WO2008024702A2 - Dispersions de nanoparticules d'oxyde de zinc - Google Patents

Dispersions de nanoparticules d'oxyde de zinc Download PDF

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Publication number
WO2008024702A2
WO2008024702A2 PCT/US2007/076291 US2007076291W WO2008024702A2 WO 2008024702 A2 WO2008024702 A2 WO 2008024702A2 US 2007076291 W US2007076291 W US 2007076291W WO 2008024702 A2 WO2008024702 A2 WO 2008024702A2
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WO
WIPO (PCT)
Prior art keywords
dispersion
dispersions
zno
zinc oxide
coating composition
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.)
Ceased
Application number
PCT/US2007/076291
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English (en)
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WO2008024702A3 (fr
Inventor
Detlef Burgard
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.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals Inc
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
Priority claimed from US11/524,471 external-priority patent/US20070078190A1/en
Priority claimed from US11/583,439 external-priority patent/US20100096601A1/en
Priority claimed from US11/832,393 external-priority patent/US8512467B2/en
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Publication of WO2008024702A2 publication Critical patent/WO2008024702A2/fr
Publication of WO2008024702A3 publication Critical patent/WO2008024702A3/fr
Anticipated expiration legal-status Critical
Ceased 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • 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
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • 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
    • C01P2006/65—Chroma (C*)

Definitions

  • the instant invention relates to zinc oxide (ZnO) nanoparticle dispersions and to such dispersions having a defined color, and films obtained from such dispersions.
  • the inventive zinc oxide dispersions can be used as a UV-absorber, for catalytic applications, electronic applications, production of antifungal or antibacterial materials, sensors, actuators, photovoltaic devices, conductive coatings, among other applications
  • UV protecting agents are preferrably transparent and, in some cases, colorless in the final application. For some applications or end-uses these agents are permanent, non migratory and stable against degradation.
  • Organic UV protecting agents or absorbers can be migratory and have unacceptable long term stability (e.g., less than 10 years). In some cases organic UV absorbers are not stable against oxidation or at relatively high temperatures. Inorganic UV absorbers (e.g.
  • inorganic absorbers may not be transparent and/or colorless, or they may be photocatalytically active and in some cases adversely affect a surrounding polymeric matrix when exposed to UV.
  • dispersions which can be used as an inorganic transparent UV blocking additive for preparing transparent materials or coatings with low haze levels.
  • a white dispersion will be produced when mixing a white powder, e.g. ZnO with a colorless liquid (e.g. water, ethanol, toluene, among others).
  • a colorless liquid e.g. water, ethanol, toluene, among others.
  • ZnO nanoparticie dispersions in colorless solvents have a yellow color tone.
  • Such yellow zinc oxide nanoparticie dispersions can show improved properties in comparison to white ZnO dispersions.
  • Commercial, white nanoparticie ZnO dispersions and the inventive yellow dispersions were used as a UV absorbing additive in an acrylic coating. The haze values of the acrylic coatings were measured and the haze values were significantly lower for the coatings made from the inventive yellow dispersions.
  • Figure 1 is a plot of color as represented by the CIE L * a*b * parameters.
  • This invention solves problems associated with conventional UV absorbers by providing zinc oxide dispersions which can be used as an inorganic transparent UV blocking additive to transparent coatings or materials.
  • the zinc oxide particles will normally range in size from about 5 to about 200 nanometers with a mean particle size of about 50nm.
  • the dispersion will normally comprise or consist essentially of about 10 "3 to about 95 wt. % of zinc oxide nanoparticles and about 0.1 to about 50wt.% of at least one dispersing agent.
  • suitable dispersing agents comprise at least one member selected from the group consisting of diammoniumcitrate, catechols (e.g.
  • pigment affinic groups e.g., Byk 190, methoxy-ethoxy-ethoxy-acetic acid, oligo- or polyacrylic acids and their compounds, mixtures thereof, among others.
  • the dispersion can also comprise at least one carrier or diluent.
  • the carrier can be aqueous (e.g., deionized water), or based upon one or more suitable organic compounds.
  • suitable organic compounds can comprise at least one member selected from the group consisting of isoproproxyethanol, ethanol, toluene, alcohol, butanol, isoacyl alcohol, cetone, acetone, MEK, dicetone, diole, carbitole, glycole, diglycole, triglycole, glycol ether, ethoxy-, propoxy-, isopropoxy-, butoxyethanol- acetate, ester, glycolester, ethyl acetate, butyl acetate, butoxyethyl acetate, alcane, toluene, xylene, acrylic acid, methacrylic acid, acrylate or methacrylate monomers as well as their derivatives, among other suitable substrates.
  • the amount of carrier can range from about
  • the dispersions can be prepared by any suitable methods such as stirring, shaking, all kind of milling, e.g. media milling, three roll milling, high speed dispersing, rotor stator techniques, sonication, jet milling, to name a few applicable techniques
  • the inventive dispersions can be employed for preparing transparent materials or coatings with low haze levels and other desirable properties.
  • the inventive dispersions can be used for making a coating or film having a haze of about lower or equal to 0.5 to about 3.0 when measured in accordance with ASTM D1003.
  • the coating is also normally transparent as determined by ASTM D1003.
  • the thickness of the coating will typically be about 100 nm to about 50 microns.
  • inventive dispersion can be added to a wide range of polymeric formulations and systems.
  • examples of such systems including acrylic, polyurethane, epoxy, polyesters, polyethers, polyolefines, siloxanes, organic inorganic (nano)composites, among others.
  • the amount of dispersion that is added to the polymeric formulation will normally range from about 10 "3 wt.% to about 80 wt.% of the formulation.
  • inventive dispersions can be added to the foregoing formulations and systems by any suitable method.
  • suitable methods comprise shaking, stirring, the previously described milling/dispersing processes, dynamic, static mixers or other blending techniques.
  • inventive dispersion can be applied onto any suitable substrate.
  • suitable substrates comprise at least one member selected from the group consisting of glass, polymeric substrates, e.g. PC, PMMA, PET, PVC, PE, PP, PVB, PA, polyesters, polyamides, epoxy, polyurethanes, siloxanes, cotton, linen, wool, textiles, nonwovens, among other suitable substrates.
  • the inventive dispersion after incorporated into a suitable coating composition and the coating applied onto a suitable substrates.
  • suitable substrates comprise at least one member selected from the group consisting of e.g. PC, PMMA, PET, PVC, PE, PP, PVB, PA, polyesters, polyamides, epoxy, polyurethanes, siloxanes, cotton, linen, wool, textiles, nonwovens,
  • either the dispersion or a coating composition comprising the dispersion can be applied onto a suitable substrate and heated treated (e.g., to a temperature greater than 100C).
  • the heat treatment can be sufficient to remove substantially all components other than ZnO nanoparticles.
  • the remaining ZnO coated substrate can be employed in a wide range of applications including, without limitation, such as UV-absorber, catalyst, electronic device, antifungal or antibacterial material, sensor, actuator, photovoltaic device, conductive material, bearing, among other applications.
  • the dispersion can include at least one additive such as wetting agents, surfactants, defoamers, and other additives used to formulate inks, coatings and adhesives.
  • additives such as wetting agents, surfactants, defoamers, and other additives used to formulate inks, coatings and adhesives.
  • Example 1 [0016] 3 g of Diammoniumcitrate were dissolved in 237 g deionized water. While stirring, 60 g of nanoparticle ZnO, primary particle size 30 nm, were slowly added. The mixture was pumped through a flow cell (a "flow cell” is a continuously working reactor wherein the dispersion was ultrasonically agitated), and ultrasonically agitated for 2.5 h. After that, the dispersion was milled with a Netzsch MiniCer at 2500 - 3000 rpm. for 160 min.
  • a flow cell is a continuously working reactor wherein the dispersion was ultrasonically agitated
  • Example 3 [0018] 70 g of nanoparticle ZnO (as described in Example 1 ), 4.2 g
  • Methoxy-ethoxy-ethoxy-acetic acid and 23 g Isopropoxyethanol were mixed in a beaker.
  • the mixture was further homogenized using a three roller mill (i.e., Exakt 80E).
  • the resulting paste was diluted with ethanol while stirring until a solid content of about 30 wt. % ZnO was achieved.
  • the dispersion was pumped through a flow cell and ultrasonically agitated for 2.5 h. After that, the dispersion was milled with a Netzsch MiniCer at 2500 - 3000 rpm for 160 min.
  • a commercial aqueous dispersion of nanoparticle ZnO (solid content 45 wt.%) was mixed with an aqueous acrylic emulsion (solid content 50 wt.%, particle size about 400 nm).
  • the acrylic solid to ZnO solid ratio was adjusted to 0.7 : 0.3.
  • the resulting mixture was coated on glass with a wet coating thickness of 24 g/m 2 . The coating was dried for 5 min at 120 0 C.
  • the resulting haze value (measured with Haze Gard Plus, Byk Gardner and in accordance with ASTM D 1003), was 34.
  • Example 6 [0021] Example 5 was repeated except that instead of the commercial dispersion of Example 5, the dispersion of Example 2 was used. The resulting haze value of the coating was 2.9.
  • Example 7 [0022] 40 g Pentaerythritol tetraacrylate, 10 g Hexanedioldiacrylate and 2 g lrgacure 184 were dissolved in 50 g ethanol. To this solution, 1.5 g of ZnO dispersion of Example 3 were added. The solution was coated onto a glass sheet with a wet coating thickness of 50 ⁇ m. The coating was cured by UV radiation (1760 mJ/cm 2 ). The transparency in the visible of the resulting coating was 90.2 % and the haze value was 0.5.
  • Figure 1 illustrates the relationship among color parameters wherein L * corresponds to the brightness, a * the red/green parameter, b * the yellow/blue parameter, C * the Saturation and h * the color angle or hue of the testing Sample.
  • a positive a * parameter indicates a red color whereas a negative a* corresponds to green.
  • a positive b* parameter indicates a yellow color whereas a negative b * corresponds to blue.
  • Table 1 illustrates that the inventive ZnO dispersions all have a b * value greater than 10.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des dispersions de nanoparticules d'oxyde de zinc (ZnO) et de telles dispersions présentant une couleur définie, et des films obtenus à partir de ces dispersions. Les dispersions d'oxyde de zinc peuvent être utilisées comme absorbants UV, pour des applications catalytiques, des applications électroniques, la fabrication de matériaux antifongiques ou antibactériens, des capteurs, des actionneurs, des dispositifs photovoltaïques, des revêtements conducteurs, entre autres applications.
PCT/US2007/076291 2006-08-21 2007-08-20 Dispersions de nanoparticules d'oxyde de zinc Ceased WO2008024702A2 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US83908606P 2006-08-21 2006-08-21
US60/839,086 2006-08-21
US11/524,471 US20070078190A1 (en) 2005-09-30 2006-09-21 Use of 2,3-dihydroxynaphthalene-6-sulfonic acid salts as dispersants
US11/524,471 2006-09-21
US11/583,439 US20100096601A1 (en) 2005-10-27 2006-10-19 Molecules with complexing groups for aqueous nanoparticle dispersions and uses thereof
US11/583,439 2006-10-19
US11/832,393 US8512467B2 (en) 2006-08-21 2007-08-01 Zinc oxide nanoparticle dispersions
US11/832,393 2007-08-01

Publications (2)

Publication Number Publication Date
WO2008024702A2 true WO2008024702A2 (fr) 2008-02-28
WO2008024702A3 WO2008024702A3 (fr) 2008-05-29

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012062219A (ja) * 2010-09-16 2012-03-29 Mitsui Mining & Smelting Co Ltd アルミニウムドープ酸化亜鉛粒子及びその製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3674451D1 (de) * 1985-04-29 1990-10-31 Bbc Brown Boveri & Cie Verfahren zur herstellung eines spannungsabhaengigen keramischen widerstandes auf der basis von zno.
US5320874A (en) * 1992-06-18 1994-06-14 The Goodyear Tire & Rubber Company Rubber surface identification coating and rubber products prepared therefrom
EP1481020A2 (fr) * 2002-02-04 2004-12-01 Nanophase Technologies Corporation Dispersions stables de nanoparticules dans un milieu aqueux
US20100096601A1 (en) * 2005-10-27 2010-04-22 Distefano Frank Vito Molecules with complexing groups for aqueous nanoparticle dispersions and uses thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012062219A (ja) * 2010-09-16 2012-03-29 Mitsui Mining & Smelting Co Ltd アルミニウムドープ酸化亜鉛粒子及びその製造方法

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Publication number Publication date
WO2008024702A3 (fr) 2008-05-29

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