EP2445974A1 - Modifizierte zno-nanopartikel - Google Patents

Modifizierte zno-nanopartikel

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Publication number
EP2445974A1
EP2445974A1 EP10725770A EP10725770A EP2445974A1 EP 2445974 A1 EP2445974 A1 EP 2445974A1 EP 10725770 A EP10725770 A EP 10725770A EP 10725770 A EP10725770 A EP 10725770A EP 2445974 A1 EP2445974 A1 EP 2445974A1
Authority
EP
European Patent Office
Prior art keywords
zinc oxide
nanoparticles
modified
oxide nanoparticles
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10725770A
Other languages
German (de)
English (en)
French (fr)
Inventor
Richard Riggs
Andrey Karpov
Simon Schambony
Wolfgang Best
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10725770A priority Critical patent/EP2445974A1/de
Publication of EP2445974A1 publication Critical patent/EP2445974A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • 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
    • 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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

Definitions

  • the present invention relates to methods for producing modified zinc oxide nanoparticles.
  • Another object of the invention are modified zinc oxide nanoparticles.
  • Uses of modified zinc oxide nanoparticles, in particular as UV absorbers also in the finishing of plastics, are likewise provided by the invention.
  • Further objects of the invention are materials which contain modified zinc oxide nanoparticles which have been produced by this process or contain modified zinc oxide nanoparticles and processes for the stabilization of materials by the addition of modified zinc oxide nanoparticles.
  • metal oxides such as titanium dioxide (OO 2) or zinc oxide (ZnO) for protection against UV radiation has long been known from the prior art.
  • inorganic UV absorbers as described in the prior art, have various advantageous technical features, e.g. increased migration stability, high thermal stability or stability to light-induced degradation on.
  • a disadvantage is often the property of the metal oxides by their photocatalytic activity to accelerate the degradation of the surrounding matrix, for example a polymer matrix. Remedy here, for example, provide amorphous layers containing silicon oxides or aluminum oxides, which are applied to the UV-absorbing metal oxide.
  • WO 90/06874 A1 describes UV-absorbing chemically inert compositions containing particles consisting of ZnO with a shell of, for example, SiO 2 and Al 2 O 3. The particles are prepared in an aqueous slurry.
  • WO 93/22386 A1 describes methods for producing particles which are surrounded by a dense envelope of amorphous silica (SiO 2). In this case, particles suspended in aqueous solution are reacted with alkali metal silicates at a pH of 7 to 11.
  • EP 0 998 853 A1 describes metal oxide powders which are surrounded by a dense silica shell of 0.1 to 100 nm.
  • the production of silica-coated metal oxide powder is carried out in aqueous solution with the aid of silicic acids.
  • Silica-coated TiO 2 particles have a reduced photocatalytic activity according to EP 0 998 853 A1.
  • EP 1 167 462 A1 describes metal oxide particles with a silica shell, which are further treated with a water repellent.
  • the silica shell is formed with the aid of tetraalkoxysilanes in aqueous solution.
  • the water repellents used are alkylalkoxysilanes.
  • EP 1 284 277 A1 describes metal oxide particles coated with silicon dioxide and a process for their preparation. EP 1 284 277 A1 furthermore describes the use of these particles in sunscreens wherein the coated metal oxide particles have a reduced photocatalytic activity compared to metal oxide particles without a shell.
  • H. Wang, et al. (Chemistry Letters, 2002, 630-631) describe ZnO nanoparticles coated with silica using a two-step procedure. First, a mixture of a tetraethoxysilane, ethanol and aqueous ammonia solution is prepared. Thereafter, ZnO nanoparticles are added to this solution. The ZnO particles provided with silica sheaths of about 20 nm show a reduced photocatalytic activity.
  • WO 03/104319 A1 describes powders containing ZnO fine particles with a silica shell and also thermoplastic resins which contain such particles. According to WO 03/104319 A1, the coated ZnO TeN chen have a reduced photocatalytic activity and a reduced leakage of zinc ions.
  • nanoparticles are obtained by reacting precursors with siloxy compounds.
  • the nanoparticles preferably contain a SiO 2 coating and / or further functionalization, inter alia organofunctional neat silanes.
  • silica coated ZnO particles according to WO 2007/134712 A1 a reduced photocatalytic activity.
  • the above-mentioned silica-modified zinc oxide particles are prepared in aqueous solution.
  • the modified zinc oxide particles prepared by these methods generally have unsatisfactory solubility in many organic solvents or hydrophobic polymers. Furthermore, there is a need for modified ZnO nanoparticles having a still further reduced photocatalytic activity over the prior art.
  • the object of the present invention was therefore to provide modified zinc oxide particles which are readily soluble in organic solvents and hydrophobic polymers. Another object of the invention was to provide modified zinc oxide particles which have a reduced photocatalytic activity.
  • Expressions of the form Ca-Cb in the context of this invention designate chemical compounds or substituents having a certain number of carbon atoms.
  • the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
  • Further specification of the chemical compounds or substituents is made by terms of the form C 3 -Cb-V.
  • V stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl, propyl, isopropyl or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1
  • Dimethylpropyl 1, 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl- 2-methylpropyl, or C 7 -Cio-alkyl, such as heptyl, octyl, 2-ethyl-hexyl, 2,4,4-trimethylpentyl, 1, 1, 3,3-tetramethylbutyl, nonyl or decyl and their isomers.
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to dinuclear, more preferably a mononuclear aromatic ring system.
  • C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are bonded via an oxygen atom (-O-), for example C 1 -C 10 -alkoxy or C 2 -C 20 -alkoxy, preferably C 1 C10 alkyloxy, particularly preferably Ci-C3-alkoxy, such as methoxy, ethoxy, propoxy.
  • nanoparticles are understood as meaning particles having a particle size of 1 nm to 500 nm.
  • the term (nano) particle also uses the term "(nano) particle”.
  • the particle size of nanoparticles in particular also of nanoparticulate modified ZnO, a number of different methods are available to the person skilled in the art, which depend on the composition of the particles and can yield partly deviating results with respect to the particle size.
  • the particle size can be measured by measurements using a trans- emission electron microscopy (TEM), dynamic light scattering (DLS) or measurements of the UV absorption wavelength.
  • TEM trans- emission electron microscopy
  • DLS dynamic light scattering
  • Particle sizes are determined in the context of the present application, if possible, by means of a TEM or alternatively by measurement of the DLS. With an ideal spherical shape of the nanoparticles, the particle size would correspond to the particle diameter.
  • the agglomerates (secondary particles), which may have arisen as a result of a juxtaposition of nanoparticles, of the initially formed primary particles may also be greater than 500 nm.
  • the primary and secondary particles can have different shapes, for example spherical, needle-shaped or even irregularly shaped.
  • zinc oxide nanoparticles or “ZnO nanoparticles” refers to particles consisting essentially of zinc oxide, which particles, depending on the respective ambient conditions, may also have a certain hydroxide concentration on their surface, as is known to the person skilled in the art the prior art is known (dissertation, B.
  • the ZnO nanoparticles are ZnO / zinc hydroxide / zinc oxide hydrate particles
  • anions of a zinc salt may be on the ZnO surface, for example, acetate groups in the case of Use of Zn (OAc) 2 or Zn (OAc) 2 dihydrate (compare Sakohara et al., J. Chem. Eng. Jap. 2001, 34, 15-21; Anderson et al., J. Phys. Chem.
  • the ZnO nanoparticles as primary particles preferably have a particle diameter of less than 500 nm, particularly preferably less than 200 nm, in particular from 10 to 100 nm.
  • ZnO nanoparticles can also be present as agglomerates.
  • These secondary particles generally have particle diameters of 50 nm to 1000 .mu.m, preferably from 80 nm to 500 .mu.m, in particular from 100 to 1000 nm.
  • modified zinc oxide nanoparticles refers to ZnO nanoparticles which interact with a shell containing silicon and oxygen, for example a shell containing silicate.
  • the type of interaction is basically arbitrary, but preferably the interaction occurs via a chemical bond Furthermore, it can also be an ionic interaction (Coulomb interaction) to an interaction on Hydrogen bonds and / or act on a dipole / dipole interaction. Of course, the interaction may also be a combination of the above possibilities.
  • the modified ZnO nanoparticles preferably have a particle diameter of less than 500 nm, more preferably less than 200 nm and, in particular, the particle diameter of the modified zinc oxide nanoparticles is from 10 to 100 nm.
  • solvent is also used for diluents
  • the compounds dissolved in the solvent are present either in solution, in suspension, in dispersed form or in emulsified form in the solvent or in contact with the solvent of solvents.
  • dissolved modified ZnO nanoparticles in the solvent are understood as meaning particles suspended or dispersed in the solvent.
  • Liquid formulations of the modified ZnO nanoparticles are solutions, dispersions or suspensions of the modified ZnO nanoparticles.
  • Solid formulations of the modified ZnO nanoparticles are solid phase mixtures containing modified ZnO nanoparticles, for example dispersions of the modified ZnO nanoparticles in a polymeric matrix, such as in polymers, oligomeric olefins, waxes, e.g., Luwax®, or in a masterbatch.
  • Zinc oxide nanoparticles are commercially available or can be prepared by methods known to those skilled in the art, for example by so-called dry or wet processes.
  • the dry process involves the combustion of metallic zinc.
  • Finely divided zinc oxide is mainly produced by wet-chemical precipitation processes.
  • Zinc oxide nanoparticles are used in step a. used in the process according to the invention and are present in a solvent. This is preferably a dispersion or suspension of the zinc oxide nanoparticles in the solvent. Most preferably, the zinc oxide nanoparticles are suspended in the solvent. The zinc oxide nanoparticles may also be in situ in step a. be generated in the solvent.
  • the solution of zinc oxide nanoparticles is prepared by methods known to those skilled in the art for the preparation of solutions, dispersions or suspensions of zinc oxide particles in liquids.
  • the content of zinc oxide nanoparticles in the solution of step a. may vary within a wide range, for example, depending on the stability of the dispersion or suspension. In general, from 0.1 to 50 wt .-% zinc oxide nanoparticles, based on the amount of solvent used. Preference is given to from 1 to 30 wt .-% zinc oxide nanoparticles, in particular from 10 to 30 wt .-% zinc oxide nanoparticles, based on the amount of solvent.
  • the solvents used are preferably polar solvents or mixtures thereof. In the context of the process according to the invention, all solvents having a dielectric constant greater than 10, preferably greater than 15, are suitable as polar solvents.
  • the polar solvent used are preferably alcohols, ethers, amides, amines.
  • the amines can be either the same or different from the amines in step a. of the method according to the invention.
  • Particularly preferred solvents used are methanol, ethanol, 1-propanol, 2-propanol, THF, DMF, pyridine or ethanolamine.
  • suitable polar solvents are methanol, ethanol, 1-propanol, 2-propanol.
  • the content of water in the solvent in the reaction in the context of the inventive method less than 5 wt .-% water, based on the total amount of solvent and water.
  • the solvent preferably contains less than 2% by weight of water, more preferably less than 1% of water.
  • water is used essentially less than 0.5% by weight, in particular less than 0.2% by weight, of water.
  • the amines used in the process according to the invention are preferably primary amines.
  • the primary amines used are preferably amino alcohols such as ethanolamine, propanolamine, ethers containing amines such as 2-methoxyethylamine, 3-methoxypropylamine, polyethylene glycolamine, C 1 -C 20 -alkylamines such as methylamine, butylamine or octadecylamine. Most preferred are ethanolamine, methylamine or butylamine.
  • step a Preference is given in step a.
  • the content of ammonia or amines in the solution of step a. may vary within a wide range, for example, depending on the solubility of the ammonia or amines. In general, from 0.01 to 10 molar equivalents of ammonia or amine, based on the ZnO. From 0.1 to 3 molar equivalents of ammonia or amine, in particular from 0.2 to 2 molar equivalents of ammonia or amine, based on ZnO, are preferred.
  • the zinc oxide nanoparticles are first dissolved in a solvent, and then the solution is fed to ammonia or amine as a gas.
  • the zinc oxide nanoparticles can be dissolved in a solvent in which ammonia or amine has already been introduced.
  • step c Organosilane added.
  • the zinc oxide nanoparticles and ammonia or amine are separately dissolved independently in a solvent.
  • Zinc oxide nanoparticles and ammonia or amine are preferably dissolved in the same solvent.
  • To prepare the solution of step a. The solutions of zinc oxide nanoparticles and ammonia or amine are mixed with one another by the customary methods known to the person skilled in the art for mixing liquids. The mixing can take place here in one step, in individual steps or continuously.
  • the solution of the zinc oxide nanoparticles is preferably initially introduced and the solution of the ammonia or amine is added.
  • step b. and c. the solution from step a. Tetraalkyl orthosilicate and optionally organosilane added and the dissolved zinc oxide nanoparticles are in the presence of ammonia or amine with the compounds of step b. and c. implemented.
  • the alkyl groups of the tetraalkyl orthosilicates are, independently of one another, preferably C 1 -C 20 -alkyl groups.
  • preference is given as tetraalkyl orthosilicate to tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl Lorthosilicate, or tetrabutyl orthosilicate used.
  • tetramethyl orthosilicate or tetraethyl orthosilicate is used.
  • the content of tetraalkyl orthosilicate in the process according to the invention can vary within a wide range, for example, depending on the reactivity of the silicate or the desired shell thickness or density. In general, from 0.01 to 1.0 molar equivalents of tetraalkyl orthosilicate, based on ZnO used. Preference is given to from 0.05 to 0.5 molar equivalents of tetraalkyl orthosilicate, in particular from 0.1 to 0.3 molar equivalents of tetraalkyl orthosilicate, based on the ZnO.
  • step c The process according to the invention preferably uses mono-, di-, tri-C 1 -C 20 -alkylsilanes, C 1 -C 20 -alkoxysilanes, C 1 -C -trialkoxy-C 3 -C 6 -alkylsilanes, aminoalkylsilanes, ester-containing silanes or polyalkoxysilanes as optional organosilanes.
  • triethoxyoctadecylsilane, triethoxyisooctylsilane, triethoxyisobutylsilane, triethoxypropylsilane, trimethoxyhexadecylsilane, PEG-silane, triethoxy-methacryloyloxypropylsilane, aminopropylsilane are used.
  • d-C2o-trialkoxy-C3-Ci8-alkylsilanes are used.
  • Pre-condensed oligomeric silanes are also used, for example Dynasilan® 9896 from Evonik.
  • the content of optional organosilanes in the process according to the invention can vary within a wide range, for example, depending on the reactivity of the silane or the desired shell thickness or density.
  • from 1 to 50% by mol of organosilane, based on the ZnO are used.
  • Tetraalkyl orthosilicates and organosilanes can be added either directly or as solutions to the zinc oxide nanoparticles dissolved in the solvent in the presence of ammonia or amines (steps b and c).
  • the solvent used, if present, is preferably the same solvent as for the zinc oxide nanoparticles and / or the ammonia and the amines.
  • the process of the invention is usually arbitrary.
  • the addition of the organosilane can be carried out before, during or after the addition of the tetraalkyl orthosilicate. Preferably, first the tetraalkyl orthosilicate and then the organosilane is added.
  • the tetraalkyl orthosilicates and the organosilanes are initially introduced in the solvent and then zinc oxide nanoparticles and ammonia or amines are added.
  • initially zinc oxide nanoparticles and ammonia or amines are introduced into the solvent and then tetraalkyl orthosilicates and the organosilanes are added.
  • zinc oxide nanoparticles, tetraalkyl orthosilicates and organosilanes are initially introduced in the solvent and then ammonia or amines are added.
  • reaction takes place at a temperature in the range from 0 to 200 ° C.
  • the reaction preferably takes place at temperatures in the range from 30 to 150 ° C., in particular from 50 to 100 ° C.
  • the pressure is of minor importance for carrying out the process according to the invention. In general, all steps are carried out at an external pressure equal to atmospheric pressure (1 atm), but may be carried out under superatmospheric or slight negative pressure.
  • the modified zinc oxide nanoparticles preference is given to obtaining primary particles having a size distribution which according to DLS is essentially monodisperse. Depending on the solvent and the concentration used, however, larger agglomerates may occur.
  • the polar solvent is removed by any method which results in a residue containing the modified zinc oxide nanoparticles becomes.
  • the polar solvent is partially or completely removed by distillation, filtration, centrifugation, decanting or spray drying. Particularly preferred is the distillation.
  • the modified zinc oxide nanoparticles are subjected to a drying step.
  • the drying takes place by the methods known to the person skilled in the art, for example by the use of a drying cabinet, optionally at elevated temperature and / or underpressure.
  • step a in step a. optional surface-active substances are present, which increase the stability of the dispersion of the ZnO nanoparticles in the solvent.
  • surface-active substances substances having an HLB value (according to Griffin) of 0 to 9, in particular from 0.5 to 5, are preferably used in the process according to the invention (step a).
  • Particularly preferred surface-active substances used are ionic, nonionic, betainic, zwitterionic surfactants, in particular anionic surfactants.
  • Surfactants are generally commercially available and can of course be used as mixtures.
  • the amount of surfactants may vary widely depending on, for example, the particular solvent. Are preferred in
  • Another object of the present invention are modified zinc oxide nanoparticles having Si-O-alkyl groups and are soluble in organic solvents, obtainable by the reaction of a. Zinc oxide nanoparticles dissolved in a solvent in the presence of ammonia or amines with b. a tetraalkyl orthosilicate and with c. optionally an organosilane, with the proviso that the reaction takes place at a content of less than 5 wt .-% water based on the total amount of solvent and water.
  • modified zinc oxide nanoparticles are preferred in which the reaction takes place at a content of less than 2% by weight of water, more preferably less than 1% of water.
  • modified ZnO nanoparticles in which essentially anhydrous at less than 0.5 wt .-% water, in particular less than 0.2 wt .-% water is used.
  • Modified zinc oxide nanoparticles which can be prepared, for example, by the method according to the invention described above, have significant differences in the composition compared with the zinc oxide nanoparticles of the prior art.
  • the modified zinc oxide nanoparticles according to the invention contain, after their preparation, Si-O-alkyl groups, depending on the tetraalkyl orthosilicate used, for example Si-Od-b groups.
  • the particles according to the invention have a content of 0.1 to 50% of the originally present Si-O-alkyl groups.
  • the particles according to the invention particularly preferably have a content of from 1 to 30% of the originally present Si-O-alkyl groups, in particular from 5 to 15%.
  • the particles according to the invention are also soluble in (nonpolar or polar) organic solvents, preferably in solvents having a relative permittivity of from 2 to 50, particularly preferably in solvents having a relative permittivity of from 3 to 40, in particular from 10 to 40, while the particles of the prior art are not soluble in these solvents.
  • the solubility of the particles according to the invention is, as already mentioned above, also to be understood as meaning a suspension whose particles as a rule have only a slight tendency to sedimentation and which as a rule is transparent and which scatters the visible light only slightly.
  • the modified zinc oxide nanoparticles according to the invention do not exhibit a dense or crystalline Si02 sheath as described in the prior art, for example in EP 1 167 462 A1, EP 1 284 277 A1 or WO 03/104319 A1.
  • the modified zinc oxide nanoparticles according to the invention have an amorphous shell around the core of zinc oxide, which, in addition to Si02, also contains other silicate or silane structures which have not completely reacted or hydrolyzed.
  • the exact composition of the shell is unknown.
  • the inhomogeneity of the shell structure is due to only partial hydrolysis of the tetraalkyl orthosilanes and / or orthosilanes, since only small amounts of water are present in the reaction.
  • Another object of the present invention are inanimate organic materials, in particular plastics, paints or inks containing modified ZnO nanoparticles or modified ZnO nanoparticles prepared according to the invention.
  • plastics, paints or inks containing modified ZnO nanoparticles or modified ZnO nanoparticles prepared according to the invention Preferably, from 0.001 to 50% by weight of zinc oxide nanoparticles are present Preference is given to contain from 0.01 to 10 wt .-% zinc oxide nanoparticles, in particular from 0.1 to 5 wt .-% zinc oxide nanoparticles are included.
  • Preferred inanimate organic materials are plastics (polymers).
  • the polymers are preferably polyolefins, in particular polyethylene or polypropylene, polyamides, polyacrylonitriles, polyacrylates, polymethacrylates, polycarbonates, polystyrenes, copolymers of styrene or methylstyrene with dienes and / or acrylic derivatives, acrylonitrile-butadiene-styrenes (ABS), polyvinyl chlorides, polyvinyl acetals, Polyurethanes, polyureas, epoxy resins or polyesters.
  • Organic polymers may also be copolymers, blends or blends of the above polymers.
  • Particularly preferred polymers are polyolefins, polystyrenes, polyacrylates, polyurethanes, polyureas, epoxy resins, polyamides, in particular polyethylene or polypropylene.
  • the plastics can be present as any desired shaped bodies.
  • the plastics are in the form of sheets or films.
  • the moldings are preferably plastic films, sheets or bags.
  • Zinc oxide nanoparticles are preferably contained from 0.001 to 50% by weight, more preferably from 0.01 to 10% by weight zinc oxide nanoparticles are contained, in particular from 0.1 to 5% by weight zinc oxide nanoparticles are contained.
  • Another object of the invention is the use of moldings according to the invention in agriculture, as packaging material, in particular in cosmetics, or in the automotive industry.
  • the modified ZnO nanoparticles absorb light having a wavelength in the range from 400 to 200 nm, more preferably from 370 to 200 nm. In general, the absorption of the modified ZnO nanoparticles also in the range below 200 nm.
  • Another object of the present invention is therefore the use of modified zinc oxide nanoparticles or modified zinc oxide nanoparticles prepared according to the inventive method, as a UV absorber in inanimate organic materials.
  • Another object of the present invention is the use of modified zinc oxide nanoparticles or modified zinc oxide nanoparticles prepared according to the inventive method, as stabilizers for inanimate organic materials.
  • the modified zinc oxide nanoparticles or modified zinc oxide nanoparticles prepared by the process according to the invention are preferably used as UV absorbers or stabilizers when the inanimate organic materials are plastics, paints or paints. Particularly preferred are plastics. Furthermore, the plastics are preferably in the form of sheets or films.
  • the incorporation of the modified ZnO nanoparticles into inanimate organic materials is carried out analogously to known methods for incorporating ZnO nanoparticles into such materials. Examples include the equipment of polymers (plastics) with zinc oxide during an extrusion step or the preparation of solid or liquid cosmetic formulations containing zinc oxide.
  • Another object of the present invention are inanimate organic materials, preferably plastics, paints or inks, in particular plastics, which contain further additives in addition to the modified ZnO nanoparticles according to the invention or inventively prepared.
  • Further additives are, for example, UV absorbers.
  • Other additives are usually used from 0.0001 to 30 wt .-% based on the amount of inanimate organic material. These are preferably used from 0.1 to 10 wt .-% based on the amount of inanimate organic material used, in particular from 0.1 to 5 wt .-%.
  • the further additives can be used according to the customary amounts known to the person skilled in the art.
  • UV absorbers are often commercial products. They are sold, for example, under the trade name Uvinul® from BASF SE or Tinuvin® from Ciba.
  • the UV absorbers comprise compounds of the following classes: benzophenones, benzotriazoles, cyanoacrylates, cinnamic acid esters, para-aminobenzoates, naphthalimides.
  • other known chromophores are used, e.g. Hydroxyphenyltriazines or oxalanilides. Such compounds are used, for example, alone or in mixtures with other light stabilizers in cosmetic applications, for example sunscreens or for the stabilization of organic polymers.
  • Further examples of UV absorbers are:
  • substituted acrylates such as, for example, ethyl or isooctyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate (mainly 2-ethylhexyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate), methyl ⁇ -methoxycarbonyl- ⁇ -phenyl acrylate, methyl ⁇ -methoxycarbonyl- ⁇ - (p-methoxyphenyl) acrylate, methyl or butyl ⁇ -cyano- ⁇ -methyl- ⁇ - (p-methoxyphenyl) acrylate, N- ( ⁇ -methoxycarbonyl- ⁇ -cyanovinyl) -2-methylindoline , Octyl-p-methoxycinnamate, isopentyl-4-methoxycinnamate, urocaninic acid or its salts or esters; Derivatives of p-aminobenzoic acid, in particular esters thereof, for example, eth
  • 2-hydroxybenzophenone derivatives e.g. 4-hydroxy, 4-methoxy, 4-octyloxy, A-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy, 2'-hydroxy-4,4' - dimethoxy-2-hydroxybenzophenone and 4-methoxy-2-hydroxybenzophenone-sulfonic acid sodium salt;
  • Esters of 4,4-diphenylbutadiene-1, 1-dicarboxylic acid e.g. the bis (2-ethylhexyl) ester;
  • Benzylidene camphor or its derivatives as described, for. As mentioned in DE-A 38 36 630, e.g. 3-Benzylidene camphor, 3 (4'-methylbenzylidene) d-1-camphor;
  • Dibenzoylmethanes e.g. 4-tert-butyl-4'-methoxydibenzoylmethane
  • 2,4,6-triaryltriazine compounds such as 2,4,6-tris ⁇ N- [4- (2-ethylhex-1-yl) oxycarbonylphenyl] amino ⁇ -1, 3,5-triazine, 4,4 ' - ((6- ((tert.
  • Suitable UV absorbers are also described in lines 14 to 30 ([0030]) on page 6 of EP 1 191 041 A2. These are incorporated herein by reference, and this reference is made to the disclosure of the present invention.
  • inanimate organic materials in particular polymers (plastics), paints or inks which contain modified ZnO nanoparticles and UV absorbers as further additives, can be stabilized against the action of UV light.
  • Another object of the present invention is a method for stabilizing inanimate organic materials, in particular polymers against the action of light, free radicals or heat, wherein the materials, in particular polymers modified ZnO nanoparticles are added, optionally as further additives light-absorbing compounds, for example UV absorbers and / or stabilizers, for example containing HALS compounds. Furthermore, can be stabilized in this way also paints or colors against the action of light, radicals or heat.
  • the stabilizers are compounds that stabilize organic polymers against degradation upon exposure to oxygen, light (visible, infrared and / or ultraviolet light) or heat. They are also referred to as antioxidants, radical scavengers or as light stabilizers, cf. Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 3, 629-650 (ISBN-3-527-30385-5) and EP-A 1 110 999, page 2, line 29 to page 38, line 29. With such stabilizers Virtually all organic polymers can be stabilized, cf. EP-A 1 1 10 999, page 38, line 30 to page 41, line 35.
  • the stabilizers described in the EP application belong to the class of compounds of the pyrazolones, the organic phosphites or phosphonites, the sterically hindered phenols and the sterically hindered phenols.
  • hindered amines stabilizers of the so-called HALS type or HALS stabilizers, see Römpp, 10th edition, volume 5, pages 4206-4207.
  • HALS stabilizers Other additives which may furthermore be considered are HALS stabilizers.
  • HALS stabilizers are often commercial products. They are sold, for example, under the trademark Uvinul® or Tinuvin® from BASF SE. Examples are Tinuvin 770 (CAS No. 52829-07-9), Uvinul 4050 H (CAS No. 124172-53-8) or Uvinul 5050 (CAS No. 93924-10-8).
  • the HALS stabilizers comprise compounds containing groups of formula IIa or those of formula IIb,
  • R 1 , R 2 , R 3 and R 4 are the same or different and independently of one another
  • Ci-Ci2-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably CrC 4 -AlkVl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, in particular R 1 , R 2 , R
  • C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl,
  • X 5 is an oxygen atom, a sulfur atom, an NH group, an N- (C 1 -C 4 -alkyl) group, a carbonyl group,
  • a 2 is a single bond or a spacer.
  • spacer A2 are para-phenylene, meta-phenylene, preferably C 1 -C 20 -alkylene, branched or unbranched, it being possible for one to six non-adjacent CH 2 groups to be replaced by one sulfur atom, also oxidized, or one oxygen atom ,
  • spacers may be mentioned:
  • Preferred spacers A 2 are C 2 -C 10 -alkylene groups, branched or unbranched, such as -CH 2 -CH 2 -, - (CH 2 Js-, - (CH 2 J 4 -, - (CH 2 J 5 -, - ( CH 2 J 6 -, - (CH 2 J 7 -, - (CH 2 J 8 -, - (CH 2 J 9 -,
  • X 6 is hydrogen, oxygen, O-C 1 -C 8 -alkyl, preferably C 1 -C 6 -alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy , n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, more preferably methoxy or ethoxy
  • C 1 -C 12 -alkyl preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2
  • HALS are:
  • piperidine derivatives e.g. the polymer of dimethyl butanedioate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol or poly-6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2, 4-diyl (2,2,6,6-tetramethyl-4-piperidinyl) imino-1,6-hexanediyl (2,2,6,6-tetramethyl-14-piperidinyl) imino, and polycondensates from dimethyl succinate and 1 - (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine which are particularly well suited as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
  • piperidine derivatives e.g. the polymer of dimethyl butanedioate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol or poly-6- (1,1,3,3
  • auxiliaries are, for example, substances which at least largely prevent the fogging of films or molded parts made of plastics, so-called antifogging agents.
  • antifogging agents are also suitable as polymer additives.
  • anti-fogging agents for organic polymers from which in particular plates or films are produced.
  • Such polymer additives are described, for example, by F. WyNn, in Plastics Additives Handbook, 5th Edition, Hanser, ISBN 1-56990-295-X, pages 609-626. According to the invention, therefore, modified ZnO nanoparticles containing auxiliaries as further effect substances can be used Use anti-fogging or anti-fogging agents.
  • auxiliaries are lubricants such as oxidized polyethylene waxes and antistatic agents for organic polymers.
  • antistatic agents cf. the aforementioned reference F. WyNn, Plastics Additives Handbook, pp. 627-645.
  • Suitable further additives are flame retardants, which are described, for example, in Römpp, 10th edition, pages 1352 and 1353 and in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 14, 53-71. According to the invention, therefore, fined ZnO nanoparticles, which contain flame retardants as flame retardants for polymers as further effect substances.
  • stabilizers and auxiliaries are described, for example, under the brand names Uvinul®, Tinuvin®, Chimassorb® and Irganox® by BASF or Ciba, Cyasorb® and Cyano® by Cytec, Lowilite®, Lowinox®, Anox®, Alkanox®, Ultranox® and Weston® from Chemtura and Hostavin® and Hostanox® from Clariant.
  • Stabilizers and auxiliaries are described for example in Plastics Additives Handbook, 5th edition, Hanser Verlag, ISBN 1-56990-295-X.
  • additives include organic dyes that absorb light in the visible range, or optical brighteners. Such dyes and optical brighteners are described in detail, for example, in WO 99/40123, page 10, line 14 to page 25, line 25, to which reference is expressly made. While organic dyes have an absorption maximum in the wavelength range from 400 to 850 nm, optical brighteners have one or more absorption maxima in the range from 250 to 400 nm. Optical brighteners emit fluorescence radiation in the visible range when irradiated with UV light. Examples of optical brighteners are compounds from the classes of bisstyrylbenzenes, stilbenes, benzoxazoles, cu- marine, pyrenes and naphthalenes.
  • optical brighteners are sold under the trademarks Tinopal®, Uvitex®, Ultraphor® (BASF SE) and Blankophor® (Bayer). Optical brighteners are also described in Römpp, 10th Ed., Vol. 4, 3028-3029 (1998) and in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 24, 363-386 (2003). According to the invention, therefore, it is possible to use modified ZnO nanoparticles which contain organic dyes or brighteners as further effect substances for coloring or lightening polymers.
  • IR dyes which are sold for example by BASF SE as Lumogen® IR.
  • Lumogen® dyes include compounds of the classes of perylenes, naphthalimides, or quaterylenes.
  • modified ZnO nanoparticles according to the invention can be subsequently modified further on their surface using methods known from the prior art.
  • Another object of the present invention are liquid formulations containing modified ZnO nanoparticles or modified ZnO nanoparticles prepared according to the invention.
  • liquid formulations according to the invention or the solutions prepared according to the invention, in particular dispersions or suspensions can be used directly as such or after concentration or dilution.
  • the liquid formulations of the invention may contain conventional additives (additives), for.
  • additives for.
  • thickener thickener
  • antifoaming agents for.
  • bactericides for.
  • protective colloids can be anionic, nonionic, cationic or zwitterionic in nature.
  • liquid formulations according to the invention or the suspensions prepared according to the invention can be formulated with conventional binders, for example aqueous polymer dispersions, water-soluble resins or with waxes.
  • binders for example aqueous polymer dispersions, water-soluble resins or with waxes.
  • the modified ZnO nanoparticles according to the invention are contained in the liquid formulations and can be obtained from these liquid formulations by removing the volatile constituents of the liquid phase, even in powder form.
  • the powder particles of the invention may be present either isolated, in agglomerated form, or partially filmed.
  • the powders according to the invention are accessible, for example, by evaporation of the liquid phase, freeze-drying or by spray-drying.
  • liquid formulations according to the invention are obtainable by redispersing the powders according to the invention, for example in nonpolar solvent.
  • Another object of the present invention are solid formulations containing modified ZnO nanoparticles or modified ZnO nanoparticles prepared according to the invention.
  • Solid formulations according to the invention contain the modified ZnO nanoparticles, depending on the application, in different concentrations.
  • the proportion of modified ZnO nanoparticles in the range of 0.1 to 80 wt .-% and in particular in the range of 0.5 to 50 wt .-% based on the total weight of the solid formulation.
  • the solid formulations are a mixture of the modified ZnO nanoparticles of the invention in a polymeric support material, e.g. Polyolefins (e.g., low or high density polyethylene, polypropylene), styrene homo- or copolymers, polymers of chlorinated alkenes (e.g., polyvinyl chloride), polyamides, polyesters (e.g., polyethylene or polybutylene terephthalate), polycarbonates, or polyurethanes.
  • a polymeric support material e.g. Polyolefins (e.g., low or high density polyethylene, polypropylene), styrene homo- or copolymers, polymers of chlorinated alkenes (e.g., polyvinyl chloride), polyamides, polyesters (e.g., polyethylene or polybutylene terephthalate), polycarbonates, or polyurethanes.
  • a polymeric support material e.g.
  • Solid formulations of the invention are also mixtures of the modified ZnO nanoparticles with relatively low molecular weight matrices, e.g. Polyethylene waxes.
  • the modified ZnO nanoparticles can be introduced into the molten matrix, for example, by dispersing at elevated temperature, the solid formulation being formed on cooling.
  • the solid formulation may also contain auxiliaries which improve the distribution of the modified ZnO nanoparticles in the solid matrix (dispersants).
  • auxiliaries which improve the distribution of the modified ZnO nanoparticles in the solid matrix (dispersants).
  • waxes can be used for this purpose.
  • the solid formulations may be used neat or after dilution to the use concentration.
  • Solid formulations are, for example, the formulations obtained after the removal of the volatile constituents of the liquid formulations described above. These are generally mixtures / dispersions of modified ZnO nanoparticles with / in poly- or oligomers (in the masterbatch, in waxes, for example Luwax® from BASF SE), which are present as powders or waxes.
  • modified ZnO nanoparticles according to the invention in the form of their solid or liquid formulations or powders are preferably used for equipping, for example for stabilizing, in particular with respect to UV radiation, organic polymers.
  • the particles can be introduced both into the organic polymer as a solid or liquid formulation and as a powder by the usual methods. incorporating polymers. Mention may be made, for example, of the mixture of the particles with the organic polymers before or during an extrusion step.
  • Organic polymers here are to be understood as meaning any plastics, preferably thermoplastics, in particular films, fibers or shaped bodies of any desired shape. These are also referred to simply as organic polymers in the context of this application. Further examples of the equipment or stabilization of organic polymers with polymer additives can be found in the Plastics Additives Handbook, 5th edition, Hanser Verlag, ISBN 1-56990-295-X.
  • the organic polymers are preferably polyolefins, in particular polyethylene or polypropylene, polyamides, polyacrylonitriles, polyacrylates, polymethacrylates, polycarbonates, polystyrenes, copolymers of styrene or methylstyrene with dienes and / or acrylic derivatives, acrylonitrile-butadiene-styrenes (ABS), polyvinyl chlorides, polyvinyl acetals , Polyurethanes or polyesters.
  • Organic polymers may also be co-polymers, blends or blends of the above polymers. Particularly preferred polymers are polyolefins, in particular polyethylene or polypropylene.
  • thermoplastic polymer In order to stabilize a thermoplastic polymer against UV exposure, it is possible, for example, to melt the polymer first in an extruder, a particle powder prepared according to the invention containing modified ZnO nanoparticles into the polymer melt at a temperature of, for example, 180 to 200 ° C. C (polyethylene) or, for example, about 280 0 C (polycarbonate) incorporates and produces a granulate, from which then by known methods films, fibers, or molded parts are prepared, which are stabilized against the action of UV radiation.
  • C polyethylene
  • 280 0 C polycarbonate
  • the amount of modified ZnO nanoparticles in the organic polymer sufficient to stabilize the polymer can vary over a wide range depending on the application.
  • the stabilized polymers preferably contain from 0.1 to 10% by weight of the modified ZnO nanoparticles based on the total weight of the mixture. Most preferably from 0.5 to 5.0 wt .-%.
  • the production process of the modified ZnO nanoparticles according to the invention allows a very efficient and controlled access to the particles.
  • the modified ZnO nanoparticles according to the invention are present, for example, as constituents of liquid formulations or of powders and can easily be converted into organic compounds Incorporating polymers.
  • the modified ZnO nanoparticles according to the invention exhibit a reduced photocatalytic activity in organic polymers and thus avoid the undesired premature degradation of the polymer matrix.
  • modified ZnO nanoparticles according to the invention are particularly suitable for equipping organic polymers against the action of UV rays or light.
  • the suspension was cooled and the reaction product settled overnight.
  • the supernatant was filtered off with suction and the residue was washed with 1 l of isopropanol.
  • the residue was washed a total of 3 times with isopropanol.
  • the nanoparticulate (10nm diameter) zinc oxide was stored as a suspension in isopropanol.
  • the suspension was cooled and the reaction product settled overnight.
  • the supernatant was filtered off with suction and the residue was washed with 1 l of methanol.
  • the residue was washed with methanol three times.
  • the nanoparticulate (about 90 nm diameter) zinc oxide was stored as a suspension in methanol.
  • Luwax® A ethylene homopolymer, BASF SE
  • Luwax® A ethylene homopolymer, BASF SE
  • ZnO in solution containing 0.1 g ZnO
  • the solvent was removed at 75 ° C / 1 mbar. The result was a homogeneous, colorless wax.
  • Luwax® EVA 1 Part of the solid was incorporated into Luwax® EVA 1 (see incorporation in Luwax®).
  • 0.718 g of zinc oxide as suspension (about 2.5% by weight in isopropanol, 1 eq of ZnO, "10 nm") and 1.81 ml of aqueous ammonia solution (3 eq of Nhb, 25% strength ammonia solution was used) were initially charged and heated with stirring to 50 0 C. Then, 0.27 g of tetramethyl orthosilicate (0.2 eq., relative to ZnO) was added. the suspension was stirred for 1 h at 50 0 C. After the reaction, a part of the suspension was transferred to. Luwax® A (see incorporation in Luwax®) incorporated.
  • Example 6 triethoxyisobutylsilane
  • Example 7 triethoxypropylsilane
  • Example 8 triethoxyhexadecylsilane
  • Example 9 Dynasilan® 9896 (Evonik)
  • Examples 10 and 11 Variation of the tetraalkyl orthosilicate amount 1 g of zinc oxide as a suspension (about 2.5% by weight in isopropanol, 1 eq of ZnO, "10 nm") and 5.29 ml of methanolic ammonia (3 eq of NH 3 based on ZnO, a 7N ammonia solution was used) and heated with stirring to 50 0 C. Thereafter xg tetramethyl orthosilicate (y eq. Relative to ZnO) and then 0.972 g of 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane (0.15 eq. Relative to ZnO) was added. The transparent solution was stirred for 20 h at 50 0 C. A portion of the solution was in Luwax® A (see incorporation into Luwax®) incorporated.
  • Lupolen® is the trade name for a polyethylene (LDPE) from Basell.
  • the Luwax® preparations of the examples and comparative examples were incorporated into Lupolen® using a mini-extruder and processed into a 100 ⁇ m thick film.
  • the concentration was 1% by weight of ZnO based on the total amount of wax and polyethylene.
  • the films were exposed (artificial sunlight) and the UV absorption spectra were measured. As a measure of the transparency of the films, the transmission was determined. A decrease in the transparency due to the exposure is due to the photocatalytic action of ZnO, which causes a destruction. tion of the polymer matrix entails. The higher the transmission during exposure, the less photocatalytically active is the ZnO present.
  • Solasorb® UV200 from Croda ZnO, as UV absorber for plastics, dispersion with 60 wt.% Solids content
  • Maxlight ZS® from Showa Denko (SiO 2 -coated 30 nm ZnO particles) were also measured for comparison.
  • FIG. 1 The measured relative transmission as a function of the wavelength ( ⁇ ) of 200 to 800 nm for comparative experiment 3.
  • FIG. 2 The measured relative transmission as a function of the wavelength ( ⁇ ) of 200 to 800 nm for Example 3.
  • Figures 1 and 2 show transmission spectra recorded for the films of Comparative Experiment 3 and for Example 3.
  • the results show that for the comparative experiment 3 (Fig. 1), the transmission in the wavelength range of about 350 to 800 nm already after 7 days (curve : 7) has clearly decreased from the initial situation (curve: 0), since the film becomes cloudy due to the decomposition of the polymer matrix, while for the film of Example 3 (FIG. 2) after 15 days (curve: 15) and also after 50 Days (curve: 50) no change from the starting situation can be observed.

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