized silicate is then used as an organic solution in further coating compositions.
  • a disadvantage of this method is that the catalyst has to be removed from the product in a complicated manner by means of washes in order to stop the reaction.
  • the resulting powders can no longer be completely redispersed, which leads to larger agglomerates in the product and thus to a reduced transparency of the coating.
  • US 2006/0251901 A1 describes the modification of colloidal silicates with various silanes in the presence of solvents and subsequent separation of water and incorporation, for example into radiation-curable coating compositions.
  • the colloidal silicate used is an alkaline silicate.
  • the object of the present invention was to provide radiation-curable coating compositions with low viscosity which contain finely divided silicates prepared starting from inexpensive commercially available products, wherein the silicates should be distributed uniformly in the coating composition. The reduction in visa In this case, the viscosity should be carried out with little or as little as possible use of solvent and / or reactive diluents.
  • At least one compound (S) which has at least one at least monoalkoxylated silyl group and at least one group which is reactive with the organic coating composition in an amount of from 0.1 to 20 ⁇ mol per m 2 surface area of (K), such as
  • At least one compound (M) having at least one radically polymerisable group wherein the (S) surface-modified particles (K) present in (M) have a half-width of the particle size distribution (measured by analytical ultracentrifuge) of at least 8 nm.
  • the silicate particles (K) used have an average particle diameter of 1 to 150 nm, preferably 2 to 120, more preferably 3 to 100 and most preferably 4 to 80 nm.
  • the content of silica is from 10 to 60% by weight, preferably from 20 to 55, particularly preferably from 25 to 40% by weight. It is also silica sols can be used with a lower content, but the excess water must then be separated by distillation in a later step.
  • the aqueous solutions (K) are colloidal solutions of polyalkanoic acid, which may contain a small proportion of alkali metal, alkaline earth metal, ammonium, aluminum, iron (II), iron (III) and / or or zirconium ions, preferably alkali metal, alkaline earth metal, ammonium and / or iron (II) ions, particularly preferably alkali metal, alkaline earth metal and / or ammonium ions, very particularly preferably alkali metal and / or alkaline earth metal ions and in particular re alkali metal ions.
  • alkali metal ions sodium and / or potassium ions are preferred, with sodium ions being particularly preferred.
  • alkaline earth metal ions magnesium, calcium and / or beryllium ions are preferred, magnesium and / or calcium ions are particularly preferred, magnesium ions are very particularly preferred.
  • the molar ratio of metal ions to silicon atoms in (K) is from 0: 1 to 0.1: 1, preferably from 0.002 to 0.04: 1.
  • the silica sols (K) used preferably have a pH of the aqueous phase of from 2 to 4, preferably from 2 to 3, but it is possible, although less preferably, for the sol to be at a pH to to 12, preferably up to 1 and more preferably up to 10 to leave.
  • an aqueous colloidal solution is understood as meaning a solution of optionally stabilized silica particles having an average particle diameter between 1 and 150 nm. If the solution should change in the course of storage, the solution is preferably further processed in a period in which the properties of the silica particles do not change significantly after the preparation. Typically, this period can be from 6 hours to 14 days.
  • SOI is meant in this document a colloidally disperse, incoherent (i.e., each particle is freely mobile) solution of a solid in water, here as silica sol a colloidally disperse solution of silica in water.
  • the acidic aqueous silica sols (K) used can be obtained, for example, in three different ways:
  • low molecular weight silicas preferably water glass, i. salt-like particles with a diameter below 1 nm, or - by condensation of esters of low molecular weight silicas.
  • the aqueous solutions of alkaline silica sols generally have a pH of from 7 to 11, preferably from 8 to 11, more preferably from 8 to 10, and most preferably from 9 to 10.
  • alkaline silica sols are commercially available and thus represent a readily available and preferred starting material for the process described.
  • the particles in these alkaline silica sols usually have an average particle diameter of 1 to 150 nm, preferably 2 to 120, more preferably 3 to 100 and most preferably 4 to 80
  • the content of silica, calculated as SiO 2 is from 15 to 60% by weight, preferably from 20 to 55, particularly preferably from 25 to 40% by weight. It is also possible to use alkaline silica sols with a lower solids content, but the excess water content must then be removed by distillation in a later step.
  • the alkaline silica sols can be stabilized with the above metal ions.
  • the molar ratio of metal ions to silicon atoms in (K) is from 0: 1 to 0.1: 1, preferably from 0.002 to 0.04: 1.
  • the pH of these alkaline silica sols is generally at least 8, preferably 8 to 12, particularly preferably 8 to 11 and very particularly preferably 8 to 10.
  • the preparation of the silica sols (K) to be used from these alkaline silica sols is carried out by adjusting the desired pH in these silica sols, for example adding mineral acids or adding the alkaline silica sols with an ion exchanger.
  • the acidification can be carried out with any acids, preferably with hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, methylsulfonic acid, para-toluenesulfonic acid or by addition with an acidic ion exchanger, preferably by acidification with hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or Acetic acid, particularly preferably with hydrochloric acid, nitric acid or sulfuric acid, and most preferably by acidification with sulfuric acid.
  • silica sols (K) it is a preferred embodiment to prepare the silica sols (K) by adding alkaline silica sols with an ion exchanger. This has the consequence that in the silica sols (K) the electrolyte content is low, for example less than 0.2% by weight and preferably less than 0.1% by weight.
  • Electrolytes are understood to mean other inorganic ionic constituents than silicates, hydroxides and protons. These electrolytes, which originate predominantly from the stabilization of the alkaline silica sols, are added to the suspension in order to stabilize the particles after their preparation.
  • silica sol (K) from water glass by acidification, for example with an ion exchanger or by adding mineral acid.
  • Potassium and / or sodium silicate which more preferably has a ratio of 1-10 mol of SiO 2 to 1 mol of alkali oxide, very particularly preferably 1.5-6 and in particular 2-4 mol of SiO 2 to 1 mol of alkali oxide, is preferably used as the water glass.
  • the reaction mixture is allowed to react until a silica sol (K) of the desired size is formed, and then proceeds to the process.
  • the low molecular weight silicic acids are normally stable only in highly dilute aqueous solutions with a content of a few% by weight and are usually concentrated before further use.
  • the preparation of the silica sols (K) can be carried out by condensation of esters of low molecular weight silicas. These are usually d- to C 4 -AlkVl-, especially ethyl esters of oligo- and especially orthosilicic acid, which form in acidic or basic silica sols (K).
  • the resulting acidified solution may be mixed with 0 to 10 times, preferably 0.2 to ⁇ times, more preferably 0.4 to 3 times, and most preferably 0.5 to 2 times the amount of water ( based on the amount of silica sol used) and 0.1 to 20 times, preferably 0.3 to 10 times, more preferably 0.5 to ⁇ fachen and most preferably 1 to 2 times the amount (based on the amount of added silica sol) is added to at least one organic solvent (L).
  • a preferred embodiment is to add no additional water.
  • the solvent (L) can be added to the reaction mixture before or during the reaction with the silane (S), preferably before or during and more preferably before the reaction with the silane.
  • the organic solvent (L) is selected according to the following criteria: Under the mixing conditions, it should have both sufficient miscibility with water and miscibility with the organic coating composition.
  • the miscibility with water under the reaction conditions should be at least 20% by weight (based on the finished water-solvent mixture), preferably at least 50% by weight and particularly preferably at least 80% by weight. If the miscibility is too low, there is a risk that the modified silica sol forms a gel or flocculates larger nanoparticle aggregates.
  • the coating composition should be completely soluble in the solvent (L) or the water-solvent mixture. Furthermore, the solvent (L) should have a boiling point of less than 80 0 C in a pressure range of atmospheric pressure to 50 hPa, so that it is easily separable by distillation.
  • the solvent (L) forms an azeotrope or heteroazeotrope with water under the conditions of the distillation, so that the distillate forms an aqueous and an organic phase after the distillation.
  • Suitable solvents (L) are ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-chloro-2-propanol, cyclopentanol, cyclohexanol, 1, 4-dioxane, tetrahydrofuran, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-ethoxyethanol, 2-methyl-2-propanol, 2-methoxyethanol, dimethylformamide, acetonitrile and acetone.
  • water and solvent (L), or their mixture can be carried out in one pour, in portions or continuously.
  • At least one compound (S) is added to the reaction mixture which contains at least one, preferably exactly one, at least one, for example one to three, preferably exactly triple alkoxylated silyl group and at least one, preferably exactly has a group that is reactive with the organic coating composition.
  • alkoxylated silyl groups are groups
  • R 1 is C 1 to C 20 -alkyl, preferably Cibis C 4 -alkyl and n is an integer from 1 to 3, preferably 3.
  • Examples of C 1 - to C 20 -alkyl are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, n-octyl, 2- Ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
  • C 1 to C 4 -alkyl are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
  • Preferred radicals R 1 are methyl, ethyl, n-butyl and tert-butyl, more preferably methyl and ethyl.
  • Groups which are reactive with the organic coating composition are those which preferably have the same group as the radiation-curable coating composition.
  • Free-radically polymerizable groups are, for example, allyl ether, vinyl ether, acrylate or methacrylate groups, preferably vinyl ether, acrylate or methacrylate groups, and more preferably acrylate or methacrylate groups, which are referred to briefly herein as (meth) acrylate groups particularly preferably acrylate groups.
  • These reactive groups are usually connected by spacer groups with the silyl groups.
  • spacer groups are divalent organic radicals having 1 to 20 carbon atoms, for example alkylene or arylene groups, preferably alkylene groups.
  • Examples of these are methylene, 1,2-ethylene (-CH 2 -CH 2 -), 1, 2-propylene (-CH (CH 2 ) -CH 2 -) and / or 1, 3-propylene (-CH 2 -CH 2 -CH 2 -), 1, 2, 1, 3 and / or 1, 4-butylene, 1, 1-dimethyl-1, 2-ethylene, 1, 2-dimethyl-1, 2-ethylene, 1 , 6-hexylene, 1, 8-octylene or 1, 10-decylene, preferably methylene, 1, 2-ethylene, 1, 2 or 1, 3-propylene, 1, 2, 1, 3 or 1, 4 Butylene, particularly preferably methylene, 1, 2-ethylene, 1, 2 and / or 1, 3-propylene and / or 1, 4-butylene and most preferably methylene, 1, 2-ethylene, 1, 2 and / or 1, 3-propylene.
  • Preferred compounds (S) are, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, isooctyltrimethoxysilane, N- (3-triethoxysilylpropyl) methoxyethoxyethoxyethylcarbamate (PEG3TES), N- (3-triethoxysilylpropyl ) methoxyethoxyethoxyethyl carbamate (PEG2TES), 3- (methacryloyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloxy) methyltriethoxysilane, 3- (Methacryloxy) ethyltriethoxysilane, 3- (methacryloxymethyl
  • the reaction of the silica sol (K) with at least one compound (S) takes place in a pH range which corresponds to the isoelectric point of the silica sol used ⁇ a pH unit. In most cases, this is a pH of 2 to 4.
  • the acidification can be carried out with any acids, preferably with hydrochloric acid, salicylic acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, methylsulfonic acid, para-toluenesulfonic acid or else by passing over acidic ion exchangers, preferably by acidification with hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid , Acetic acid or ion exchangers, particularly preferably with hydrochloric acid, nitric acid, sulfuric acid or ion exchangers, and very particularly preferably by acidification with sulfuric acid or ion exchangers.
  • the surface of the silica sol (K) used is modified so that the compatibility between the originally polar silica sol and the mostly non-polar coating composition is improved.
  • complete modification of the surface brings no further advantages. Therefore, it is usually sufficient if (S) is used in an amount of 0.1 to 20 micromol per m 2 surface area of (K), preferably in 0.25 to 15, particularly preferably 0.5 to 10 and particularly preferably 1 to 8 micromol per m 2 surface area of (K).
  • the reaction is preferably carried out in a manner such that not more than 20 mol% of the silane (S) used remain unreacted in the reaction mixture, preferably not more than 15 mol%, more preferably not more than 10 mol% and most preferably not more than 5 mol%.
  • reaction with (S) is carried out with stirring at a temperature of 10 to 60 ° C., preferably from 20 to 50, particularly preferably from 20 to 40 ° C.
  • the compound (S) is added in amounts of from 0.1 to 40% by weight, preferably from 0.5 to 30% by weight and more preferably from 1 to 20% by weight, based on the SiO 2 content.
  • samples of (K) are reacted with such amounts of (S) that, for example, 20, 40, 60, 80 and 100% of the hydroxy groups on the surface of (K) are modified with (S).
  • S amounts of (S) that, for example, 20, 40, 60, 80 and 100% of the hydroxy groups on the surface of (K) are modified with (S).
  • the silica sol (K) is generally present as a 3 to 30% strength by weight colloidal solution, the ratio of water to solvent (L) generally being 10 : 90 to 90:10 (v / v), preferably 25:75 to 75:25, and more preferably 40:60 to 60:40.
  • the radiation-curable coating compositions are in principle not limited.
  • they in the absence of the nanoscale silicate particles, optionally as a mixture of several radiation-curable compounds, they have a viscosity at 25 ° C. of not more than 4000 mPas (according to DIN EN ISO 3219 in a cone-plate rotational viscometer at a shear rate of 2500 S -1 ), preferably not more than 3000 mPas, particularly preferably not more than 2000 mPas, very particularly preferably not more than 1500 and in particular not more than 1000 mPas.
  • the condition is that the coating composition should have a boiling point above the boiling point of the solvent under the conditions of distillation, preferably at least 10 0 C higher, more preferably at least 25 0 C and most preferably at least 40 0 C higher.
  • These may be phenols, quinones, hydroquinones, N-oxyls, aromatic amines, especially phenylenediamines, sulfonamides, oximes, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds or metal salts.
  • inhibitors are described, for example, in DE 10258329 A1, paragraphs [0012] to [0043] and [0051] to [0071], especially [0051] to [0054] and [0069] to [0071], which are hereby incorporated by reference present disclosure.
  • N-oxyls such as, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4- Acetoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, 4,4 ', 4 "-tris (2,2,6, 6-tetramethyl-piperidine-N-oxyl) phosphite or 3-oxo-2,2,5,5-tetra-methyl-pyrrolidine-N-oxyl, phenols and naphthols, such as p-aminophenol, p-nitrosophenol , 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-methyl-2,6-tert-butylphenol ( 2,6-)
  • Preferred combinations are hydroquinone monomethyl ether and triphenyl phosphite as well as hydroquinone monomethyl ether and phenothiazine.
  • the inhibitors are usually added in amounts of 1 to 1000 ppm, preferably 5 to 800, particularly preferably 10 to 500 and very particularly preferably 20 to 300 ppm.
  • the added inhibitors are aerobic inhibitors that require the presence of molecular oxygen (O 2) to be fully effective. It may be a particularly preferred embodiment to employ as inhibitors a combination of at least one aerobic and at least one anaerobic inhibitor.
  • Aerobic inhibitors act only in the presence of oxygen, such aerobic inhibitors are, for example, phenolic polymerization inhibitors, such as hydroquinone monomethyl ether.
  • oxygen-containing gas air or a mixture of air and a gas inert under the reaction conditions may be preferably used.
  • Nitrogen, helium, argon, carbon monoxide, carbon dioxide, water vapor, lower hydrocarbons or mixtures thereof can be used as the inert gas.
  • the oxygen content of the oxygen-containing gas may be, for example, up to 21% by volume, preferably 1 to 21, particularly preferably 5 to 21 and very particularly preferably 10 to 20% by volume. Of course, if desired, higher oxygen contents can also be used, for example up to 50% by volume.
  • the coating composition is coated during mixing with the silicate with an oxygen-containing gas and / or passed through the mixture.
  • an oxygen-containing gas Deutschengeperlt, for example, by a dip or a frit, and / or used as a stripping gas.
  • the finished coating composition is to be cured by free radicals, for example by activation of photoinitiators (see below), it is advantageous to carry out the desired curing under an inert atmosphere in which the content of molecular oxygen is reduced.
  • anaerobic polymerization inhibitors e.g. Phenothiazine
  • Phenothiazine do not require oxygen, but are consumed by oxygen in non-polymerization-inhibiting side reactions.
  • the distilling off of water and the organic solvent (L) is carried out under normal or reduced pressure, preferably at 10 hPa to normal pressure, particularly preferably at 20 hPa to normal pressure, very particularly preferably at 50 hPa to normal pressure and in particular at 100 hPa to normal pressure.
  • the temperature at which the distillation takes place depends on the boiling point of water and / or organic solvent (L) at the respective pressure.
  • the distillation conditions are chosen so that water and the organic solvent form an azeotrope under the conditions.
  • the temperature is preferably not more than 80 ° C., preferably not more than 70 ° C.
  • the distillation can be carried out batchwise, semicontinuously or continuously.
  • the heat supply to the stirred tank via internal and / or external heat exchanger conventional design and / or double wall heater, preferably external circulation evaporator with natural or forced circulation.
  • the mixing the reaction mixture is carried out in a known manner, for. B. by stirring, pumping or natural circulation.
  • the distillation is preferably carried out by passing the distillation charge over a falling-film evaporator or a heat exchanger.
  • Suitable distillation apparatuses for this purpose are all distillation apparatuses known to the person skilled in the art, e.g. Circulation evaporator, thin film evaporator, falling film evaporator, wiper blade evaporator, optionally with each attached rectification columns and stripping columns.
  • Suitable heat exchangers are, for example, Robert evaporators or tube or plate heat exchangers.
  • water and solvent (L) are distilled off to the extent that the content of silicates in the coating composition is from 5 to 80% by weight, preferably from 20 to 60 and particularly preferably from 20 to 50% by weight.
  • the residual content of water in the finished product should be less than 5% by weight, preferably less than 3, particularly preferably less than 2, very particularly preferably less than 1, in particular less than 0.5 and especially less than 0.3% by weight.
  • the residual content of solvent (L) in the finished product should be less than 15% by weight, preferably less than 10, particularly preferably less than 5, very particularly preferably less than 3, in particular less than 2 and especially less than 1% by weight.
  • the reaction mixture remains from the addition of the organic solvent (L) until the end of the distillation, i. until reaching the above-mentioned desired residual water content in the finished product, in the acidic range, i. the pH is less than 7, preferably less than 6, more preferably less than 5, and most preferably less than 4. Since the pH can only be determined uncertainly with decreasing water content, the addition of basic compounds into the reaction mixture is alternative dispensed with the end of the distillation.
  • Basic compounds in this sense are those which upon addition of the same amount of the basic compound in an amount of water corresponding to the volume of the reaction mixture are capable of raising the pH from pH 7 to at least pH 8 or above.
  • this includes hydroxides, carbonates, bicarbonates, basic oxides, primary, secondary or tertiary amines or ammonia.
  • the removal of the water can be carried out instead of the distillation by absorption, pervaporation or diffusion through membranes.
  • the coating composition is at least one radiation-curable compound having at least one free-radically polymerizable group.
  • Suitable radiation-curable compounds are those which have at least one free-radically polymerizable group. These may be those with one and / or those having more than one ethylenically unsaturated group.
  • compounds having multiple, i. at least two, co-polymerisable, ethylenically unsaturated groups around vinyl ether or (meth) acrylate compounds particularly preferably the acrylate compounds, i. the derivatives of acrylic acid.
  • Preferred vinyl ether and (meth) acrylate compounds contain 2 to 20, preferably 2 to 10 and most preferably 2 to 6 copolymerizable, ethylenically unsaturated double bonds.
  • the number average molecular weight M n of the compounds is preferably below 15,000, more preferably 300-12,000, most preferably 400-5,000 and in particular 500-3,000 g / mol (determined by gel permeation chromatography with polystyrene as standard and Tetrahydrofuran as eluent).
  • (meth) acrylate compounds may be mentioned (meth) acrylic acid esters and in particular acrylic acid esters and vinyl ethers of polyfunctional alcohols, in particular those which contain no further functional groups or at most ether groups in addition to the hydroxyl groups.
  • examples of such alcohols are, for example, bifunctional alcohols, such as ethylene glycol, propylene glycol and their more highly condensed representatives, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, etc., 1, 2, 1, 3 or 1, 4-butanediol, 1, 5 Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentylglycol, alkoxylated phenolic compounds, such as ethoxylated and / or propoxylated bisphenols, 1, 2-, 1, 3- or 1, 4- Cyclohexanedimethanol, trifunctional and higher functional alcohols, such as glyce
  • the alkoxylation products are obtainable in a known manner by reacting the above alcohols with alkylene oxides, in particular ethylene oxide or propylene oxide.
  • the degree of alkoxylation per hydroxyl group is preferably 0 to 10, ie 1 mol of hydroxyl group can be alkoxylated with up to 10 mol of alkylene oxides.
  • polyester (meth) acrylates which are the (meth) acrylic esters or vinyl ethers of polyesterols, and urethane, epoxide or melamine (meth) acrylates.
  • Urethane (meth) acrylates are e.g. obtainable by reacting polyisocyanates, preferably based on (cyclo) aliphatic diisocyanates, with at least one, preferably exactly one isocyanate-reactive group and at least one free-radically polymerizable group, and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.
  • the diisocyanates are preferably isocyanates having 4 to 20 C atoms.
  • Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate or cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-
  • hexamethylene diisocyanate 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane, particularly preferred is hexamethylene diisocyanate.
  • Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates of preferably (cyclo) aliphatic diisocyanates or mixtures thereof.
  • (Cyclo) aliphatic means cycloaliphatic or aliphatic.
  • Isocyanate-reactive groups can be, for example, -OH, -SH, -NH 2 and -NHR 2 where R 2 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl iso-butyl, sec-butyl or tert-butyl.
  • the compounds may e.g. Monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid or vinyl ethers with di- or polyols, which preferably have 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
  • 2-aminoethanol 2- (methylamino) - ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2- (2-aminoethoxy) ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or vinylacetic acid.
  • 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1, 4-butanediol monoacrylate, 3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate and the monoacrylates of polyethylene glycol of molecular weight from 106 to 238.
  • 2-hydroxyethyl (meth) acrylate 2- or 3-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, glyceryl mono (meth) acrylate , Pentaerythritol tri (meth) acrylate and 4-hydroxybutyl vinyl ether.
  • the urethane (meth) acrylates preferably have a number-average molecular weight M n of from 500 to 20,000, in particular from 750 to 10,000, particularly preferably from 750 to 3,000 g / mol (determined by gel permeation chromatography using polystyrene as standard). dard).
  • the urethane (meth) acrylates preferably have a content of from 1 to 5, more preferably from 2 to 4 moles of (meth) acrylic groups per 1,000 g of urethane (meth) acrylate.
  • Epoxide (meth) acrylates are obtainable by reacting epoxides with (meth) acrylic acid.
  • Suitable epoxides are, for example, epoxidized olefins or glycidyl ethers, e.g. Bisphenol A diglycidyl ethers or aliphatic glycidyl ethers such as butanediol diglycidyl ether.
  • Melamine (meth) acrylates are obtainable by reacting melamine with (meth) acrylic acid or its esters.
  • the epoxide (meth) acrylates and melamine (meth) acrylates preferably have a number average molecular weight M n of 500 to 20,000, particularly preferably from 750 to 10,000 g / mol and very particularly preferably from 750 to 3,000 g / mol; the content of (meth) acrylic groups is preferably 1 to 5, more preferably 2 to 4 per 1000 g of epoxy (meth) acrylate or melamine (meth) acrylate (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent).
  • carbonate (meth) acrylates which contain on average preferably 1 to 5, in particular 2 to 4, particularly preferably 2 to 3 (meth) acrylic groups and very particularly preferably 2 (meth) acrylic groups.
  • the number average molecular weight M n of the carbonate (meth) acrylates is preferably less than 3,000 g / mol, more preferably less than 1,500 g / mol, more preferably less than 800 g / mol (determined by gel permeation chromatography with polystyrene as standard, solvent tetrahydrofuran).
  • the carbonate (meth) acrylates are readily obtainable by transesterification of carbonic acid esters with polyhydric, preferably dihydric alcohols (diols, eg hexanediol) and subsequent esterification of the free OH groups with (meth) acrylic acid or transesterification with (meth) acrylic esters, as it eg in EP-A 92,269. They are also available by reacting phosgene, urea derivatives with polyvalent, e.g. dihydric alcohols.
  • the radiation-curable, free-radically or cationically polymerizable compounds having only one ethylenically unsaturated, copolymerizable group are often reactive diluents, that is to say compounds of low viscosity which simultaneously participate in the polymerization reaction.
  • C 1 -C 20 -alkyl (meth) acrylates vinylaromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, ethylenically unsaturated nitrites, vinyl ethers of alcohols containing from 1 to 10 carbon atoms, ß-unsaturated carboxylic acids and their anhydrides and aliphatic hydrocarbons having 2 to 8 carbon atoms and 1 or 2 double bonds.
  • Preferred (meth) acrylic acid alkyl esters are those having a C 1 -C 10 -alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are e.g. Vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
  • ⁇ , ⁇ -Unsaturated carboxylic acids and their anhydrides can be, for example, acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, maleic acid or maleic anhydride, preferably acrylic acid.
  • vinyl aromatic compounds are e.g. Vinyltoluene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene into consideration.
  • nitriles are acrylonitrile and methacrylonitrile.
  • Suitable vinyl ethers are e.g. Vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
  • non-aromatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds may be mentioned butadiene, isoprene, and ethylene, propylene and isobutylene.
  • N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam can be used.
  • the silicate-containing coating composition obtained according to the invention can still be mixed with photoinitiators.
  • the photoinitiators may already be present during mixing with the silicates.
  • photoinitiators known to those skilled in the art may be used, e.g. those in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or K.
  • KT Oldring (Eds), SITA Technology Ltd, London.
  • Suitable examples include mono- or Bisacylphosphinoxide Irgacure® 819 (bis (2,4,6-tri-methylbenzoyl) phenylphosphine oxide), as described for example in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 are described or EP-A 615 980, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin ® TPO), ethyl-2,4,6-trimethylben- zoylphenylphosphinat, benzophenones, hydroxyacetophenones, phenylglyoxylic acid and its derivatives or mixtures these photoinitiators.
  • Irgacure® 819 bis (2,4,6-tri-methylbenzoyl) phenylphosphine oxide
  • Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4 ' -Methoxyacetophenone, ⁇ -methylanthraquinone, tert-butylanthraquinone, anthraquinone-carboxylic acid ester, benzaldehyde, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluororon, 1-in
  • non-yellowing or slightly yellowing photoinitiators of the phenylglyoxalic acid ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • phosphine oxides ⁇ -hydroxyketones and benzophenones are preferred.
  • mixtures of different photoinitiators can be used.
  • the photoinitiators may be used alone or in combination with a photopolymerization onspromotor, e.g. benzoic, amine or similar type.
  • a photopolymerization onspromotor e.g. benzoic, amine or similar type.
  • further typical coatings additives for example antioxidants, antioxidants, stabilizers, activators and the like.
  • accelerators, fillers, pigments, dyes, degassing agents, brighteners, antistatic agents, flame retardants, thickeners, thixotropic agents, leveling agents, binders, antifoams, fragrances, surface-active agents, viscosity modifiers, plasticizers, plasticizers, tackifying resins (tackifiers), Chelating agent or compatibilizer can be used.
  • a post-curing accelerator e.g. Tin octoate, zinc octoate, dibutyltin laureate or diaza [2.2.2] bicyclooctane.
  • photochemically and / or thermally activatable initiators for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate or benzopinacol, as well as, for example, those thermally activatable initiators having a half life of 80 0 C of more than 100 hours, such as di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, silylated pinacols, the z.
  • photochemically and / or thermally activatable initiators for example potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-ter
  • ADDID 600 commercially available under the trade name ADDID 600 from Wacker or hydroxyl-containing amine-N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6, 6-tetramethylpiperidine-N-oxyl etc.
  • chelating agents e.g. Ethylenediamine and their salts and ß-diketones are used.
  • Suitable fillers include silicates, e.g. For example, by hydrolysis of silicon tetrachloride available silicates such as Aerosil ® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates etc. Since silicates are uniformly introduced by the method in a coating composition, it represents a preferred embodiment, no further Add fillers.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ® grades from Ciba-Spezialitatenchemie) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. For example, bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used. Stabilizers are usually used in quantities from 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation used.
  • silicate-containing coating compositions and paint formulations according to the invention are particularly suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as cement blocks and fiber cement boards, or metals or coated metals, preferably plastics or Metals, which may be present as films, for example.
  • the thickness of such a layer to be cured as described may be from 0.1 ⁇ m to several mm, preferably from 1 to 2000 ⁇ m, more preferably 5 to 1000 ⁇ m, most preferably from 10 to 500 ⁇ m and in particular from 10 to 250 ⁇ m.
  • substrates coated with a multilayer coating according to the invention are also the subject of the present invention.
  • the substrates are coated by customary methods known to the person skilled in the art, at least one coating composition being applied to the substrate to be coated in the desired thickness and the volatile constituents of the coating composition, if appropriate with heating, being removed. This process can optionally be repeated one or more times.
  • the application to the substrate can in a known manner, for. Example by spraying, filling, doctoring, brushing, rolling, rolling, casting, lamination, injection molding or coextrusion done.
  • the coating thickness is usually in a range of about 3 to 1,000 g / m 2 and preferably 10 to 200 g / m 2 .
  • a method for coating substrates in which the coating composition is applied to the substrate and optionally dried, cured with electron beams or UV exposure under an oxygen-containing atmosphere or preferably under inert gas, optionally at temperatures up to the height of the drying temperature and then at temperatures up to to 160 0 C, preferably between 60 and 160 0 C, thermally treated.
  • the method for coating substrates can also be carried out so that after application of the coating composition initially at temperatures up to 160 0 C, preferably between 60 and 160 ° C, thermally treated and then with electron beams or UV exposure under oxygen or preferably under inert gas is hardened.
  • the curing of the films formed on the substrate can optionally be carried out exclusively thermally. In general, however, the coatings are cured both by irradiation with high-energy radiation and thermally.
  • Curing can also be done in addition to or instead of thermal curing
  • NIR radiation is carried out, wherein NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 microns, preferably from 900 to 1500 nm is designated.
  • thermal, NIR and / or radiation curing can take place after each coating operation.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, pulse emitters, metal halide lamps, electronic flash devices, which make radiation curing without a photoinitiator possible, or excimer radiators.
  • the radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or excimer radiators.
  • the radiation dose for UV curing which is usually sufficient for crosslinking, is in the range from 80 to 3,000 mJ / cm 2 .
  • radiation sources can be used for the curing, e.g. two to four.
  • the irradiation may preferably also in the absence of oxygen, for. B. under inert gas atmosphere, are performed.
  • inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases.
  • the irradiation can be carried out by covering the coating mass with transparent media.
  • Transparent media are z.
  • plastic films glass or liquids, eg. B. water. Particular preference is given to irradiation in the manner described in DE-A1 199 57 900.
  • Another object of the invention is a process for the coating of substrates, wherein i) coating a substrate with a silicate-containing coating composition as described above,
  • step iii) optionally irradiating the film formed in step ii) with high energy radiation, whereby the film is precured, then optionally mechanically working the precured film coated article or contacting the surface of the precured film with another substrate,
  • the steps iv) and iii) can also be performed in reverse order, d. H.
  • the film may first be cured thermally or by NIR radiation and then with high energy radiation.
  • the surface-modified particles (K) in the form as dispersed in the radiation-curable coating composition (M) have a half-width of the particle size distribution of at least 8 nm, preferably of at least 9 nm, being particularly preferred of at least 10, most preferably at least 1 1, in particular at least 13 nm and especially at least 15 nm.
  • the commercially available analytical ultra-centrifuge "OPTIMA XLI (Proteome Lab Upgrade)" Beckman Coulter GmbH, 47807 Krefeld, Germany is used.
  • the samples are diluted with ethanol to a concentration of the particles of 10 g / l. Subsequently, the samples are rolled for at least 10 minutes until they are homogenized. The sedimentation is carried out at 25 ° C.
  • G (s) is obtained, a mass-weighted distribution of the sedimentation constants s, which is converted into a mass-weighted diameter distribution g (d) by means of the Stokes-Einstein relation:
  • silicate-containing radiation-curable coating compositions have a lower viscosity than silicate-containing radiation-curable coating compositions which contain the same amount of surface-modified silicate particles which have a lower half-width. This viscosity behavior was unpredictable from the known prior art.
  • a basic silica sol having a SiO 2 solids content of 30% by weight and an average particle size of 30 nm (Levasil® 100, HCStark GmbH, Leverkusen, Germany) were mixed with 20 g of a strongly acidic cationic ion exchanger ( Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufmün, Germany), stirred for 30 minutes at room temperature, with a Adjusted pH of 2.3, and the ion exchanger is subsequently removed by filtration.
  • a strongly acidic cationic ion exchanger Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufmün, Germany
  • the suspension was admixed with 80 g of 1-propanol, 30 g of ethoxylated trimethylolpropane triacrylate (Laromer® 8863, BASF, Ludwigshafen, Germany), 0.2 g of triphenylphosphite and 40 mg of 4-methoxyphenol.
  • the volatiles were removed by means of a thin-film evaporator at 65 0 C and 50 mbar.
  • a flowable, transparent coating composition with a SiO 2 solids content of 48% was obtained which has a water content of 0.2% by weight and a propanol content of 0.17% by weight and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 0.88 Pa * s, as measured on the cone and plate viscometer at 23 ° C., with a shear rate of 5000 s -1 .
  • the width of the particle size distribution at half height (half-width) of this sample, which was determined by means of analytical ultracentrifuge, is 27.9 nm.
  • the suspension was admixed with 80 g of 1-propanol, 40 g of ethoxylated trimethylolpropane triacrylate (Laromer® 8863, BASF, Ludwigshafen, Germany), 0.3 g of triphenyl phosphite and 50 mg of 4-methoxyphenol.
  • the volatiles were removed by means of a thin-film evaporator at 65 0 C and 50 mbar. This gave a flowable, transparent coating composition having a SiO 2 solids content of 48%, which had a water content of 0.5% by weight. % and a propanol content of 0.6 wt .-% and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 1.68 Pa * s, measured on the cone-plate viscometer at 23 ° C., with a shear rate of 2500 s -1 .
  • the width of the particle size distribution at half height (half-width) of this sample, which was determined by means of analytical ultracentrifuge, is 1 1, 2 nm.
  • a basic silica sol with a SiC "2 solids content of 30% by weight and a mean particle size of 9 nm (Levasil® 300, HCStark GmbH, Leverkusen, Germany) were mixed with 20 g of a strongly acidic cationic ion exchanger in a glass beaker ( Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufmün, Germany), stirred for 30 minutes at room temperature, with a pH of 2.3, and the ion exchanger was subsequently removed by filtration.
  • the suspension was admixed with 80 g of 1-propanol, 30 g of ethoxylated trimethylolpropane triacrylate (Laromer® 8863, BASF, Ludwigshafen, Germany), 0.2 g of triphenylphosphite and 40 mg of 4-methoxyphenol.
  • the volatiles were removed by means of a thin-film evaporator at 65 0 C and 50 mbar.
  • a flowable, transparent coating composition with a SiO 2 solids content of 48% was obtained which has a water content of 0.3% by weight and a propanol content of 0.22% by weight and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 4.32 Pa * s, measured on the cone-plate viscometer at 23 ° C., with a shear rate of 1250 S -1 .
  • the width of the particle size distribution at half height (half-width) of this sample was determined by analytical ultracentrifuge is 6.6 nm.
  • a basic silica sol having a SiO 2 solids content of 30% by weight and an average particle size of 30 nm (Levasil® 100, HCStark GmbH, Leverkusen, Germany) were mixed with 30 g of a strongly acid cationic ion exchanger ( Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufmün, Germany), stirred for 30 minutes at room temperature, with a Adjusted pH of 2.4, and the ion exchanger is removed by filtration.
  • a strongly acid cationic ion exchanger Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufmün, Germany
  • the suspension was admixed with 300 ml of 1-propanol, 90 g of trimethylolpropane triacrylate (Laromer® TMPTA, BASF, Ludwigshafen, Germany), 0.125 g of 4-methoxyphenol and 0.5 g of triphenyl phosphite.
  • a flowable, transparent coating composition with a SiO 2 solids content of 48% was obtained which has a water content of 0.2% by weight and a propanol content of 0.7% by weight and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 1.64 Pa * s, measured on the cone-plate viscometer at 23 ° C., with a shear rate of 2500 S -1 .
  • the width of the particle size distribution at half the height (half-width) of this sample was determined by analytical ultracentrifuge, is 27.6 nm.
  • a basic silica sol having a SiC "2 solids content of 40% by weight and an average particle size of 15 nm (Levasil® 200, HCStark GmbH, Leverkusen, Germany) were mixed with 40 g of a strongly acidic cationic ion exchanger in a glass beaker ( Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufmün, Germany), stirred for 30 minutes at room temperature, with a pH of 2.4, and the ion exchanger was subsequently removed by filtration.
  • the suspension was admixed with 250 ml of 1-propanol, 100 g of trimethylolpropane triacrylate (Laromer® TMPTA, BASF, Ludwigshafen, Germany), 0.125 g of 4-methoxyphenol and 0.5 g of triphenyl phosphite.
  • the volatiles were removed at temperatures of 45 0 C to 70 0 C and under reduced pressure (100 to 50 mbar).
  • a flowable, transparent coating composition with a SiO 2 solids content of 48% was obtained which has a water content of 0.2% by weight and a propanol content of 0.84% by weight and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 1.96 Pa * s, measured on a cone-plate viscometer at 23 ° C., with a shear rate of 2500 s -1 .
  • the width of the particle size distribution at half height (half-width) of this sample was determined by analytical ultracentrifuge, is 10.9 nm.
  • a glass beaker 400 g of a basic silica sol having a SiC "2 solids content of 30% by weight and an average particle size of 9 nm (Levasil® 300, HCStark GmbH, Leverkusen, Germany) with 40 g of a strongly acidic cationic ion exchanger ( Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufmün, Germany), stirred for 30 minutes at room temperature, with a pH of 2.4, and the ion exchanger was subsequently removed by filtration.
  • a strongly acidic cationic ion exchanger Amberjet® 1200 (H)
  • Sigma Aldrich Chemie GmbH Taufmün, Germany
  • the suspension was admixed with 300 ml of 1-propanol, 90 g of trimethylolpropane triacrylate (Laromer®TMPTA, BASF, Ludwigshafen, Germany), 0.125 g of 4-methoxyphenol and 0.5 g of triphenyl phosphite.
  • Laromer®TMPTA trimethylolpropane triacrylate
  • the suspension was admixed with 300 ml of 1-propanol, 90 g of alkoxylated trimethylolpropane triacrylate (Laromer® PO 33F, BASF, Ludwigshafen, Germany), 0.125 g of 4-methoxyphenol and 0.5 g of triphenyl phosphite.
  • a flowable, transparent coating composition with a SiO 2 solids content of 48% was obtained which has a water content of 0.2% by weight and a propanol content of 0.12% by weight and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 0.78 Pa * s, measured on a cone and plate viscometer at 23 ° C., with a shear rate of 5000 s -1 .
  • the width of the particle size distribution at half height (half width) of this sample, which was determined by analytical ultracentrifuge is 28.2 nm.
  • the suspension was admixed with 250 ml of 1-propanol, 100 g of alkoxylated trimethylolpropane triacrylate (Laromer® PO 33F, BASF, Ludwigshafen, Germany), 0.125 g of 4-methoxyphenol and 0.5 g of triphenyl phosphite.
  • a flowable, transparent coating composition with a SiO 2 solids content of 48% was obtained which has a water content of 0.2% by weight and a propanol content of 0.62% by weight and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 1.84 Pa * s, measured on the cone-plate viscometer at 23 ° C., with a shear rate of 2500 s -1 .
  • the width of the particle size distribution at half height (half-width) of this sample, which was determined by analytical ultracentrifuge, is 1 1, 0 nm.
  • the suspension was admixed with 300 ml of 1-propanol, 90 g of alkoxylated trimethylolpropane triacrylate (Laromer® PO 33F, BASF, Ludwigshafen, Germany), 0.125 g of 4-methoxyphenol and 0.5 g of triphenyl phosphite.
  • a flowable, transparent coating composition having a SiO 2 solids content of 48% and having a water content of 0.2% by weight and a propanol content of 0.73% by weight was obtained and which is storable for at least 3 months.
  • the coating composition had a Brookfield viscosity of 3.52 Pa * s, measured on the cone-plate viscometer at 23 ° C., with a shear rate of 1250 S -1 .
  • the width of the particle size distribution at half height (half-width) of this sample was determined by analytical ultracentrifuge, is 6.7 nm.

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  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention décrit des matières de revêtement peu visqueuses, contenant des silicates et durcissables par exposition à un rayonnement, ainsi qu'un procédé permettant la dispersion homogène de nanoparticules inorganiques dans des matières de revêtement durcissables par exposition à un rayonnement, afin d'obtenir une réduction de la viscosité.
PCT/EP2008/056418 2007-05-25 2008-05-26 Matières de revêtement peu visqueuses, contenant des silicates et durcissables par exposition à un rayonnement Ceased WO2008145634A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP07108911 2007-05-25
EP07108911.4 2007-05-25
PCT/EP2008/056270 WO2008145585A1 (fr) 2007-05-25 2008-05-21 Procédé permettant de repartir des silicates dans des matières de revêtement
EPPCT/EP2008/056270 2008-05-21

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WO2008145634A1 true WO2008145634A1 (fr) 2008-12-04

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PCT/EP2008/056270 Ceased WO2008145585A1 (fr) 2007-05-25 2008-05-21 Procédé permettant de repartir des silicates dans des matières de revêtement
PCT/EP2008/056418 Ceased WO2008145634A1 (fr) 2007-05-25 2008-05-26 Matières de revêtement peu visqueuses, contenant des silicates et durcissables par exposition à un rayonnement

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US8969452B2 (en) 2008-12-17 2015-03-03 Basf Se Quick-drying coating compounds
CN102596381B (zh) 2009-11-05 2015-08-12 阿克佐诺贝尔化学国际公司 二氧化硅水分散体
CN102558970B (zh) * 2011-12-16 2014-04-09 江南大学 一种采用溶胶稀释制备低粘度uv涂料色浆的方法
CN104744645B (zh) * 2015-01-07 2019-02-19 北京金汇利应用化工制品有限公司 一种高耐性有机无机复合改性水性丙烯酸环氧酯树脂的制备方法

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Publication number Priority date Publication date Assignee Title
DE102019217820A1 (de) 2018-11-21 2020-05-28 Basf Se Verfahren zur Herstellung von Dekorbeschichtungen auf mineralischen Substraten

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