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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G9/00—Compounds of zinc
  • C01G9/02—Oxides; Hydroxides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/256—Heavy metal or aluminum or compound thereof

Definitions

• the invention relates to water- and halogen-free dispersions containing primary particulate redispersed zinc oxide particles with an average diameter between 1 and 200 nm and amino alcohols, a process for the preparation of the dispersions and the use of these dispersions for the production of moldings and coatings.
• Zinc oxide nanoparticle dispersions in which the particles are primarily disperse are known from WO 00/50503.
• zinc acetate dihydrate commercially available or made in situ from coarse-particle zinc oxide, water and glacial acetic acid
• the purification and concentration of the reversibly agglomerated particles initially obtained as a slurry is carried out by sedimentation, removing the supernatant, refilling with fresh methanol while stirring and again sedimentation.
• the brine (dispersions, colloidal solutions) is then formulated by suitable compression of the particles for gel and redispersion in water and / or organic solvents, if appropriate with the addition of surface-modifying substances.
• Transparent, highly effective UV protective coatings based on condensation-crosslinking sol / gel materials can be produced from primary particulate dispersed zinc oxide (nano-ZnO dispersion) (EP 1 146 069 A2).
• nano-ZnO dispersion primary particulate dispersed zinc oxide
• the water-free nano-zinc oxide dispersion in dichloromethane or chloroform described in WO 00/50503 is used for this.
• the use of halogenated solvents is prohibitive for the commercial marketing of these coatings and the brine they contain.
• zinc oxide is particularly good in amino alcohols or mixtures of amino alcohols with halogen-free and water-free organic solvents. redisperse primary particles and formulate them into highly concentrated, stable dispersions from which molded articles and coatings containing primary particle dispersed Zihkoxid can be produced.
• the invention relates to water-free and halogen-free dispersions which contain amino alcohols and primary particulate redispersed zinc oxide (nano-ZnO) with an average particle diameter (determined by means of ultracentrifugation) of 1 to 200 nm.
• the dispersions according to the invention consist of the primary particulate redispersed zinc oxide particles and the water- and halogen-free dispersion medium.
• the mixtures according to the invention preferably contain nano-zinc oxide with an average particle diameter, determined by means of ultracentrifugation, between 5 and 50 nm, particularly preferably between 5 and 20 nm.
• primary particulate redispersible or redispersed zinc oxide means that the proportion of the zinc oxide used which cannot be broken up again into its primary particles or is not broken down in the dispersion in question is less than 15% by weight, in particular less accounts for 1% by weight of the total amount of zinc oxide used.
• the water-free and halogen-free dispersion medium preferably consists essentially of pure amino alcohols or their mixtures with water-free and halogen-free solvents.
• the proportion of water-free and halogen-free solvents in the total amount of the dispersion medium is between 0 and 96% by weight.
• Amino alcohols of the formula (I) are preferably used as amino alcohols.
• R 1 and R 2 independently of one another represent a C 1 -C 3 -alkyl radical or are part of an aliphatic or aromatic C 5 -C 20 radical or correspond to the radical - (CH 2 ) x -OH, and
• x is an integer from 1 to 30.
• R 1 and R 2 in formula (I) are particularly preferably the radical (CH 2 ) x -OH, where x is 2, 3 or 4.
• Triethanolamine is very particularly preferred.
• Alcohols, esters and / or ketones, in particular C 2 -C 6 -monoalcohols, are preferably used as the water- and halogen-free solvent.
• the zinc oxide concentrations of the primary particle-redispersed particles in the dispersion medium are generally between 0.1 and 75% by weight, preferably 10 and 50% by weight, in particular 20 and 40% by weight.
• the dispersions of primary particulate redispersed particles according to the invention are notable for the fact that they are stable in storage and show no tendency towards particle agglomeration, solid precipitation, segregation, gelling, solidification, discoloration and / or curing, even after weeks and months.
• the zinc oxide dispersions according to the invention are produced by dispersing a primary particulate redispersible zinc oxide in the dispersion medium.
• primary particulate redispersible zinc oxides in the form of methanolic suspensions or gels are used, which were prepared, for example, according to WO 00/50503.
• the zinc oxide concentrations here are generally between 5 and 75% by weight, preferably between 25 and 50% by weight.
• the conductivity of the methanolic liquid phase is less than 200 S / cm, preferably less than 10 mS / cm.
• dispersions containing methanol are removed by distillation, which improves the state of dispersion of the particles, which is noticeable by increasing translucency of the dispersion.
• state-of-the-art homogenization processes can be used, such as devices such as high-speed stirrers (e.g. IKA-Ultra-Turrax ® T25 basic, IKA-Werke GmbH & Co KG, D-79219 Staufen), ultrasonic dispersers (e.g. Use UP200S, UP400S, Dr. Hielscher GmbH, D-14513 Berlin) and / or jet dispersers (Chem. Ing. Tech. (69), 6/97, pp. 793-798; EP 07667997).
• UV-absorbing and / or biocidal coatings and or shaped articles can be produced using the zinc oxide particle dispersions according to the invention.
• Coatings are understood to mean polymer systems for coating materials such as metals, plastics or glass as well as creams, ointments, gels or similar solid or flowable formulations for use in the cosmetic or pharmaceutical field.
• a preferred embodiment of the invention is shaped articles which contain inorganic and / or organic polymers and primarily particulate-dispersed zinc oxide particles.
• a further preferred embodiment of the invention are coatings which contain inorganic and / or organic polymers and primarily particulate-dispersed zinc oxide particles.
• the organic polymers are preferably polyurethanes, polyacrylates, polyamides and / or polyesters, in particular polycarbonates.
• the inorganic polymers are preferably condensation-crosslinked sol / gel materials.
• the ultracentrifuge measurements were carried out on approximately 0.5% by weight ZnO dispersions in a dispersion medium composed of ethylene glycol / water (weight ratio 2: 1).
• the TEM recordings were carried out using ZnO dispersions in ethylene glycol / water (weight ratio 2: 1), which were dropped onto a carbon TEM grid, evaporated and then measured.
• the dispersion according to the invention was characterized by recording and evaluating the UV absorption spectrum of the ZnO particles, preferably in the range between 450 and 300 nm. For this purpose, a sample of the dispersion was diluted to 1/500 in ethylene glycol / water (weight ratio 2: 1) and measured against a mixture of ethylene glycol / water (weight ratio 2: 1). qualitative
• Oligomeric cc / o- ⁇ OSi [(CH 2 ) 2 Si (OC 2 H 5 ) 2 (CH 3 )] ⁇ 4 was used as polyfunctional organosilane in the subsequent experiments. Its preparation was carried out as described in US Pat. No. 6,136,939, Example 2.
• the coupling agent an alkoxysilane-modified polyurethane, was produced as follows:
• dispersions prepared according to Examples 2 and 3 were each treated three times with a
• Nozzle jet disperser homogenized at 1500 bar. In this way, the extinction ratio E 350 / E 4 QQ of the dispersion from Example 2 to 250 and from Example 3 to 175 could be improved.
• Example 8 Preparation of a UV protection formulation with nano-ZnO
• Example 9 Removing the low boilers from the UV protection formulation from Example 8
• Example 10 Production of a further UV protection formulation with nano-ZnO
• the UV protection formulation prepared according to Example 10 was spun
• UV protective formulation prepared according to Example 10 was also applied to glass, the application being carried out by spinning at 4 different maximum speeds (200, 400, 600 and 800 rpm). In this way, 4 glass plates with different layer thicknesses were obtained after curing (60 min at 125 ° C.).
• the coatings produced in this way provide excellent UV protection below approx. 375 nm (high extinction and sharp extinction edge) and have no scatter or absorption in the visible light range.
• Example 12 Production of a UN protective coating with nano-ZnO in organic binder
• Baysilone ® OL17 (10% by weight in xylene) (GE Bayer Silicones, Leverkusen) and Modaflow ® (1% by weight in xylene), (Solutia Germany GmbH, Mainz) as leveling agents and
• the UV protective formulation prepared according to Example 12 was applied by spinning (maximum speed 1500 rpm, 20 seconds holding time) to polycarbonate plates provided with an adhesion promoter as described. After curing, 60 minutes at 130 ° C, an optically perfect and well adhering film would be obtained.
• the UV protective formulation prepared according to Example 12 was also applied to glass, the application being carried out by spinning (maximum speeds 1000 rpm, 20 seconds holding time). After curing (60 min at 130 ° C) an optically perfect and well adhering film was obtained.
• the coating produced in this way provides excellent UV protection below approx. 375 nm (high extinction and sharp extinction edge) and has no scatter or absorption in the visible light range.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Paints Or Removers (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Colloid Chemistry (AREA)

Applications Claiming Priority (3)

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• 2002
  • 2002-09-23 DE DE10244212A patent/DE10244212A1/de not_active Withdrawn
• 2003
  • 2003-09-10 WO PCT/EP2003/010024 patent/WO2004029161A1/de active Application Filing
  • 2003-09-10 JP JP2004538882A patent/JP4585315B2/ja not_active Expired - Fee Related
  • 2003-09-10 CA CA2501378A patent/CA2501378C/en not_active Expired - Lifetime
  • 2003-09-10 AU AU2003264285A patent/AU2003264285A1/en not_active Abandoned
  • 2003-09-10 MX MXPA05003060A patent/MXPA05003060A/es not_active Application Discontinuation
  • 2003-09-10 CN CNA038226731A patent/CN1685018A/zh active Pending
  • 2003-09-10 EP EP03798155A patent/EP1546266A1/de not_active Withdrawn
  • 2003-09-22 US US10/667,575 patent/US20040071958A1/en not_active Abandoned

Non-Patent Citations (1)

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