• 专利附录
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    • 专利摘要:
    The invention relates to a method for producing a composition for preparing nanostructured forms and layers, consisting of bringing an aqueous and/or alcoholic sol of a compound of an element selected from silicon and the main and sub-group metals into contact with species which have hydrolyzable alkoxy groups and which include at least one organically modified alkoxysilane or a precondensate derived therefrom, in conditions which lead to the (further) hydrolysis of the species and then removing any alcohol which has formed or which may optionally have been present originally. The invention is characterized in that enough alcohol is removed to leave a residual amount of not more than 20 wt.% in the composition.
    公开号:KR20010042528A
    申请号:KR1020007011168
    申请日:1999-04-08
    公开日:2001-05-25
    发明作者:아르팍에르투그룰；욘스커게하르트；쉬라헤르만；스미드트헬무트
    申请人:슈미트 헬무트；인스티투트 퓌어 노이에 마테리알리엔 게마인누찌게 게엠베하；
    IPC主号:
    专利说明:

    Nanostructured forms and layers and method for producing them using stable water-soluble precusors}
    The prior art already knows how to produce transparent materials comprising organic / inorganic composites using precursors comprising water for use in coatings.
    In particular, JP-A-53-6339 describes the synthesis of composites starting from silanes modified with organic activity and organic inertly modified silanes and hydrolyzing in the presence of phosphoric acid as an aqueous silica sol and hydrolysis catalyst. . Alcohol from this condensation reaction is not removed.
    JP-A-63-37168 is crosslinked by free radicals in the presence of colloidal silica and a nonionic surfactant, and is modified to have organic activity with acrylate-based monomers dispersed in an aqueous medium. Silane's organic radicals also describe the synthesis of composites from free radicals, which constitute a system of crosslinking. Hydrolysis and condensation reactions are carried out in separate reaction steps. Here too, the alcohol resulting from the condensation reaction is not removed.
    JP-A-63-37167 also describes similar content for systems in which the silane component has radicals that cationicly crosslink.
    US-A-5411787 describes the synthesis of composites from colloidal particles having a size smaller than 20 nm with a polymeric binder, one or more aminosilane components dispersed in water. Even in this case, alcohol produced by hydrolysis of the silane is not removed.
    US-A-4799963 describes the preparation of silane-based composites in which colloidal silica or nanoscale cerium oxides are additionally incorporated.
    The cited references do not suggest anything about the mechanism of action, and furthermore, very little information is available on the pot life of the described system. In addition, although numerically reanalyzing the synthesis shows that the residual solvent amount is more than 10% by volume, in most cases, information on the residual solvent amount is insufficient.
    FIELD OF THE INVENTION The present invention relates to nanostructured moldings and layers and methods of making them via stable water soluble precursors, and more particularly, to nanostructured moldings and layers suitable for optical purposes.
    By conducting the research based on the above-described prior art, control coating of the colloidal system with functional silanes can reduce water sensitivity during the hydrolysis and condensation reactions, and is particularly suitable for industrial applications. We have completed a system that can be used to produce a stable system for the production of superlayers.
    It is therefore an object of the present invention to provide a process for producing stable nanostructured moldings and layers via stable water soluble intermediates and preferably suitable for optical purposes.
    The aqueous, electrostatically stabilized (and therefore extremely concentration-sensitive) colloidal suspension and active monomeric or small weight component (silane or precondensate thereof) according to the invention can be applied by coating, As a result, it does not show the effect described by Stern (Stern (Z. Elektrochem., 508 (1924))) during the enrichment process, that is, the cohesive effect of two particles with the same charge when they approach each other. Otherwise it was found that there was no spontaneous chemical reaction between the reactive surface groups of the two particles. The concentration and shifting of the reaction equilibrium towards the result can be achieved by removing the alcohol (generally methanol or ethanol) resulting from the condensation reaction under reduced pressure, together with the formation of the surface condensate, resulting in very high storage stability ( 14 days) and a relatively low residual solvent amount (generally not more than 20% by weight, preferably 10% by weight).
    Of surface modifier / particle bonds (e.g., hydrogen bonds or metal-oxygen bonds (-Al-O-Si-, Ti-O-Si-, etc., see, eg Chem. Mat. 7 (1995), 1050-52)). Because of the reversibility, the above-described process can proceed in the opposite direction when heat is applied, so that the particles can be solidified and crosslinked. Further reactions can also occur through appropriately selected organic groups on the surface modifiers (eg, reactions between these groups).
    In this way, for example, an aqueous sol such as boemite, TiO 2 , ZrO 2 or SiO 2 sol, as well as an aqueous sol of an organic sol of the main and transition metal compounds of the periodic table, It is possible to remove and, if necessary, react in a manner that produces a stable and clear solution for a relatively long time with subsequent dispersion of the liquid residue in water. Removal of such solvents (alcohols) is necessary to carry out the reaction of coating the particles with organically modified alkoxysilanes to the extent that a liquid system stable to hydrolysis and condensation reactions is produced. Using conventional methods, this system can be applied for coating purposes and, if necessary, can be thermally and photochemically cured using a suitable catalyst, depending on what functional group of the organically modified alkoxysilane is. In the case of thermosetting, an inorganic network structure is produced and if an appropriate organic group is used, organic crosslinking is also generated therein. The resulting nanocomposite is characterized by high transparency. If used as a layer, it shows good adhesion and very high scratch resistance for a very large number of substrates.
    Thus, the present invention relates to an aqueous and / or alcoholic sol of a compound consisting of silicon and elements selected from the main and transition group metals of the periodic table, and one or more organically modified alkoxysilanes derived from or derived from hydrolyzable alkoxy groups. Of the nanostructures comprising contacting the species comprising the prehydrolysates under conditions that result in (additional) hydrolysis of these species with subsequent removal of the resulting alcohol and any alcohol originally present. It provides a method for preparing a composition for molding and layer production, characterized in that the alcohol is removed such that the alcohol content in the composition is 20% by weight, preferably 15% by weight, in particular 10% by weight or less.
    The present invention also provides a composition obtainable by the above process and used in the manufacture of substrates equipped with nanostructured moldings and nanostructured layers.
    The process according to the invention differs from similar processes of the prior art, in particular because a significant proportion of the solvents (alcohols) present in the system are removed from the system. This shifts the equilibrium of hydrolysis and condensation reactions towards the product and stabilizes the solution system. In general, at least 30% by weight, in particular 50% by weight and preferably 70% by weight of the theoretical amount of alcohol produced by hydrolysis of the alkoxy group is removed. More preferably at least 80% by weight, most preferably up to 90% by weight of the alcohol is removed. This figure does not include other alcohols originally present (eg from the starting material solution; assuming 100% removal of the alcohol), but include the amount of alcohol already produced during the preparation of the precondensates used. As a result, it is clear that 10-80% (preferably 20-50%) of condensed (hydrolyzed) silane groups undergo condensation reactions.
    The alcohol is removed from the reaction system, preferably under reduced pressure, to avoid excessive thermal loading of the system. In general, when alcohol is removed from the system, its temperature should not exceed 60 ° C, in particular 50 ° C, more preferably 40 ° C.
    Hereinafter, the starting materials used in the process of the present invention will be described in more detail.
    The solution used may be an aqueous solution, an alcoholic solution or an aqueous / alcoholic solution. Simple aqueous solutions are recommended. If a solution containing an alcohol is used, it is preferred that the alcohol has one to four carbon atoms, i.e., any of the methanol, ethanol, propanol, isopropanol or butanol isomers.
    The solution of the present invention comprises one or more compounds (preferably one compound) consisting of silicon and one or more components selected from main and transition group metals. The main group and transition group metals are preferably the main group elements of Groups 3 and 4 (particularly Al, Ga, Ge and Sn) of the periodic table and the transition elements of Groups 3 to 5 (particularly Ti, Zr, Hf, V, Nb and Ta). Alternatively, other metal compounds such as, for example, Zn, Mo, and W can have beneficial results.
    The constituent compounds preferably include oxides, oxidized hydrates, sulfides, selenides or phosphates, more preferably oxides and hydrates. Thus, the compounds present in the solutions used by the present invention in particular include (preferably) SiO 2 , Al 2 O 3 , AlOOH (particularly boehmite), TiO 2 , ZrO 2 and mixtures thereof.
    The solution used in the course of the invention generally has a solids content of 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 30% by weight.
    Species comprising hydrolyzable alkoxy groups used in the process of the present invention include at least one organically modified alkoxysilane and / or precondensates derived therefrom. Organically modified alkoxysilanes suitable for the present invention are of the general formula (I):
    R ' 4-X Si (OR) X (I)
    Wherein the radicals R may be equivalent to or different from each other (preferably equivalent) or are unsubstituted (preferably unsubstituted), 1 to 8, preferably 1 to 6, more preferably 1 to Hydrocarbon groups with four carbon atoms (particularly methyl and ethyl). The radicals R ′ may be the same or different from one another and are each unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms, and x is 1, 2 or 3.
    Alkyl, alkenyl, aryl, alkylaryl, arylalkyl, arylalkenyl and alkenylaryl radicals (preferably in each case 1 to 12, more preferably 1 to 8 carbon sources) And cyclic), which may be interrupted by oxygen, sulfur or nitrogen atoms to NR '' (R '' = hydrogen or C 1-4 alkyl), halogen, unsubstituted or substituted amino, Amide, carboxyl, mercapto, isocyanato, hydroxyl, alkoxy, alkoxycarbonyl, acryloyloxy, methacryloyloxy or one or more substituents from an epoxy group.
    Among the alkoxysilanes of the general formula (I), at least one alkoxysilane having one or more radicals R ′ having a group capable of addition-polymerization (including polyaddition) or condensation-polymerization is particularly preferred. have.
    The groups capable of this addition-polymerization or condensation-polymerization reaction are preferably epoxy groups or (preferably activated) carbon-carbon multiple bonds (especially double bonds), particularly preferably of the above-mentioned groups ( Meta) acrylate groups.
    Thus, particularly preferred as organically modified alkoxysilanes of general formula (I) for use in the present invention are x 2 or 3, especially 3, and the radical (the only radical) R 'is ω-glycidyloxy-C 2 -6 alkyl or ω- (meth) acryloyloxy-C 2-6 alkyl.
    Specific examples of such silanes include 3-glycidyloxypropyltri (meth) ethoxysilane, 3,4-epoxybutyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3- (meth) acryloyloxypropyl tri (meth) ethoxysilane and 2- (meth) acryloyloxyethyl tri (meth) ethoxysilane. Further examples of suitable compounds where x is 1 or 2 are 3-glycidyloxypropyldimethyl (meth) ethoxysilane, 3-glycidyloxypropylmethyldi (meth) ethoxysilane, 3- (meth) acrylic Royloxypropylmethyldi (meth) ethoxysilane and 2- (meth) acryloyloxyethylmethyldi (meth) ethoxysilane.
    Tetramethoxysilane, tetraethoxysilane, tetra-n-pro as alkoxysilanes which may be used alone if desired but preferably together with alkoxysilanes comprising said groups capable of addition-polymerization or condensation-polymerization reactions. Foxysilane, tetra-n-butoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, ethyltrimethoxysilane, phenylethyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxy Silane, cyclohexylmethyldimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyltriethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane and phenyldimethylethoxy There is silane.
    In particular, if the moldings and layers of the nanostructures of the present invention should have dirt repellency, water repellency, and low surface energy, fluorinated directly attached to silicon, together with organically modified alkoxysilanes As the alkyl radical, a silane having an alkyl radical having at least four carbon atoms (and preferably at least three fluorine atoms) located at α and β of the silicon having no fluorine atom can be used, for example For example, (tridecafluoro-1,1,2,2, -tetrahydrooctyl) methyldiethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, ( Heptadeca-fluoro-1,1,2,2, tetrahydrodecyl) methyldiethoxysilane and (heptadecafluoro-1,1,2,2, -detrahydrodecyl) triethoxysilane.
    Of course, in addition to the above silanes (particularly organically modified silanes), the chemical species having a hydrolyzable alkoxy group used according to the present invention may further comprise other chemical species than silanes. Examples of such non-silane compounds are alkoxides (preferably C 1-4 alkoxy groups) of aluminum, titanium, zirconium, tantalum, niobium, tin, zinc, tungsten, germanium and boron. Specific examples of such compounds include aluminum sec-butylate, titanium isopropoxide, titanium propoxide, titanium butoxide, zirconium isopropoxide, zirconium propoxide, zirconium butoxide, zirconium ethoxide, tantalum ethoxide, Tantalum butoxide, niobium ethoxide, niobium butoxide, tin t-butoxide, tungsten (VI) ethoxide, germanium ethoxide, germanium isopropoxide and di-t-butoxyaluminotriethoxysilane.
    Particularly in the case of relatively reactive alkoxides (eg alkoxides such as Al, Ti, Zr, etc.), it may be advisable to use them in the form of complexes. Suitable examples of such complexes are, for example, unsaturated carboxylic acids and meta Β-dicarbonyl compounds, such as methacrylic acid, acetylacetone, ethyl acetoacetate. If a species comprising an alkoxy group which can be hydrolyzed in addition to the organically modified alkoxysilane is used, the molar ratio of the organically modified alkoxysilane to the other species is 2: 1, in particular at least 5: 1 and more Preferably at least 10: 1.
    If an organically modified alkoxysilane is used, preferably containing a group capable of addition-polymerization or condensation-polymerization in the preparation method of the present invention, it is preferable to incorporate an initiator component in addition to the corresponding composition, It is preferable that the molar ratio of the initiator and the organic group generally does not exceed 0.15: 1.
    For example, when silanes of general formula (I) containing epoxy groups are used, suitable initiators in particular include imidazoles, amines, acid anhydrides and Lewis acids. If imidazole is used, 1-methylimidazole is particularly preferred. Preferred examples of other imidazole initiators are 2-methylimidazole and 2-phenylimidazole. Examples of the initiator among the primary, secondary and tertiary amines include ethylenediamine, diethylenetriamine, triethylenetetramine, 1,6-diaminohexane, 1,6-bis (dimethylamino) hexane and tetramethylethylenediamine , N, N, N ', N ", N" -pentamethyldiethylenetriamine, 1,4-diazabicyclo [2.2.2] octane, cyclohexane 1,2-diamine, 2- (aminomethyl) -3,3,5-trimethylcyclopentylamine, 4,4'-diaminocyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, bis (4-amino-3-methylcyclohexyl) methane, 1 , 8-diamino-p-methane, 3- (aminoethyl) -3,3,5-trimethylcyclohexylamine (isophoronediamine), piperazine, piperidine, eurotropin, bis (4-aminophenyl Methane and bis (4-aminophenyl) sulfone. The amines used as initiators can be functionalized with silanes. For example, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane and aminopropyltri Ethoxysilane. In addition, borontrifluoride additives of amines such as for example BF 3 -ethylamine may be used. Moreover, ethylbicyclo [2.2.1] heptene-2,3-dicarboxylic anhydride, hexahydronaphthalenedicarboxylic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and also [3 Organic crosslinking can occur in the presence of an acid anhydride (preferably with a tertiary amine), such as-(triethoxysilyl) propyl] succinic anhydride. In addition, suitable catalysts for the organic crosslinking of epoxy groups are, for example, alkoxides of (optionally prehydrolyzed) aluminum, titanium and zirconium (eg Al (OC 2 H 4 OC 4 H 9 ) 3 ) and propionic acid. Organic carboxylic acid.
    When using the silane of the formula (I) having a (meth) acrylate group, a thermal polymerization catalyst or a general photopolymerization catalyst common to the composition may be added to the composition. Preferred examples of thermal catalysts used are azobisisobutyronitrile, diacyl peroxides (eg dibenzoyl peroxide and dilauroyl peroxide), peroxydicarbonates, alkyl peresters, perketal, alkyl or aryl perlocks Side, ketone peroxide and hydroperoxide.
    It is of course possible to incorporate in the composition a pure organic component which reacts with the reactive groups of the silanes of general formula (I), which can lead to further crosslinking reactions during the curing process. For example, when using silanes containing (meth) acrylate groups, specific examples of useful crosslinkers include bisphenol A bisacrylate, bisphenol A bismethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacryl Latex, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 2,2,3,3-tetrafluoro-1,4-butanediol diacrylate and dimetha Acrylate, 1,1,5,5-tetrahydroperfluoropentyl-1,5-diacrylic And dimethacrylate, hexafluorobisphenol A diacrylate and dimethacrylate, octafluoro-1,6-hexanediol diacrylate and dimethacrylate, 1,3-bis (3-methacrylo) Yloxypropyl) detrakis (trimethylsiloxy) disiloxane, 1,3-bis (3-acryloyloxypropyl) tetrakis (trimethylsiloxy) disiloxane, 1,3-bis (3-methacryloyl Oxypropyl) tetramethyldisiloxane and 1,3-bis (3-acryloyloxypropyl) tetramethyldisiloxane.
    If hydrophilic nanostructured moldings and layers are required, such hydrophilic components can be incorporated, for example, in addition to the compositions of the present invention. To this end, a component capable of covalently binding to the inorganic matrix (for example, a component having a free hydroxyl group such as 2-hydroxyethyl (meth) acrylate) or a hydrophilic component capable of freely moving in the matrix (eg, Surfactants) or combinations thereof.
    Conditions according to the invention which result in (additional) hydrolysis of species comprising alkoxy groups which can be hydrolyzed and / or corresponding precondensates are preferably at least 0.5 per alkoxy group which can be hydrolyzed. contains mol of H 2 O. This amount of water is generally already present because of the water in the sol. If not, this amount of water must be added separately.
    More preferred is the presence of a hydrolysis (and condensation) catalyst of the alkoxy group. Preferred catalysts for this purpose are acidic catalysts such as aqueous (mineral) acids such as HCl.
    The proportion of starting material used (chemical species comprising alkoxy groups which can be hydrolyzed with the sol) is preferably such that the content of solids derived from the sol in the final molding or in the final layer (after curing), 1 to 50% by weight and preferably 5 to 30% by weight.
    A method of contacting an aqueous and / or alcoholic sol with a species containing an alkoxy group that can be hydrolyzed under conditions that result in the hydrolysis of the species is familiar to those skilled in the art and is described in more detail in the examples below. do. After removing the solvent (alcohol) from the composition (which generally means that 10 to 80%, preferably 20 to 50% of the first hydrolyzable alkoxy groups undergo condensation), water is added By adjusting the resultant composition to a suitable viscosity it may be advantageous for certain purposes. The viscosity of the composition, in particular for coating purposes, is preferably less than 5000 mPas, more preferably less than 3000 mPas.
    In order to produce a substrate with a nanostructured molding and a nanostructured layer using the composition according to the invention, the composition can be introduced into a mold or applied to the substrate and then-especially in the case of the production of the layer, if necessary If so, prior to drying at room temperature or slightly elevated temperature—thermal (and additionally, if necessary, photochemical) curing is carried out. In the case of layer production, all conventional coating techniques such as dipping, flowcoating, rolling, spraying, knife coating, spin coating or Screen printing can be used.
    The curing temperature is generally in the range from 90 to 300 ° C., preferably from 110 to 200 ° C., in particular in the production of the layer, depending on the temperature stability of the substrate to be coated.
    As already mentioned at the outset, the compositions of the present invention are suitable for coating onto a very wide substrate and without surface treatment, and in many cases exhibit very good adhesion and extremely good scratch resistance. Particularly preferred substrates for the production of layers are glass, transparent plastics and opaque plastics and metals. Examples of suitable plastics include polycarbonate, poly (meth) acrylate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polypropylene and polyethylene, with the preferred metal base being aluminum.
    Thus the compositions obtainable according to the invention are suitable for many applications. Examples of such applications are in particular:
    Coatings to increase scratch and wear resistance:
    -Top coat of household goods and vehicles
    Transparent polymer and opaque polymer
    -Metal base
    -Ceramic and glass materials
    Coatings to improve the wear and corrosion resistance of precious and common metals:
    -Mg: engine wall, glasses frame, exercise equipment, wheel rim, carrying case
    -Al: Body of vehicle, wheel rim, exterior material, furniture, heat exchanger
    Steel: compression molds for manufacturing parts, sanitary facilities
    -Zn: roof structure, firearm, airbag-accelerometer mass
    -Cu: door facility, heat exchanger, wash basin
    Coatings to Improve Purification:
    With regard to examples of this application, reference may be made to DE-A-19544763.
    Coatings to improve part demoulding and coatings to reduce tack:
    -Metal and Polymer Conveyor Belts
    -Rolls for polymerization
    -Compression mold for producing polystyrene parts
    -Graffiti-resistant coating of top coat and exterior materials
    Coating for anti-condensation effect:
    -Glassware in vehicles
    -Glasses
    Mirrors (e.g. bathroom mirrors, rear mirrors and cosmetic mirrors)
    Optical components (eg spectroscopic mirrors, laser prisms);
    Elements for encapsulation (eg housing for meteorological instruments);
    Anti-reflective coating:
    -Polymer or glass cover of display elements (eg automotive instrument panel, display window glass);
    Coatings for food-related applications:
    Diffusion barrier layers (eg to prevent diffusion of gases, acetaldehyde, lead ions or alkali metal ions, odorants and odors);
    Coatings for Hollow Glass Products:
    -Coating of beverage bottles to increase the explosion pressure;
    -Painting to colorless glass through coating
    Production of optical moldings and self-supporting films:
    -Nanomixed Glasses Lens
    -Scratch and wear resistant packing film
    The present invention is explained in more detail through the following examples. In all these examples, the solvent (ethanol) produced by hydrolysis was removed at least approximately 95% or more.
    Example 1
    (3-glycidyloxy propyl) silane (GLYEO) 27.8 g (0.1 mol) of silica sol ( 30 wt% SiO 2 concentration of the aqueous solution, Bayer prepared Levasil) in the tree were mixed in 27.8g. The mixture was stirred at room temperature for 5 hours. Then, the ethanol generated from the hydrolysis was removed by distillation (rotary evaporator, maximum reactor temperature 40 ° C). This residue was mixed with 1.11 g (0.0005 mol) of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (DIAMO) and stirred at room temperature for 1 hour.
    The resulting system was used to coat polycarbonate and aluminum sheets and CR-39 lenses. The polycarbonate sheet is pretreated by corona discharge. The coated polycarbonate and the aluminum sheet were left at room temperature for 30 minutes and then cured at 130 ° C. for 4 hours. The CR-39 lens was left at room temperature for 30 minutes and then cured at 90 ° C for 4 hours.
    Example 2
    Example 1 was repeated using 3.05 g (0.001 mol) of [3- (triethoxysilyl) propyl] succinic anhydride (GF20) instead of DIAMO. The wear resistance of the polycarbonate coated with this composition was measured by a Taber wear test (wheel material CS 10F, 1000 revolutions, wheel load 500 g), resulting in 7% diffuse-light loss.
    Example 3
    In place of the silica sol boehmite suspension (Disperal Put P3 2.78 g in distilled water 25 g) Example 1 was repeated using.
    Example 4
    Example 3 was repeated using 3.78 g (0.01 mol) of Al (OEtOBu) 3 as catalyst instead of DIAMO.
    Example 5
    27.8 g (0.1 mol) of GLYEO was mixed with 27.8 g of the silica sol described above in Example 1. After the mixture was stirred at room temperature for 5 hours, ethanol produced by hydrolysis was removed as described in Example 1. The residue was mixed with 2.84 g (0.01 mol) of TiO 2 sol prepared by the method described below and stirred at room temperature for 1 hour.
    TiO 2 sol was prepared by dissolving 28.42 g (0.1 mol) of tetraisopropyl oltotitanate (Ti (OiPr) 4 ) in 60 ml of isopropanol and adding concentrated hydrochloric acid to the solution in a 1: 1 molar ratio. After stirring for 2 hours at room temperature, volatile components were removed by rotary evaporator and the residue was dissolved in 70 ml of water.
    Example 6
    139.0 g (0.5 mol) of GLYEO was mixed with 62.4 g (0.3 mol) of tetraethoxysilane (TEOS). The reaction mixture was mixed with HCl-acid boehmite suspension (12.82 g of nano boehmite powder in 128.20 g of 0.1 N HCl solution) and stirred at room temperature for 5 hours. Ethanol produced by the hydrolysis was removed by distillation as described in Example 1. Next, 3.78 g (0.01 mol) of Al (OEtOBu) 3 was added to the mixture and stirred at room temperature for 1 hour.
    The polycarbonate plates pretreated by corona discharge and the plasma-pretreated CR-39 lens were coated with the composition thus prepared and thermally cured at 130 ° C. and 90 ° C. for one hour, respectively.
    Example 7
    29.0 g (0.1 mol) of 3-methacryloyloxypropyltriethoxysilane were mixed with 29.0 g of the silica sol described above in Example 1 and stirred at room temperature for 16 hours. This mixture was mixed with 13.0 g (0.1 mol) of 2-hydroxyethyl methacrylate (as hydrophilic component) and stirred at room temperature for 30 minutes. The alcohol produced by hydrolysis was then removed from the reaction mixture by distillation (as described above in Example 1). 0.48 g of dibenzoyl peroxide (1 mol% in the presence of double bonds) was added to the concentrated reaction mixture.
    The composition thus prepared was applied to thin polymethacrylate plates pretreated by corona discharge and thermally cured at 95 ° C. for 4 hours.
    Example 8
    55.6 g of 3-glycidyloxypropyltriethoxysilane were mixed with 0.51 g of tridecafluoro-1,1,2,2, tetrahydrooctyl-1-triethoxysilane and stirred. The resulting mixture was mixed with 10.85 g of 0.1 N HCl (corresponding to the stoichiometric amount of water required for hydrolysis of the alkoxysilane). After stirring for 24 hours at room temperature, 55.6 g of the silica sol described above in Example 1 was added and the mixture was stirred for 4 hours at room temperature. The alcohol produced by hydrolysis was removed by rotary evaporator as described above in Example 1 (removal amount 26.4 g). Then, 2.22 g of DIAMO was added and the mixture was further stirred at room temperature for one hour.
    Example 9
    278.42 g of GLYEO was hydrolyzed with 10 g of the reaction product of 3-isocyanatopropyltriethoxysilane and polyethylene glycol 600 and 54 g of 0.1 N HCl at room temperature with stirring for 5 hours. Ethanol produced by prehydrolysis was removed by rotary evaporator (reactor temperature 25 ° C., 30-40 mbar). Next, 926 g of the silica sol described above in Example 1 was incorporated into the mixture with stirring, and the mixture was stirred at room temperature for 16 hours. Then 11.12 g of DIAMO was added as an initiator and the mixture was further stirred at room temperature for one hour. The silicone-based nonionic surfactant was then added with vigorous stirring.
    The float glass substrate coated with the composition was cured in a drying oven at 130 ° C. for 4 hours.
    Example 10
    Example 1 was repeated using 1.32 g (0.005 mol) trimethoxysilylpropyldiethylenetriamine (TRIAMO) instead of DIAMO.
    Example 11
    Example 1 was repeated using 0.74 g (0.01 mol) propionic acid as the initiator instead of DIAMO.
    Example 12
    Example 1 was repeated using 3.87 g (0.01 mol) of Al (OEtOBu) 3 as initiator instead of DIAMO.
    Example 13
    Example 1 was repeated using 0.41 g (0.005 mol) of 1-methylimidazole as the initiator instead of DIAMO.
    Example 14
    Example 1 was repeated using 5.27 g (0.01 mol) of a mixture obtained by purifying 3-aminopropyltriethoxysilane (AMEO) and GF20 with a molar ratio of 1: 1 instead of DIAMO under ice cooling.
    Example 15
    Example 6 was repeated using 95.5 g of the silica sol described above in Example 1 in place of the HCl-acid boehmite suspension and increasing the amount of catalyst by five times.
    The polycarbonate plates pretreated by corona discharge and the plasma-pretreated CR-39 lens were coated with the resulting composition and thermally cured for one hour at 130 ° C. and 90 ° C., respectively.
    Example 16
    27.8 g (0.1 mol) of GLYEO was mixed with 13.5 g of 0.1 N hydrochloric acid and stirred at room temperature for 2 hours. 27.8 g of organosol (30% by weight SiO 2 in isopropanol, Bayer PPL 6454-6456) was added to the prehydrolyzate and the mixture was stirred at room temperature for 5 hours. Next, ethanol and isopropanol solvent produced by hydrolysis were removed by distillation. The residue was mixed with 18.9 g of H 2 O (pH 3.2). Next, 1.11 g (0.0005 mol) of DIAMO was added with vigorous stirring and the mixture was stirred at room temperature for 1 hour.
    The resulting composition was used to coat polycarbonate and aluminum foil and CR-39 lenses. The polycarbonate sheet is pretreated by corona discharge. The coated polycarbonate and the aluminum sheet were left to stand at room temperature for 30 minutes and then thermally cured at 130 ° C. for 4 hours. The CR-39 lens was left at room temperature for 30 minutes and then cured at 90 ° C. for 4 hours.
    Example 17
    139.0 g (0.5 mol) of GLYEO was mixed with 62.4 g (0.3 mol) of TEOS and stoichiometrically mixed with 0.1 N hydrochloric acid. The reaction mixture was stirred at room temperature for 16 hours. Next, ethanol produced by the hydrolysis and condensation reaction was removed by distillation. The concentrated reaction mixture was mixed with HCl-acid boehmite suspension (12.82 g of boehmite powder in 128.8 g of 0.1 N HCl solution) and stirred at room temperature for 3 hours. 3.78 g (0.01 mol) of Al (OEtOBu) 3 was added dropwise to this mixture. The coating material thus prepared was stirred at room temperature for approximately 4 hours.
    Corona-pretreated polycarbonate sheets and plasma-pretreated CR-39 lenses were coated and thermally cured at 130 ° C. and 90 ° C. for 1 hour, respectively.
    Example 18
    139.0 g (0.5 mol) of GLYEO was mixed with 62.4 g (0.3 mol) of TEOS and stoichiometrically mixed with 0.1 N hydrochloric acid. The reaction mixture was stirred at room temperature for 16 hours. Next, ethanol produced by the hydrolysis and condensation reaction was removed by distillation. The concentrated reaction mixture was mixed with an acidified 30% by weight silica sol solution (see Example 1) and stirred at room temperature for 3 hours. 18.9 g (0.05 mol) of Al (OEtOBu) 3 was added dropwise to this mixture. The coating material thus prepared was stirred at room temperature for approximately 4 hours.
    Corona-pretreated polycarbonate sheets and plasma-pretreated CR-39 lenses were coated and thermally cured at 130 ° C. and 90 ° C. for 1 hour, respectively.
    Example 19
    27.8 g (0.1 mol) of GLYEO was mixed with 0.51 g of fluorosilane (see Example 8; 1 mol% relative to GLYEO) and stirred. This mixture was mixed with 5.46 g of 0.1 N hydrochloric acid corresponding to the stoichiometric amount of water required for hydrolysis of the alkoxysilane. This mixture was then stirred at room temperature for 24 hours. Subsequently, ethanol produced by the hydrolysis and condensation reaction was removed by distillation. The residue was mixed with 3.87 g (0.01 mol) of Al (OEtOBu) 3 and 27.8 g of acidified silica sol (see Example 1) and stirred at room temperature for 3 hours.
    Example 20
    27.8 g (0.1 mol) of GLYEO was mixed with 0.255 g of fluorosilane (see Example 8; 0.5 mol% relative to GLYEO) and stirred. This mixture was mixed with 5.46 g of 0.1 N hydrochloric acid corresponding to the stoichiometric amount of water required for hydrolysis of the alkoxysilane. The mixture was then stirred at room temperature for 24 hours and then the ethanol produced by hydrolysis was removed by rotary evaporator. The amount removed is approximately 13 g and corresponds to approximately 95%. The residue was dispersed with boehmite suspension (Dispersal P3 2.78 g in 25 ml of 0.1 N hydrochloric acid solution), 1.89 g (0.005 mol) of Al (OEtOBu) 3 was mixed and stirred at room temperature for 1 hour.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] A method of preparing a composition for molding and layering nanostructures, the method comprising: an aqueous and / or alcoholic sol of a compound consisting of silicon and elements selected from main group and transition group metals of the periodic table, and having at least one hydrolyzable alkoxy group Species comprising organically modified alkoxysilanes or prehydrolysates derived therefrom result in (additional) hydrolysis of these species and subsequent removal of the resulting alcohol and any alcohol originally present. And contacting under conditions, wherein the alcohol is removed such that the alcohol content in the composition is 20% by weight or less.
    [2" claim-type="Currently amended] The method according to claim 1, wherein the amount of alcohol removed is at least 30% by weight, preferably at least 30% by weight, of the total amount of the predetermined alcohol originally present and the amount of alcohol theoretically produced by hydrolysis of all alkoxy groups present from the beginning. Is an amount corresponding to 50% by weight.
    [3" claim-type="Currently amended] The method of claim 1 or 2, wherein after the removal of the alcohol, water is added to the composition to adjust the suitable viscosity.
    [4" claim-type="Currently amended] The process according to any of claims 1 to 3, wherein an aqueous sol is used.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4, wherein the compound constituting the sol is derived from at least one element selected from silicon and from Groups 3 and 4 of the Periodic Table and from Groups 3 to 5 transition metals. In particular from Si, Al, Sn, Ti, Zr.
    [6" claim-type="Currently amended] The process according to claim 1, wherein the compound constituting the sol comprises one or more oxides (hydrates), sulfides, selenides or phosphates, in particular oxides (hydrates).
    [7" claim-type="Currently amended] The process according to claim 1, wherein the sol is SiO 2 , Al 2 O 3 , AlOOH, TiO 2 and / or ZrO 2 sol.
    [8" claim-type="Currently amended] 8. The method of claim 1, wherein the organically modified alkoxysilane comprises at least one compound of general formula (I).
    R ' 4-x Si (OR) X (I)
    Wherein the radical R is an unsubstituted or substituted hydrocarbon group having from 1 to 8 carbon atoms and the radicals R 'are an unsubstituted or substituted hydrocarbon group having from 1 to 20 carbon atoms equal or different from each other and x is 1, 2 or 3 way.
    [9" claim-type="Currently amended] The radical R according to claim 8, wherein the radical R is a C 1-4 alkyl group, in particular methyl and ethyl, x is 2 or 3, especially 3, and at least one of the radicals R 'or radicals R' is addition-polymerization or condensation-polymerization. How to have a group that can react.
    [10" claim-type="Currently amended] 10. Process according to claim 9, wherein the group capable of addition-polymerization or condensation-polymerization is an epoxy group or preferably an activated carbon-carbon multiple bond, more preferably a (meth) acrylate group.
    [11" claim-type="Currently amended] The compound according to claim 8, wherein at least one of the radicals R ′ or radicals R ′ is an ω-glycidyloxy-C 2-6 alkyl group or an ω- (meth) acryloyloxy-C 2. -6 alkyl group.
    [12" claim-type="Currently amended] The process according to claim 9, wherein a catalyst for the addition-polymerization or condensation-polymerization reaction is added to the composition.
    [13" claim-type="Currently amended] 13. A condition according to any one of claims 1 to 12, wherein the conditions resulting in (additional) hydrolysis of species having an alkoxy group that can be hydrolyzed are (a) at least 0.5 mol per alkoxy group that can be hydrolyzed. H 2 O and (b) preferably the presence of an acidic catalyst for the hydrolysis reaction.
    [14" claim-type="Currently amended] Process according to claim 1, wherein the sol is added such that the amount of sol solid in the finished molding or finished layer is from 1 to 50% by weight, in particular from 5 to 30% by weight of each of the molding or layer. .
    [15" claim-type="Currently amended] A composition for forming a nanostructured molding and a layer of a nanostructure obtained by the method according to any one of claims 1 to 14.
    [16" claim-type="Currently amended] A method for producing a substrate having a nanostructured molding and a layer of nanostructures, the composition prepared by the method according to any one of claims 1 to 14
    (a) incorporation into a mold;
    (b) applied to the substrate;
    Then thermal curing and, if necessary, additionally photochemical curing.
    [17" claim-type="Currently amended] The method of claim 16 wherein the substrate is made of glass, plastic or metal.
    [18" claim-type="Currently amended] A substrate having a nanostructured molding and a layer of nanostructures obtainable by the method of claim 16 or 17.
    [19" claim-type="Currently amended] Optical use of a substrate with a nanostructured molding according to claim 18 and with a layer of nanostructures.
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    同族专利:
    公开号 | 公开日
    DE59911048D1|2004-12-16|
    NO20004877D0|2000-09-28|
    EP1086162A2|2001-03-28|
    NO331461B1|2012-01-09|
    JP4597368B2|2010-12-15|
    CA2327312A1|1999-10-21|
    EP1086162B1|2004-11-10|
    CZ20003683A3|2001-01-17|
    PL213503B1|2013-03-29|
    MXPA00009735A|2002-04-24|
    AT282058T|2004-11-15|
    ES2232135T3|2005-05-16|
    ES2232135T5|2014-02-24|
    EP1086162B2|2013-11-20|
    NO20004877L|2000-09-28|
    BR9909521A|2000-12-12|
    US6620514B1|2003-09-16|
    WO1999052964A2|1999-10-21|
    HU0101496A2|2001-08-28|
    CN1145659C|2004-04-14|
    PL343590A1|2001-08-27|
    HU0101496A3|2002-02-28|
    DE19816136A1|1999-10-14|
    WO1999052964A3|2000-01-20|
    JP2002511509A|2002-04-16|
    AU3813899A|1999-11-01|
    CN1301277A|2001-06-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-04-09|Priority to DE19816136.0
    1998-04-09|Priority to DE1998116136
    1999-04-08|Application filed by 슈미트 헬무트, 인스티투트 퓌어 노이에 마테리알리엔 게마인누찌게 게엠베하
    2001-05-25|Publication of KR20010042528A
    2005-08-04|First worldwide family litigation filed
    优先权:
    申请号 | 申请日 | 专利标题
    DE19816136.0|1998-04-09|
    DE1998116136|DE19816136A1|1998-04-09|1998-04-09|Nanostructured moldings and layers and their production via stable water-soluble precursors|
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