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
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
  • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/67—Particle size smaller than 100 nm
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/68—Particle size between 100-1000 nm
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • 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
  • C01P2006/12—Surface area
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/40—Coatings comprising at least one inhomogeneous layer
  • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
  • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
  • C03C2217/445—Organic continuous phases
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/40—Coatings comprising at least one inhomogeneous layer
  • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
  • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
  • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
  • C03C2217/475—Inorganic materials
• • 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
  • C08K2003/2296—Oxides; Hydroxides of metals of zinc
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives
• • 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 invention relates to a dispersion which contains nanoscale zinc oxide, a coating preparation, a method for producing the dispersion and the coating preparation, and the use of the coating preparation.
• the object of the invention was therefore to provide a transparent, UV-resistant coating for substrates, which are preferably used outdoors. Furthermore, the disadvantages described in the prior art when used outdoors, such as cracks and weakening binding to the substrate or discoloration of the substrate, should be avoided as far as possible.
• the invention relates to a dispersion which contains zinc oxide powder with a BET surface area of 10 to 200 m 2 / g, an average secondary particle size in the Dispersion of less than 300 nm and a solids content of 0.1 to 60 wt .-%, preferably from 1 to 10 wt .-%, based on the total amount of the dispersion, and the dispersion contains at least one additive.
• the dispersion according to the invention can either be aqueous or organic, or consist of a mixture which has water and organic solvents as the liquid phase, in all cases only a single liquid phase being present.
• Aqueous is to be understood to mean that the major part of the liquid phase consists of water.
• Organic is to be understood to mean that the liquid phase consists predominantly or exclusively of at least one organic solvent.
• Suitable organic solvents can be ethanol, methanol, propanol, butanol, acetone, ethyl acetate, butyl acetate, alkanes and / or ethers.
• the organic solvent can also be a reactive diluent, such as, for example, hexanediol diacrylate or tripropylene glycol diacrylate.
• An aqueous dispersion is preferred for the purposes of the invention.
• the dispersion according to the invention contains an additive.
• This can be a dispersing aid, an emulsifier, a pH regulator and / or a stabilizer.
• This can preferably be Na polyphosphate, ascorbic acid, citric acid, 6-aminohexanoic acid, stearic acid and / or salts of polyacrylic acid, in particular the sodium salt.
• the additive is preferably present in an amount of 0.1 to 5% by weight, particularly preferably 0.5 to 1.5% by weight, based on the liquid phase of the dispersion.
• the type of zinc oxide present in the dispersion according to the invention is only restricted to the extent that it has a BET surface area of 10 to 200 m 2 / g and an average secondary particle size in the dispersion of less than 300 nm.
• the dispersion according to the invention can preferably contain a zinc oxide which has a BET surface area of 10 to 200 m 2 / g and an average secondary particle size in the dispersion of less than 300 nm and which is in the form of aggregates of anisotropic primary particles.
• Anisotropic means that the arrangement of the atoms along the three spatial axes is different.
• Anisotropic primary particles are understood to mean, for example, those which are acicular, bulbous or platelet-shaped.
• the aggregates can be composed of a mixture of bulbous primary particles and acicular primary particles, the ratio of bulbous / acicular primary particles being between 99: 1 and 1:99.
• the bulbous primary particles of zinc oxide preferably have an average diameter of 10 to 50 nm and the needle-shaped primary particles preferably have a length of 100 nm to 2000 nm, a width of 10 nm to 100 nm.
• the aggregates of the zinc oxide powder can have a largely anisotropic structure, defined by a form factor F (circle) of less than 0.5.
• the size F (circle) describes the deviation of an aggregate from an ideal circular shape.
• F (Circle) is 1 for an ideal circular object. The smaller the value, the further the structure of the object is from the ideal circular shape.
• the parameter is defined in accordance with ASTM 3849-89.
• the zinc oxide powder can have on its surface an oxygen concentration as non-desorbable moisture in the form of Zn-OH and / or Zn-OH2 units of at least 40%.
• XPS X-ray photoelectron spectroscopy
• the bulk density of the zinc oxide powder can be 40 to 120 g / 1. Further may be present with the date of filing 22.09.2003 in the inventive dispersion a 'zinc oxide, as described in German Patent Application with the file reference 10342728.2.
• particles are to be understood as those which are primarily formed in the pyrogenic production process. These accumulate to form aggregates during the reaction with the formation of sintered surfaces. It is essential that these aggregates are made up of particles with different morphologies. According to the definition, an aggregate is made up of the same or approximately the same particles, the primary particles (DIN 53206). In contrast, the zinc oxide powder has aggregates which consist of particles of different morphology and are therefore not referred to as primary particles. Morphology means both isotropic and anisotropic particles. For example, they can be spherical or largely spherical particles, bulbous particles, rod-shaped particles or needle-shaped particles. It is essential that the aggregates consist of different particles and that these particles are connected to one another by sintered surfaces.
• the BET surface area of the zinc oxide powder can be between 20 and 60 m 2 / g.
• the aggregates of the zinc oxide powder according to the invention are in circular, ellipsoid, linear and branched forms.
• Zinc oxide powder may be preferred which has an approximately equally large proportion of 30-40% of ellipsoid and linear shapes and a smaller proportion of branched shapes of 20-25% and circular shapes of 2-6%.
• the zinc oxide powder can have a tamped density, determined according to DIN ISO 787/11, of at least 50 g / 1.
• the zinc oxide powder can consist of aggregates which have an average projected aggregate area of less than 10,000 nm 2 , an equivalent circle diameter (ECD) of less than 100 nm and an average circumference of less than 600 nm. These sizes can be obtained by image analysis of approx. 1000 to 2000 aggregates from TEM images. Zinc oxide powder with an average projected aggregate area of 2000 to 8000 nm 2 , an equivalent circle diameter (ECD) between 25 and 80 nm and an average circumference between 200 and 550 nm can be particularly preferred.
• the dispersion according to the invention can also contain hydrophobized zinc oxide powder.
• D3, D4 and D5 are cyclic polysiloxanes with 3, 4 or 5 units of the type -0-Si (CH 3 ) 2 -.
• octamethylcyclotetrasiloxane D4
• the dispersion according to the invention can particularly preferably comprise a zinc oxide powder hydrophobized with octyltrimethoxysilane or polydimethylsiloxane.
• the hydrophobized zinc oxide powder can preferably have a BET surface area of 10 to 50 m 2 / g.
• the hydrophobized zinc oxide powder can particularly preferably have a BET surface area of 18 ⁇ 5 m 2 / g and a carbon content of 0.5 to 1.0% by weight.
• This powder and its preparation are the subject of European patent application EP03018678-7 dated August 22, 2003.
• the hydrophobized zinc oxide powder can be obtained by spraying the surface-modifying substance onto the zinc oxide powder, which has optionally been sprayed with water, at room temperature and a subsequent heat treatment at 50 to 400 ° C. for a period of 1 to 6 hours.
• the zinc oxide powder in the dispersion according to the invention can have a lead content of at most 20 ppm and an arsenic content Not more than 3 ppm, not more than 15 ppm of cadmium, not more than 200 ppm of iron, not more than 1 ppm of antimony and not more than 1 ppm of mercury.
• Another object of the invention is a method for producing the dispersion of the invention.
• the zinc oxide powder is introduced into a liquid medium by means of high energy input under dispersing conditions.
• a high energy input is necessary in order to obtain zinc oxide particles with the required fineness of less than 300 nm in the dispersion.
• the additive can be added before, during or after the dispersion.
• the additive is intended to protect the dispersion against reagglomeration and sediment formation.
• the amount depends on the content of zinc oxide in the dispersion and the question of whether the dispersion should be transported over long distances and therefore be stable to sedimentation, or whether the dispersion should be further processed immediately after its production.
• Suitable dispersing devices which bring about a high energy input can be rotor-stator machines, planetary kneaders, ultrasonic devices or high-pressure homogenizers, for example a Nanomizer® or an Ultimizer® system.
• Another object of the invention is a coating preparation which contains the dispersion according to the invention and at least one binder.
• Suitable binders can be polyacrylates, polyurethanes, polyalkydes, polyepoxides, polysiloxanes, polyacrylonitriles and / or polyesters.
• an aliphatic urethane acrylate for example Laromer® LR8987, BASF, can be particularly suitable as the binder.
• the coating preparation according to the invention can particularly preferably contain polyacrylates and / or polyurethanes.
• the proportion of the binder in the coating preparation is preferably between 0.1 and 50% by weight. A range between 1 and 10% by weight is particularly preferred.
• the proportion of zinc oxide in the coating preparation is preferably between 0.1 and 60% by weight. A range between 1 and 10% by weight is particularly preferred.
• the coating preparation can contain compounds for changing the rheology of the coating preparation during application.
• Fillers containing silicon dioxide are particularly advantageous, with pyrogenically produced silicon dioxide being particularly preferred.
• the amount can preferably be between 0.1 and 20% by weight, based on the total coating preparation.
• the coating preparation can contain organic solvents such as ethanol, butyl acetate, ethyl acetate, acetone, butanol, THF, alkanes or mixtures of two or more of these substances in amounts of 1% by weight to 98% by weight, based on the overall coating preparation, contain.
• organic solvents such as ethanol, butyl acetate, ethyl acetate, acetone, butanol, THF, alkanes or mixtures of two or more of these substances in amounts of 1% by weight to 98% by weight, based on the overall coating preparation, contain.
• Another object of the invention is a method for producing the coating preparation according to the invention, in which a dispersion according to the invention is added to a binder under dispersing conditions.
• Another object of the invention is the use of the coating preparation according to the invention for coating substrates made of wood, PVC, plastic, steel, aluminum, zinc, copper, MDF, glass, concrete.
• the advantages of using the dispersion and coating preparation according to the invention over those according to the prior art in the outdoor area are:
• Zinc oxide dispersion D-1 Zinc oxide dispersion D-1:
• a zinc oxide powder produced according to DE-A-10212680 with a BET surface area of 20 m 2 / g is used.
• the dispersion always remains thin. After the final concentration of 53.5% by weight of zinc oxide has been reached, dispersion is continued for 2 minutes with water cooling. The dispersion is thin even after 30 days, shows no sediment and is therefore easy to handle.
• the pH is about 10.
• Zinc oxide dispersion D-2 Production analogous to D-1, but with a degree of filling of 10% by weight.
• Zinc oxide dispersion D-3 Production analogous to D-2, but using a hydrophobized zinc oxide powder and a 50:50 water / ethanol mixture (parts by volume) instead of water.
• the hydrophobized zinc oxide powder is obtained according to the European patent application with the application number 3018678.7 from August 22, 2003. It is a zinc oxide powder hydrophobicized with octyltrimethoxysilane with a BET surface area of 18 m 2 / g and a carbon content of 0.6%.
• Coating preparation based on acrylic / polyurethane B-2A / PU The zinc oxide dispersion D-2 is added under dispersing conditions to a commercially available acrylic / polyurethane binder preparation, so that a coating preparation with a zinc oxide dispersion content of 2% by weight is added .-% results.
• Acrylic-based coating preparation B-2A As for B-2A / PU, but using a commercially available acrylic binder preparation.
• the zinc oxide dispersion D-3 is added to a commercially available acrylic / polyurethane binder preparation under dispersing conditions, so that a coating preparation with a proportion of hydrophobic zinc oxide dispersion of 2% by weight results.
• Acrylic-based coating preparation B-3A Execution as for B-3A / PU, but using a commercially available acrylic binder preparation.
• UV resistance when coating wood The coating preparations from Examples B-2A / PU and B-2A are used to coat 3 pinewood samples that have been pretreated with a primer (Relius Aqua Holz Grund) (QUV-B 313; DIN EN 927-6, ISO 11507, ASTM D 4857). Pine wood samples with a zinc oxide-free sample serve as a comparison Coating preparation based on acrylic / polyurethane (Relius Aqua Siegel Gloss).
• the zinc oxide-containing coatings from Examples B-2AP and B-2A show significantly less yellowing, a significantly higher gloss and no embrittlement or cracks in the coating.
• Coating preparations from Examples B-2A / PU and B-2A, as well as a zinc oxide-free coating preparation based on acrylic / polyurethane (Relius Aqua Siegel Gloss) as a comparison, are applied to glass plates in a layer thickness of 150 ⁇ m. The hardness becomes after
• the metal plates are pretreated with a white lacquer.
• the coating compositions B-2A, B-2A / PU, B-3A and B-3A / PU and a commercially available coating composition are then treated with an organic UV filter and irradiated for 55 days in accordance with DIN53231.
• the Berger whiteness of the sample with an organic UV filter is 81.5, while the samples with the compositions B-2A and B-3A according to the invention have values of 86.5 and 86, respectively.
• the gloss (gloss angle 60 °) in the compositions B-2A / PU and B-3A / PU according to the invention is higher by a factor of 7 to 10 than in the comparative sample.
• Ultrasonic dispersion is used to produce 0.1 percent by weight dispersions (D4 to D7) of zinc oxide in water and the UV-VIS spectra of these dispersions are recorded (layer thickness 1 mm).
• the dispersion D4 (according to the invention) contains a zinc oxide powder, as described in the German patent application with the file number 10342728.2 with the filing date September 22, 2003, with a BET surface area of 25 m 2 / g.
• the dispersion D5 (comparison) contains the zinc oxide powder ZnO-410, Sumitomo Osaka, with a BET surface area of 34 m 2 / g.
• the dispersion D6 (comparison) containing the zinc oxide Z-Cote ®, nanophase having a BET surface area of 19 m 2 / g.
• the dispersion D7 (comparative) containing the zinc oxide powder Zinvisible ®, Zinc Corp. of America, with a BET surface area of 17 m 2 / g.
• FIG. 1 shows that the dispersion D4 according to the invention has a high absorption in the UV-A range with simultaneous high transparency.
• the dispersion D4 according to the invention clearly has advantages in transparency with at least comparable UV absorption. This is particularly surprising when compared with dispersion D5, in which the zinc oxide powder has a higher BET surface area than that in dispersion D4 according to the invention.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Nanotechnology (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Composite Materials (AREA)
• Inorganic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Crystallography & Structural Chemistry (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Dispersion Chemistry (AREA)
• Paints Or Removers (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Colloid Chemistry (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 2004
  • 2004-01-24 DE DE102004003675A patent/DE102004003675A1/de not_active Withdrawn
• 2005
  • 2005-01-08 AU AU2005206254A patent/AU2005206254B2/en not_active Ceased
  • 2005-01-08 JP JP2006549953A patent/JP4768633B2/ja not_active Expired - Fee Related
  • 2005-01-08 WO PCT/EP2005/000110 patent/WO2005071002A1/de active Application Filing
  • 2005-01-08 EP EP05700760A patent/EP1706449A1/de not_active Withdrawn
  • 2005-01-08 CN CNA2005800030627A patent/CN1910225A/zh active Pending
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