EP1379592A2 - Anionisch stabilisierte, wässrige dispersionen von nanopartikulärem zinkoxid, verfahren zu deren herstellung sowie deren verwendung - Google Patents
Anionisch stabilisierte, wässrige dispersionen von nanopartikulärem zinkoxid, verfahren zu deren herstellung sowie deren verwendungInfo
- Publication number
- EP1379592A2 EP1379592A2 EP02730091A EP02730091A EP1379592A2 EP 1379592 A2 EP1379592 A2 EP 1379592A2 EP 02730091 A EP02730091 A EP 02730091A EP 02730091 A EP02730091 A EP 02730091A EP 1379592 A2 EP1379592 A2 EP 1379592A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc oxide
- dispersion
- weight
- nanoparticulate
- aqueous
- 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- Withdrawn
Links
Classifications
-
- 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
-
- 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
- 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
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- 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
- C01P2006/80—Compositional purity
-
- 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
- C01P2006/90—Other properties not specified above
-
- 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
Definitions
- the present invention relates to anionically stabilized, aqueous dispersions of nanoparticulate zinc oxide, processes for their preparation and their use.
- nanoparticulate systems open the way to applications that would not be feasible with larger particles, such as UV protection using nanoparticulate inorganic UV absorbers in transparent applications, on the other hand, they enable considerable increases in effectiveness in areas of application that are as large as possible Surfaces and a homogeneous distribution of the active species is important.
- nanoparticulate zinc oxide is not readily dispersible in water.
- aqueous dispersions of zinc oxide cannot be stabilized simply by shifting the pH to values> 9.5, since if the isoelectric point is exceeded, the dispersion is destabilized.
- Another possibility of stabilization is to shift the isoelectric point to lower pH values. In principle, this can be done by using polyelectrolytes. Such a process is described in WO-A 95/24359, in which the sodium salt of a polyacrylic acid is used as a grinding additive in the grinding of zinc oxide.
- aqueous dispersions of zinc oxide nanoparticles produced according to DE 199 01 704 AI, however, no stabilizing, but rather a destabilizing effect was found when polyacrylic acid salts were added.
- stabilization methods which use the known good water dispersibility of silicate surfaces by coating zinc oxide particles with a dense, amorphous SiO 2 layer.
- US Pat. No. 5,914,101 describes aqueous dispersions of particulate zinc oxide and a stabilizer in which the zinc oxide particles are coated with a dense amorphous layer of SiO 2 in a technically complex process.
- a disadvantage of this method is that the coating leads to a great loss of chemical activity, so that the chemical properties of the zinc oxide, such as are required for catalytic purposes, for example, are lost.
- the present invention was therefore based on the object of anionically stabilized
- the object according to the invention was achieved by the zinc oxide dispersions according to the invention described in more detail below.
- the invention therefore relates to anionically stabilized, aqueous dispersions of nanoparticulate zinc oxide with an average primary particle diameter of ⁇ 30, preferably ⁇ 15 nm, and an average agglomerate size of ⁇ 100, preferred
- the surface of the zinc oxide particles having pH values> 7, preferably ⁇ 8 has a negative charge and the content of nanoparticulate zinc oxide in the dispersion is 0.01 to 30% by weight, preferably 0.05 to 20% by weight, in particular 0.05 to 15% by weight.
- a negative charge is understood to mean a negative zeta potential, which is usual
- the negative charge measured at pH values of> 7, expressed as negative zeta potential is ⁇ -30 mV, preferably ⁇ 40 mV.
- Another object of the present invention is a method for producing the anionically stabilized, aqueous zinc oxide dispersions with the aforementioned average primary particle diameters and average agglomerate sizes, which is characterized in that an aqueous zinc oxide dispersion which contains zinc oxide particles with the named primary particle diameters and agglomerate sizes, with alkali silicate solutions treated, the content of nanoparticulate zinc oxide in the dispersion being 0.01 to 30% by weight, preferably 0.05 to 20% by weight, in particular 0.05 to 15% by weight.
- the anionically stabilized zinc oxide dispersions according to the invention are then obtained, with - as mentioned - the surface of the zinc oxide particles being negatively charged at pH values of> 7.
- the process according to the invention is preferably carried out in such a way that a suitable zinc oxide is dispersed in water at pH values below its isoelectric point and by adding alkali silicate solutions (hereinafter referred to as water glass) or mixtures of water glass with bases or mixtures of water glass with bases and stabilizers in this way offset that the zinc oxide is anionically transferred without flocculating.
- the addition is preferably carried out with vigorous stirring, particularly preferably using a rotor stator Systems, such as an Ultraturrax, a jet disperser or a similar device, or under the influence of ultrasound.
- Sodium and potassium water glass should be mentioned in particular as the alkali silicates to be used.
- the use of such zinc oxides with average primary particle sizes ⁇ 30, preferably ⁇ 15 nm is particularly preferred.
- the use of zinc oxide gels or suspensions obtained by basic hydrolysis of zinc compounds in alcohols or alcohol-water mixtures, as in DE 199 07 704 A1, is very particularly preferred described.
- the zinc oxide is placed in water and dispersed by stirring.
- the resulting translucent to milky dispersion depending on the concentration and state of dispersion, contains approximately 0.01 to 30% by weight of ZnO, preferably 0.05 to 20, in particular 0.05 to 15% by weight of ZnO.
- ZnO preferably 0.05 to 20
- the methanol is preferably removed from the aqueous dispersion, e.g. by distillation.
- Suitable additives can be added to improve the dispersion stability, 6-aminohexanoic acid or comparable substances which prevent gelling are preferred.
- the average agglomerate size of the dispersed zinc oxide particles is approximately ⁇ 100, preferably ⁇ 50 nm.
- the particle sizes of the primary particles are determined by
- the temperature of the dispersion process can be between the freezing point of the dispersant and its boiling point, preferably between about 10 and 80 ° C.
- the transhipment can be carried out with aqueous alkali silicate solutions; sodium water glass is preferred.
- the silicate solution can be diluted or used undiluted.
- the concentration of the alkali silicates in the aqueous solution is approximately 0.1 to 10% by weight, preferably 0.5 to 2% by weight, based on commercially available 35% silicate solution.
- the amount of alkali silicate solution is in the
- the charge transfer or treatment of the aqueous ZnO dispersion should be such that the negative charge mentioned occurs on the surface of the ZnO particles.
- base is added to the alkali silicate solution, preferably alkali metal hydroxides.
- alkali silicate solution preferably alkali metal hydroxides.
- aqueous is particularly preferred
- the concentration of the bases in the aqueous solution is usually 1 to 10% by weight, preferably 4 to 6% by weight, based on IN NaOH.
- stabilizer is added to the silicate solution in addition to the base.
- the use of is particularly preferred
- Polyacrylic acid salts such as e.g. Polyacrylic acid Na salt with an average molecular weight of 5100.
- the amount of stabilizer added in the aqueous solution is approximately 0.01 to 1% by weight, preferably 0.05 to 0.2% by weight, based on the Salt.
- the transhipment temperature can be between the freezing point of the dispersant and its boiling point, preferably around 10 to 80 ° C, particularly preferably 20 ° C to 60 ° C.
- the transhipment is preferably carried out in a reactor equipped with an Ultraturrax.
- the conditions with regard to the zinc oxide concentration, the mixing conditions and the shear forces are chosen so that the zinc oxide does not flocculate during the transfer.
- the zinc oxide dispersion obtained in this way can be added by adding acids, such as sulfuric acid, bases, such as sodium hydroxide solution, buffering substances, such as sodium phosphates, or by using ion exchangers, such as Lewatiten®, or by dia- filtration to the desired pH.
- acids such as sulfuric acid
- bases such as sodium hydroxide solution
- buffering substances such as sodium phosphates
- ion exchangers such as Lewatiten®
- the zinc oxide dispersion thus obtained can e.g. be concentrated by distillation, by centrifugation or membrane filtration.
- the aqueous zinc oxide dispersion can first be stabilized by suitable stabilizers and then reacted with alkali silicate solutions.
- the transfer can also take place in such a way that the ZnO dispersion is first flocculated and then redispersed.
- the zinc oxide used is placed in water and dispersed by stirring.
- the resulting translucent to milky dispersion depending on the concentration and state of dispersion, contains about 0.01 to 30% by weight of ZnO, preferably 0.05 to 20, in particular 0.05 to 15% by weight of ZnO.
- the transhipment is carried out in such a way that the aqueous zinc oxide dispersion and the aqueous silicate solution are combined.
- the flocculation temperature can be between the freezing point of the dispersant and its boiling point, preferably around 10 to 100 ° C., particularly preferably 20 ° C. and 70 ° C.
- the supernatant can be separated from the flocculated product immediately, or after prolonged stirring, which can be carried out in the temperature interval specified above, by filtration, sedimentation or centrifugation.
- the separated flocculation can be redispersed by adding water, but also by water stabilizer mixtures, of which preferably water-polyelectrolyte mixtures, particularly preferably water-polyacrylic acid-sodium salt mixtures. This can be done by stirring, if appropriate at elevated temperature, preferably under high shear forces, particularly preferably by using a rotor-stator
- the redispersed portion is separated from the undispersed residue by filtration, sedimentation, centrifugation or an appropriate separation process.
- Redispersion and separation processes can be repeated several times to obtain a better yield of dispersed material.
- the zinc oxide dispersion obtained in this way can in turn be adjusted to the desired pH by adding acids or bases or by using ion exchangers.
- the zinc oxide dispersion thus obtained can e.g. be concentrated by distillation, by centrifugation or by membrane filtration.
- an aqueous zinc oxide dispersion is first destabilized by changing the pH, preferably by adding aqueous alkali metal hydroxides, separated from the supernatant after settling and subsequently with water or with water-stabilizer mixtures, of which mixtures of water and Sodium salts of polyacrylic acids are preferred, resumed.
- the dispersions obtained in this way can be converted into stable dispersions by adding aqueous alkali silicate solutions without this leading to flocculation as described above.
- Another object of the present invention is the use of the anionically stabilized dispersions of nanoparticulate zinc oxide according to the invention as a vulcanization co-activator in the vulcanization of latex molded articles.
- the anionically stabilized dispersions of nanoparticulate zinc oxide according to the invention can - as mentioned - be used as vulcanization co-activators in the production of latices based on all kinds of natural and synthetic rubbers.
- Styrene-butadiene copolymers ate carboxylated
- Styrene-butadiene copolymers ate carboxylated and with self-crosslinking groups, acrylonitrile-butadiene-styrene copolymersates,
- the zinc oxide dispersion according to the invention is added in amounts of approximately 2.0 to 0.01, preferably 0.5 to 0.05, based on 100 parts by weight of a latex mixture (dry / dry) during the vulcanization ,
- the optical determination of the colloidal ZnO content was carried out with a Shimadzu UVVIS spectrometer using 1 cm quartz cuvettes.
- centrifugation steps were carried out in a laboratory centrifuge from Heraeus (Cryofuge 6000i) with a 22.9 cm rotor (radius for
- Component A is a compound having Component A:
- component A 1670 g of component A and the entire component B were placed in separate storage vessels and via hose lines at 50 ml / min (A) and 25 nm / min (B) into a mixing chamber in which 300 ml of water were placed and which were with an Ultraturrax (IKA, T25 Basic, dispersing tool type S25N-18G) at
- the ultracentrifuge measurement of the dispersion thus obtained showed a mean agglomera- meratleton of 33 nm (d 5 o-value of the mass distribution).
- the dispersion obtained had a pH of 9, a ZnO content of 10.14% and a Q value of 32.
- An elemental analysis showed a Zn content of 8.5%, corresponding to 10.6% zinc oxide.
- the ultracentrifuge measurement showed an average agglomerate size of 28 nm (d 5 Q value of the mass distribution).
- Potassium hydroxide solution and with 1.25 parts by weight of a stabilizer, preferably a 20% potassium laurate solution, mixed and stabilized at room temperature with stirring. Then 7.8 parts by weight of the ground vulcanization paste are added at a concentration of 50%.
- a stabilizer preferably a 20% potassium laurate solution
- This vulcanization paste consists of 1.5 parts by weight of colloidal sulfur, 0.6 parts by weight of a zinc dithiocarbamate accelerator (ZDEC), 0.3 part by weight of a zinc mercapto-benzothiazole accelerator (ZMBT), and 1.0 part by weight of a phenol-based anti-aging agent and a 5% aqueous solution of a dispersant consisting of a Na salt of a condensation product of naphthalene sulfonic acid and formaldehyde. This mixture is then added to a concentration of by adding water
- This matured compound is filtered through a 100 ⁇ filter. Then the diving process takes place. This is carried out on specially prepared glass plates. These glass plates are previously immersed in an aqueous coagulant solution consisting of 15% calcium nitrate solution with an addition of 10% of a fine chalk and dried. The glass plates prepared in this way are immersed in the mixture described above for about 20 seconds in order to obtain a film deposition of about 0.20 mm.
- the films produced in this way are subjected to a non-aged strength test after a conditioning phase of 24 h in a standard atmosphere
- Modulis the strength and elongation at break are determined.
- the modulus at 300% elongation is significantly lower than in the comparison samples with zinc oxide white seal (WS) not used according to the invention or a zinc oxide with an increased surface area. This effect leads to a higher one
- the elongation at break (864% / 5 min) also shows higher values than the comparison test with 1.0 part by weight of zinc oxide white seal (790% / 5 min) or a zinc oxide with a high surface area with 0.5 part by weight (843% / 5 min).
- the assessment after aging shows significant improvements in stability after 8.16 and 24 hours storage in hot air at 100 ° C.
- the degradation of the rubber proceeds more slowly than with zinc oxides not according to the invention.
- the reduction in strength here is only 22.6%. Compared to conventional zinc oxide, the reduction in strength is 37.2%.
- 167 g of a natural latex of type HA is mixed with 5.0 parts by weight of a 10% potassium hydroxide solution and with 1.25 parts by weight of a stabilizer, preferably one
- This vulcanization paste consists of 1.5 parts by weight of colloidal sulfur, 0.6 parts by weight of a zinc dithiocarbamate accelerator (ZDEC), 0.3 part by weight of a zinc mercapto-benzothiazole accelerator (ZMBT), and 1.0 part by weight of a phenol-based anti-aging agent and a 5% aqueous solution of a dispersant consisting of a Na salt of a condensation product of naphthalene sulfonic acid and formaldehyde.
- ZDEC zinc dithiocarbamate accelerator
- ZMBT zinc mercapto-benzothiazole accelerator
- the films produced in this way are subjected to a non-aged strength test after a conditioning phase of 24 h in a standard atmosphere
- Modulis the strength and elongation at break are determined.
- the modulus at 300% and 700% elongation is significantly lower than in the comparison samples with zinc oxide white seal (WS) not used according to the invention or a zinc oxide with an increased surface area. This effect leads to greater comfort.
- WS zinc oxide white seal
- the elongation at break (925% / 5 min) also shows higher values than the comparison test with 1.0 part by weight of zinc oxide white seal (790% / 5 min) or a zinc oxide with a high surface area with 0.5 part by weight ( 843% / 5 min).
- the assessment after aging shows significant improvements in stability after 8.16 and 24 hours storage in hot air at 100 ° C.
- the degradation of the rubber proceeds more slowly than with zinc oxides not according to the invention.
- the reduction in strength here is only 19.6%. Compared to conventional zinc oxide, the reduction in strength is 37.2%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10118309 | 2001-04-12 | ||
DE10118309A DE10118309C2 (de) | 2001-04-12 | 2001-04-12 | Anionisch stabilisierte, wässrige Dispersionen von nanopartikulärem Zinkoxid, Verfahren zu deren Herstellung sowie deren Verwendung |
PCT/EP2002/003662 WO2002083797A2 (de) | 2001-04-12 | 2002-04-03 | Anionisch stabilisierte, wässrige dispersionen von nanopartikulärem zinkoxid, verfahren zu deren herstellung sowie deren verwendung |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1379592A2 true EP1379592A2 (de) | 2004-01-14 |
Family
ID=7681382
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02730091A Withdrawn EP1379592A2 (de) | 2001-04-12 | 2002-04-03 | Anionisch stabilisierte, wässrige dispersionen von nanopartikulärem zinkoxid, verfahren zu deren herstellung sowie deren verwendung |
Country Status (9)
Country | Link |
---|---|
US (1) | US20020149002A1 (de) |
EP (1) | EP1379592A2 (de) |
JP (1) | JP2004523645A (de) |
CN (1) | CN1516726A (de) |
AU (1) | AU2002302488A1 (de) |
CA (1) | CA2443573A1 (de) |
DE (1) | DE10118309C2 (de) |
MY (1) | MY134121A (de) |
WO (1) | WO2002083797A2 (de) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7683098B2 (en) * | 1996-09-03 | 2010-03-23 | Ppg Industries Ohio, Inc. | Manufacturing methods for nanomaterial dispersions and products thereof |
DE10324305A1 (de) * | 2003-05-30 | 2004-12-16 | Bayer Ag | Verfahren zur Herstellung sphärischer Zinkoxidpartikel |
US20040247989A1 (en) * | 2003-06-06 | 2004-12-09 | Colleen Legzdins | Method for making an electrode by depositing nano-particles |
TR200600501T2 (tr) * | 2003-06-24 | 2006-08-21 | Ppg Industries Ohio, Inc. | Nano parçacıklı bir fazı olan mikro parçacıklarınsulu dispersiyonları ve bunları içeren kaplama bileşimleri. |
US7605194B2 (en) * | 2003-06-24 | 2009-10-20 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
US7612124B2 (en) | 2003-06-24 | 2009-11-03 | Ppg Industries Ohio, Inc. | Ink compositions and related methods |
US7745514B2 (en) * | 2003-06-24 | 2010-06-29 | Ppg Industries Ohio, Inc. | Tinted, abrasion resistant coating compositions and coated articles |
US7671109B2 (en) | 2003-06-24 | 2010-03-02 | Ppg Industries Ohio, Inc. | Tinted, abrasion resistant coating compositions and coated articles |
US7635727B2 (en) | 2003-06-24 | 2009-12-22 | Ppg Industries Ohio, Inc. | Composite transparencies |
US7910634B2 (en) | 2004-03-25 | 2011-03-22 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
US20100184911A1 (en) * | 2009-01-22 | 2010-07-22 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
GB0418561D0 (en) | 2004-08-19 | 2004-09-22 | Ssl Int Plc | Rubber latex films having improved tear resistance |
US8455404B2 (en) * | 2005-07-15 | 2013-06-04 | Halliburton Energy Services, Inc. | Treatment fluids with improved shale inhibition and methods of use in subterranean operations |
US20100129524A1 (en) * | 2006-01-20 | 2010-05-27 | Steven Sternberger | Methods of dispensing powder coating compositions and articles coated therewith |
US8178160B2 (en) * | 2006-01-20 | 2012-05-15 | Ppg Industries Ohio, Inc. | Decorative and durable coating having a homogeneous hue, methods for their preparation, and articles coated therewith |
US20080255273A1 (en) * | 2006-11-20 | 2008-10-16 | Air Products And Chemicals, Inc. | Particulate Filled Polymers |
US8507050B2 (en) * | 2008-11-12 | 2013-08-13 | Ppg Industries Ohio, Inc. | Methods for depositing ultra thin coatings exhibiting low haze and methods for the preparation of such coatings |
WO2010089295A1 (de) | 2009-02-03 | 2010-08-12 | Bühler PARTEC GmbH | Mit phosphonocarbonsäure modifizierte zinkoxid-partikel und verwendung von zinkoxid-partikeln |
EP2241602A1 (de) | 2009-04-17 | 2010-10-20 | Bühler PARTEC GmbH | Mit Phosphonocarbonsäure modifizierte Zinkoxid-Partikel und Verwendung von Zinkoxid-Partikeln |
DE102009009182A1 (de) | 2009-02-16 | 2010-08-19 | Süd-Chemie AG | Zinkoxid-Kristallpartikel und Verfahren zu der Herstellung |
US7976624B2 (en) * | 2009-12-04 | 2011-07-12 | Ashland Licensing And Intellectual Property, Llc | Nano gel wax |
CN102295307B (zh) * | 2011-07-29 | 2013-06-26 | 西安工程大学 | 一种制备纳米氧化锌的方法 |
KR101657346B1 (ko) * | 2014-06-12 | 2016-09-13 | 주식회사 엘지화학 | 딥 성형용 라텍스 조성물 및 그 제조방법 |
CN109749168B (zh) * | 2017-11-03 | 2020-02-14 | 北京化工大学 | 一种纳米氧化锌/橡胶复合材料及制备方法 |
CN108285620B (zh) * | 2018-03-15 | 2020-06-16 | 科迈特新材料有限公司 | 一种共混橡胶用硫化活性剂及其制备方法 |
CN112024336A (zh) * | 2020-07-29 | 2020-12-04 | 安徽喜宝高分子材料有限公司 | 一种通过构建纳米防护层以提升金属防水效果的粉末涂料的制备喷涂工艺 |
US20230250300A1 (en) * | 2022-02-05 | 2023-08-10 | Resysten International Ltd. | Durable antimicrobial coating and preparation thereof |
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CA2162914A1 (en) | 1994-03-11 | 1995-09-14 | Edward A. Myszak, Jr. | Colloidal zinc oxide |
GB9616978D0 (en) * | 1996-08-13 | 1996-09-25 | Tioxide Specialties Ltd | Zinc oxide dispersions |
JP2000191489A (ja) * | 1998-12-28 | 2000-07-11 | Hakusui Tech Co Ltd | 超微粒子状酸化亜鉛・シリコ―ン分散体及びその製法、並びに紫外線遮蔽性化粧料 |
DE19907704A1 (de) | 1999-02-23 | 2000-08-24 | Bayer Ag | Nanopartikuläres, redispergierbares Fällungszinkoxid |
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2001
- 2001-04-12 DE DE10118309A patent/DE10118309C2/de not_active Expired - Fee Related
-
2002
- 2002-04-03 CN CNA028081773A patent/CN1516726A/zh active Pending
- 2002-04-03 JP JP2002582139A patent/JP2004523645A/ja active Pending
- 2002-04-03 CA CA002443573A patent/CA2443573A1/en not_active Abandoned
- 2002-04-03 AU AU2002302488A patent/AU2002302488A1/en not_active Abandoned
- 2002-04-03 WO PCT/EP2002/003662 patent/WO2002083797A2/de not_active Application Discontinuation
- 2002-04-03 EP EP02730091A patent/EP1379592A2/de not_active Withdrawn
- 2002-04-04 US US10/116,220 patent/US20020149002A1/en not_active Abandoned
- 2002-04-10 MY MYPI20021307A patent/MY134121A/en unknown
Non-Patent Citations (1)
Title |
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See references of WO02083797A2 * |
Also Published As
Publication number | Publication date |
---|---|
CA2443573A1 (en) | 2002-10-24 |
DE10118309C2 (de) | 2003-03-20 |
AU2002302488A1 (en) | 2002-10-28 |
DE10118309A1 (de) | 2002-10-24 |
JP2004523645A (ja) | 2004-08-05 |
US20020149002A1 (en) | 2002-10-17 |
CN1516726A (zh) | 2004-07-28 |
WO2002083797A3 (de) | 2003-03-13 |
MY134121A (en) | 2007-11-30 |
WO2002083797A2 (de) | 2002-10-24 |
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