EP1546266A1 - Zinc-oxide dispersions in anhydrous dispersion media that are devoid of halogen - Google Patents

Zinc-oxide dispersions in anhydrous dispersion media that are devoid of halogen

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Publication number
EP1546266A1
EP1546266A1 EP03798155A EP03798155A EP1546266A1 EP 1546266 A1 EP1546266 A1 EP 1546266A1 EP 03798155 A EP03798155 A EP 03798155A EP 03798155 A EP03798155 A EP 03798155A EP 1546266 A1 EP1546266 A1 EP 1546266A1
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EP
European Patent Office
Prior art keywords
zinc oxide
weight
halogen
dispersions
free
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.)
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EP03798155A
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German (de)
French (fr)
Inventor
Thiemo Marx
Michael Mager
Volker Wege
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Lanxess Deutschland GmbH
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Bayer MaterialScience AG
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Publication of EP1546266A1 publication Critical patent/EP1546266A1/en
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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
    • 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.

Abstract

The invention relates to anhydrous dispersions that are devoid of halogen, containing as the primary particulate redispersed zinc-oxide particles with an average diameter of between 1 and 200 nm and amino alcohols. The invention also relates to a method for producing said dispersions and to the use thereof for producing moulded parts and coatings.

Description

Zinkoxiddispersionen in halogen- und wasserfreien DispersionsmedienZinc oxide dispersions in halogen and water-free dispersion media
Die Erfindung betrifft wasser- und halogenfreie Dispersionen enthaltend primär- partikulär redispergierte Zinkoxidteilchen mit einem mittleren Durchmesser zwischen 1 und 200 nm und Aminoalkohole, ein Verfahren zur Herstellung der Dispersionen und die Verwendung dieser Dispersionen zur Herstellung von Formteilen und Überzügen.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.
Zinkoxid Nanopartikeldispersionen, in denen die Teilchen primärpartikulär dispers vorliegen, sind aus WO 00/50503 bekannt. Zur Herstellung wird Zinkacetatdihydrat (käuflich oder in situ aus grobteiligem Zinkoxid, Wasser und Eisessig hergestellt) in Methanol gelöst und durch Basenzugäbe in geeigneter Stöchiometrie die Fällung der Partikel vorgenommen. Die Aufreinigung und Aufkonzentration der zunächst als Aufschlämmung anfallenden, reversibel agglomerierten Partikel erfolgt durch Absitzen, Abnehmen des Überstandes, wieder Auffüllen mit frischem Methanol unter Rühren und erneutem Absitzen. Die Formulierung der Sole (Dispersionen, kolloidale Lösungen) erfolgt im Anschluss durch geeignete Verdichtung der Partikel zum Gel und Redispergieren in Wasser und/oder organischen Lösemitteln, gegebenenfalls unter Zusatz oberflächenmodifizierender Substanzen.Zinc oxide nanoparticle dispersions in which the particles are primarily disperse are known from WO 00/50503. For the preparation, zinc acetate dihydrate (commercially available or made in situ from coarse-particle zinc oxide, water and glacial acetic acid) is dissolved in methanol and the particles are precipitated by adding suitable stoichiometry to the base. 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.
Aus primärpartikulär dispergiertem Zihkoxid (nano-ZnO-Dispersion) können transparente, hochwirksame UV-Schutzbeschichtungen auf Basis kondensationsver- netzender Sol/Gel-Matierialien hergestellt werden (EP 1 146 069 A2). Hierfür wird die in WO 00/50503 beschriebene, wasserfreie nano-Zinkoxid-Dispersion in Dichlormethan oder Chloroform eingesetzt. Die Verwendung halogenierter Lösemittel ist allerdings für eine kommerzielle Vermarktung dieser Beschichtungen wie auch der enthaltenen Sole prohibitiv.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). The water-free nano-zinc oxide dispersion in dichloromethane or chloroform described in WO 00/50503 is used for this. However, the use of halogenated solvents is prohibitive for the commercial marketing of these coatings and the brine they contain.
Es wurde nun gefunden, dass sich Zinkoxid besonders gut in Aminoalkoholen oder Mischungen aus Aminoalkoholen mit halogen- und wasserfreien organischen Löse- mitteln primärpartikulär redispergieren und zu hochkonzentrierten, stabilen Dispersionen formulieren lässt, aus denen sich Formkörper und Überzüge enthaltend primärpartikulär dispergiertes Zihkoxid herstellen lassen.It has now been found that 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.
Gegenstand der Erfindung sind wasser- und halogenfreie Dispersionen, die Aminoalkohole und primärpartikulär redispergiertes Zinkoxid (nano-ZnO) mit einem mittleren Teilchendurchmesser (bestimmt mittels Ultrazentrifugation) von 1 bis 200 nm enthalten. Die erfindungsgemäßen Dispersionen bestehen aus den primärpartikulär redispergierten Zinkoxidpartikeln sowie dem wasser- und halogenfreien Disper- sionsmedium.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.
Die erfindungsgemäßen Mischungen enthalten neben den Aminoalkoholen bevorzugt nano-Zinkoxid mit einem mittleren Teilchendurchmesser, bestimmt mittels Ultrazentrifugation, zwischen 5 und 50 nm, besonders bevorzugt zwischen 5 und 20 nm.In addition to the amino alcohols, 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.
Angaben zur Bestimmung der Teilchengröße durch Ultrazentrifugenmessungen finden sich z.B. in H.G. Müller, Colloid. Polym. Sei., 267, 1113-1116 (1989).Information on the determination of the particle size by ultracentrifuge measurements can be found e.g. in H.G. Müller, Colloid. Polym. Sci., 267, 1113-1116 (1989).
Im Sinne der Erfindung bedeutet primärpartikulär redispergierbares bzw. redisper- giertes Zinkoxid, dass der Anteil des eingesetzten Zinkoxids, das nicht wieder in seine Primärpartikel aufgebrochen werden kann bzw. in der betreffenden Dispersion nicht aufgebrochen vorliegt, weniger als 15 Gew.-%, insbesondere weniger als 1 Gew.-% der Gesamtmenge des eingesetzten Zinkoxids ausmacht.For the purposes of the invention, 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.
Das wasser- und halogenfreie Dispersionsmedium besteht bevorzugt im wesentlichen aus reinen Aminoalkoholen oder deren Mischungen mit wasser- und halogenfreien Lösemitteln. Der Anteil der wasser- und halogenfreien Lösemittel an der Gesamtmenge des Dispersionsmediums liegt zwischen 0 und 96 Gew.-%.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.
Als Aminoalkohole werden bevorzugt Aminoalkohole der Formel (I) eingesetzt. R1R2N-(CH2)x-OH (I),Amino alcohols of the formula (I) are preferably used as amino alcohols. R 1 R 2 N- (CH 2 ) x -OH (I),
wobeiin which
R1 und R2 unabhängig voneinander für einen Cι-C3o-Alkylrest stehen oder Bestandteil eines aliphatischen oder aromatischen C5-C20-Restes sind oder dem Rest - (CH2)x-OH entsprechen, undR 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 eine ganze Zahl von 1 bis 30 ist.x is an integer from 1 to 30.
Besonders bevorzugt ist R1 und R2 in Formel (I) der Rest (CH2)x-OH, wobei x gleich 2, 3 oder 4 ist.R 1 and R 2 in formula (I) are particularly preferably the radical (CH 2 ) x -OH, where x is 2, 3 or 4.
Ganz besonders bevorzugt ist Triethanolamin.Triethanolamine is very particularly preferred.
Im einzelnen seien folgende Aminoalkohole genannt:The following amino alcohols may be mentioned:
(HO-CH2-CH2)2N-CH2-CH2-N(CH2-CH2-OH)2- N(CH2-CH2-OH)3, HO-CH2-CH2- CH2-N(CH2-CH2-OH)2, HO-CH(CH3)-CH2-CH2-N(CH2-CH2-OH)2, H-N(CH2-CH2- OH)2, CH3-N(CH2-CH2-OH)2, CH3-CH2-N(CH2-CH2-OH)2, CH3-CH2-CH2-N(CH2- CH2-OH)2, (CH3)2.CH-N(CH2-CH2-OH)2, (CH3)3C-N(CH2-CH2-OH)2, C6H5-CH2-(HO-CH 2 -CH 2 ) 2 N-CH 2 -CH 2 -N (CH 2 -CH 2 -OH) 2 - N (CH 2 -CH 2 -OH) 3 , HO-CH 2 -CH 2 - CH 2 -N (CH 2 -CH 2 -OH) 2 , HO-CH (CH 3 ) -CH 2 -CH 2 -N (CH 2 -CH 2 -OH) 2 , HN (CH 2 -CH 2 - OH ) 2 , CH 3 -N (CH 2 -CH 2 -OH) 2 , CH 3 -CH 2 -N (CH 2 -CH 2 -OH) 2 , CH 3 -CH 2 -CH 2 -N (CH 2 - CH 2 -OH) 2 , (CH 3 ) 2.CH-N (CH 2 -CH2-OH) 2 , (CH 3 ) 3 CN (CH 2 -CH 2 -OH) 2 , C 6 H 5 -CH 2 -
N(CH2-CH2-OH)2, C6H5-N(CH2-CH2-OH)25 CH3-(CH2)5-N(CH2-CH2-OH)2, CH3- (CH2)17-N(CH2-CH2-OH)2, H2N-CH2-CH2-CH2-N(CH2-CH2-OH)2, H2N-CH2-CH2- OH, (CH3)2N-CH2-CH2-OH, CH3-NH-CH2-CH2-OH, (CH3-CH2)2N-CH2-CH2-OH, (CH3)2N-(CH2)2-OH, (CH3)2N-(CH2)3-OH, (CH3)2N-(CH2)4-OH, CH3-(CH2)3- N(CH3)-CH2-CH2-OH, C6H5-CH2-N(CH3)-CH2-CH2-OH, (CH3)2N-CH2-CH2-N (CH 2 -CH 2 -OH) 2 , C 6 H 5 -N (CH 2 -CH 2 -OH) 25 CH 3 - (CH 2 ) 5 -N (CH 2 -CH 2 -OH) 2 , CH 3 - (CH 2 ) 17 -N (CH 2 -CH 2 -OH) 2 , H 2 N-CH 2 -CH 2 -CH 2 -N (CH 2 -CH 2 -OH) 2 , H 2 N-CH 2 -CH 2 - OH, (CH 3 ) 2 N-CH 2 -CH 2 -OH, CH 3 -NH-CH 2 -CH 2 -OH, (CH 3 -CH 2 ) 2 N-CH 2 -CH 2 -OH, (CH 3 ) 2 N- (CH 2 ) 2 -OH, (CH 3 ) 2 N- (CH 2 ) 3 -OH, (CH 3 ) 2 N- (CH 2 ) 4 -OH, CH 3 - (CH 2 ) 3 - N (CH 3 ) -CH 2 -CH 2 -OH, C 6 H 5 -CH 2 -N (CH 3 ) -CH 2 -CH 2 -OH, (CH 3 ) 2 N- CH 2 -CH 2 -
N(CH3)-CH2-CH2-OH, CH3-(CH2)2-N(CH3)-CH2-CH2-OH5 H2N-CH2-CH2-N(CH3)- CH2-CH2-OH.N (CH 3 ) -CH 2 -CH 2 -OH, CH 3 - (CH 2 ) 2 -N (CH 3 ) -CH 2 -CH 2 -OH 5 H 2 N-CH 2 -CH 2 -N (CH 3 ) - CH 2 -CH 2 -OH.
Als wasser- und halogenfreies Lösemittel werden bevorzugt Alkohole, Ester und/oder Ketone, insbesondere C2- bis C6-Monoalkohole eingesetzt. Die Zinkoxidkonzentrationen der primärpartü ilär redispergierten Partikel im Dispersionsmedium liegen allgemein zwischen 0,1 und 75 Gew.-%, vorzugsweise 10 und 50 Gew.-%, insbesondere 20 und 40 Gew.-%.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.
Die erfindungsgemäßen Dispersionen primärpartikulär redispergierter Teilchen zeichnen sich dadurch aus, dass sie lagerstabil sind und auch nach Wochen und Monaten keine Tendenz zu Partikelagglomeration, Feststoffausfällung, Entmischung, Vergelen, Erstarrung, Verfärbung und/oder Aushärtung zeigen.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.
Die erfindungsgemäßen Zinkoxid Dispersionen werden hergestellt, indem ein primärpartikulär redispergierbares Zinkoxid im Dispersionsmedium dispergiert wird.The zinc oxide dispersions according to the invention are produced by dispersing a primary particulate redispersible zinc oxide in the dispersion medium.
In einer besonders bevorzugten Ausführungsform der Erfindung werden primärpartikulär redispergierbare Zinkoxide in Form methanolischer Suspensionen oder Gele verwendet, die beispielsweise nach WO 00/50503 hergestellt wurden. Die Zinkoxidkonzentrationen liegen hier allgemein zwischen 5 und 75 Gew.-%, vorzugsweise zwischen 25 und 50 Gew.-%. Die Leitfähigkeit der methanolischen Flüssigphase ist kleiner als 200 S/cm, vorzugsweise kleiner als 10 mS/cm.In a particularly preferred embodiment of the invention, 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.
In einer besonders bevorzugten Ausführungsform wird in den erfindungsgemäßenIn a particularly preferred embodiment, in the invention
Dispersionen enthaltenes Methanol nach Einbringen des Zinkoxids destillativ entfernt, wodurch der Dispersionszustand der Partikel verbessert wird, was sich durch zunehmende Transluzenz der Dispersion bemerkbar macht.After the zinc oxide has been introduced, 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.
Zur Verbesserung des Dispersionsgrades der Partikel können zum Stand der Technik gehörende Homogenisierungsverfahren verwendet werden, die Geräte wie Hochge- schwindigkeitsrührer (z.B. IKA-Ultra-Turrax® T25 basic, IKA-Werke GmbH & Co KG, D-79219 Staufen), Ultraschälldispergatoren (z.B. UP200S, UP400S, Dr. Hielscher GmbH, D-14513 Berlin) und/oder Strahldispergatoren (Chem. Ing. Tech. (69), 6/97, S. 793-798; EP 07667997) einsetzen. Unter Verwendung der erfindungsgemäßen Zinkoxid-Partikeldispersionen lassen sich UV-absorbierende und/oder biozide Überzüge und oder Formkörper herstellen. Unter Überzügen werden sowohl Polymer-Systeme zur Beschichtung von Werkstoffen wie z.B. Metallen, Kunststoffen oder Glas als auch Cremes, Salben, Gele oder ähnliche feste oder fließfähige Formulierungen zur Verwendung im kosmetischen, oder pharmazeutischen Bereich verstanden.To improve the degree of dispersion of the particles, 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.
Eine bevorzugte Ausführungsform der Erfindung sind Formkörper, die anorganische und/oder organische Polymere sowie primärpartikulär dispergierte Zinkoxidteilchen enthalten.A preferred embodiment of the invention is shaped articles which contain inorganic and / or organic polymers and primarily particulate-dispersed zinc oxide particles.
Eine weitere bevorzugte Ausführungsform der Erfindung sind Überzüge, die anorganische und /oder organische Polymere sowie primärpartikulär dispergierte Zinkoxidteilchen enthalten.A further preferred embodiment of the invention are coatings which contain inorganic and / or organic polymers and primarily particulate-dispersed zinc oxide particles.
Bei den organischen Polymeren handelt es sich bevorzugt um Polyurethane, Poly- acrylate, Polyamide und/oder Polyester, insbesondere Polycarbonate.The organic polymers are preferably polyurethanes, polyacrylates, polyamides and / or polyesters, in particular polycarbonates.
Bei den anorganischen Polymeren handelt es sich bevorzugt um kondensationsver- netzte Sol/Gel-Materialien. The inorganic polymers are preferably condensation-crosslinked sol / gel materials.
Beispiele:Examples:
Die Ultrazentrifugenmessungen wurden an ca. 0.5 Gew.-%-igen ZnO Dispersionen in einem Dispersionsmedium aus Ethylenglycol/Wasser (Gewichtsverhältnis 2:1) durchgeführt.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).
Die TEM-Aufhahmen wurden anhand von ZnO-Dispersionen in Ethylenglycol/Wasser (Gewichtsverhältnis 2:1) durchgeführt, die auf ein Kohlenstoff-TEM- Grid aufgetropft, eingedampft und anschließend vermessen wurden.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.
Die Charakterisierung der erfindungsgemäßen Dispersion erfolgte durch Aufnahme und Auswertung des UV- Absorptionsspektrums der ZnO-Teilchen, vorzugsweise im Bereich zwischen 450 und 300 nm. Dazu wurde eine Probe der Dispersion in Ethylenglycol/Wasser (Gewichtsverhältnis 2:1) auf 1/500 verdünnt und gegen eine reme Mischung aus Ethylengylcol/Wasser (Gewichtsverhältnis 2:1) gemessen. QualitativeThe 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
Aussagen über den Grad der Feinteiligkeit der Dispersion werden dadurch erhalten, dass man die Extinktion der Probe bei 350 nm (E 5o, Absorptionsbereich von Zinkoxid, Transmissionsverluste durch Streuung und Absorption) durch die bei 400 nm (E 0o, außerhalb des Absorptionsbereichs von Zihkoxid, Transmissionsverluste aus- schließlich durch Streuung) dividiert. Für sehr kleine Partikel, die keine Transmissionsverluste durch Lichtstreuung verursachen ist E350/E oo sehr groß; kleinere Werte dagegen werden erhalten, wenn E 0Q durch Lichtstreuung bei großen Partikeln oder Agglomeraten zunimmt.Statements about the degree of fine particle size of the dispersion are obtained by comparing the absorbance of the sample at 350 nm (E 5 o, absorption range of zinc oxide, transmission losses due to scattering and absorption) with that at 400 nm (E 0 o, outside the absorption range of Zihkoxid, transmission losses divided by scatter only). For very small particles that do not cause transmission losses due to light scattering, E 350 / E oo is very large; however, smaller values are obtained when E 0 Q increases due to light scattering with large particles or agglomerates.
Als polyfunktionelles Organosilan wurde in den nachfolgenden Versuchen oligome- res c c/o-{OSi[(CH2)2Si(OC2H5)2(CH3)]}4 (D4-Diethoxid-Oligomer) eingesetzt. Dessen Herstellung erfolgte wie in US-A 6,136,939, Beispiel 2, beschrieben.Oligomeric cc / o- {OSi [(CH 2 ) 2 Si (OC 2 H 5 ) 2 (CH 3 )]} 4 (D4-diethoxide oligomer) 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.
Als Substrate wurden extrudierte Polycarbonat-Platten (Makrolon® 3103, Bayer AG, Leverkusen) eingesetzt. Vor der Beschichtung wurden die Platten auf ein Format vonAs substrates extruded polycarbonate sheets (Makrolon ® 3103, Bayer AG, Leverkusen, Germany) were used. Before coating, the plates were cut to a format of
10 x 10 cm zugeschnitten, durch Abspülen mit Isopropanol gereinigt und mit einem Haftvermittler versehen. Der Haftvermittler, ein Alkoxysilan-modifiziertes Polyurethan, wurde wie folgt hergestellt:10 x 10 cm cut, cleaned by rinsing with isopropanol and with a Adhesion promoter provided. The coupling agent, an alkoxysilane-modified polyurethane, was produced as follows:
a) Herstellung der Polyol-Komponente: 9,24 g eines stark verzweigten, hydroxylgrupperihaltigen Polyesters mit einem OH-a) Preparation of the polyol component: 9.24 g of a strongly branched, hydroxyl-containing polyester with an OH
Gehalt nach DIN 53240/2 von 8,6 ± 0,3 Gew.-% und einem Äquivalentgewicht von ca. 200 g/mol (Desmophen® 800, Bayer AG) wurden unter Rühren mit 3,08 g eines schwach verzweigten, hydroxylgrupperihaltigen Polyesters mit einem OH-Gehalt nach DIN 53240/2 von 4,3 ± 0,4 Gew.-% und einem Äquivalentgewicht von ca. 395 g/mol (Desmophen® 670, Bayer AG) in 3,08 g n-Butylacetat gelöst, danach wurdenContent according to DIN 53240/2 of 8.6 ± 0.3 wt .-% and an equivalent weight of about 200 g / mol (Desmophen ® 800, Bayer AG) were stirred with 3.08 g of a weakly branched, hydroxyl-containing polyester with an OH content according to DIN 53240/2 of 4.3 ± 0.4% by weight and an equivalent weight of approx. 395 g / mol (Desmophen ® 670, Bayer AG) dissolved in 3.08 g n-butyl acetate, after that
0,4 g einer 10 Gew.-%-igen Lösung von Zink(II)octoat in Diacetonalkohol, 0,2 g einer 10 Gew.-%-igen Lösung eines Verlaufshilfinittels (Baysilone® OL 17, GE Bayer Silicones, Leverkusen) in Diacetonalkohol sowie 170,5 g Diacetonalkohol zugegeben. Es wurden 186,5 g der klaren, farblosen und lagerstabilen Polyol- Komponente erhalten.0.4 g of a 10% by weight solution of zinc (II) octoate in diacetone alcohol, 0.2 g of a 10% by weight solution of a leveling agent (Baysilone ® OL 17, GE Bayer Silicones, Leverkusen) in Diacetone alcohol and 170.5 g of diacetone alcohol were added. 186.5 g of the clear, colorless and storage-stable polyol component were obtained.
b) Herstellung der Polyisocyanat-Komponente:b) Preparation of the polyisocyanate component:
462,4 g eines aliphatischen Polyisocyanats (IPDI-Trimerisat) mit einem NCO-Gehalt nach DIN EN ISO 11909 von 11,9 ± 0,4 Gew.-% und einem Äquivalentgewicht von 360 g/mol (Desmodur® Z 4470 (70 Gew.-%-ig in n-Butylacetat), Bayer AG) wurden mit 27,23 g n-Butylacetat verdünnt, danach wurden innerhalb von ca. 2 h 60,4 g n-Butylanünopropyltrimethoxysilan so zugetropft, dass die Reaktionstemperatur (Innenthermometer) nicht über 40°C stieg. Nach dem Abkühlen wurden 550 g der klaren, schwach gelben und lagerstabilen Polyisocyanat-Komponente erhalten.462.4 g of an aliphatic polyisocyanate (IPDI trimer) with an NCO content according to DIN EN ISO 11909 of 11.9 ± 0.4 wt.% And an equivalent weight of 360 g / mol (Desmodur ® Z 4470 (70 wt .-% in n-butyl acetate), Bayer AG) were diluted with 27.23 g of n-butyl acetate, then 60.4 g of n-butylanünopropyltrimethoxysilane were added dropwise over the course of about 2 hours so that the reaction temperature (internal thermometer) did not rose above 40 ° C. After cooling, 550 g of the clear, pale yellow and storage-stable polyisocyanate component were obtained.
c) Herstellung des verarbeitungsfertigen Haftvermittlersc) Production of the adhesion promoter ready for processing
Zur Herstellung des verarbeitungsfertigen Haftvermittlers wurden 42,3 g der Komponente a) und 7,7 g der Komponente b) unter Rühren vermischt; die erhaltene klare Lösung wurde innerhalb von einer Stunde verarbeitet. Der Auftrag des wie beschrieben hergestellten Haftvermittlers erfolgte durch Schleudern (2000 U/min, 20 sec Haltezeit), danach wurde dieser 60 min bei 130°C thermisch behandelt. Die so erzielte Schichtdicke lag typischerweise bei ca. 0,3-0,6 μm. Die Applikation der erfindungsgemäßen UV- Schutzformulierungen erfolgte inner- halb einer Stunde nach Aushärtung des Haftvermittlers.To prepare the ready-to-use adhesion promoter, 42.3 g of component a) and 7.7 g of component b) were mixed with stirring; the clear solution obtained was processed within one hour. The adhesion promoter produced as described was applied by spinning (2000 rpm, 20 sec holding time), after which it was thermally treated at 130 ° C. for 60 minutes. The layer thickness achieved in this way was typically around 0.3-0.6 μm. The UV protective formulations according to the invention were applied within one hour after the adhesion promoter had hardened.
Beispiel 1:Example 1:
(Nachstellung der Herstellung von nano-ZnO-Aufschlämmungen nach WO 00/50503)(Reproduction of the production of nano-ZnO slurries according to WO 00/50503)
240,35 g Zinkoxid (techn. 99,8 Gew.-%) wurden in 1320 g Methanol (techn. 99,9 Gew.-%) vorgelegt und auf 50°C temperiert. Durch Zugabe von 355,74 g Eisessig (techn. 99,9 Gew.-%) und 51,15 g VE- Wasser wurde der Feststoff gelöst und an- schließend auf 60°C temperiert. Zur Beseitigung ungelöster Anteile ZnO wurde in 3240.35 g of zinc oxide (tech. 99.8% by weight) were placed in 1320 g of methanol (tech. 99.9% by weight) and the temperature was raised to 50.degree. The solid was dissolved by adding 355.74 g of glacial acetic acid (technical grade 99.9% by weight) and 51.15 g of demineralized water and then heating to 60 ° C. To remove undissolved portions of ZnO, 3
Portionen insgesamt 34,36 g KOH (techn. 90,22 Gew.-%) zugegeben. Nach 40- minütigem Nachrühren wurde innerhalb von 8 min. eine Lösung von 290,00 g KOH (techn. 90,22 Gew.-%) in 660,00 g Methanol zugegeben. Während des gesamten Fällungsvorganges betrug die Reaktionstemperatur 60°C. Nach einer Reifungszeit von 35 min. wurde der Reaktionsansatz durch äußere Eiskühlung auf Raumtemperatur gekühlt. Über Nacht sedimentierten die ZnO-Partikel und der salzhaltige Überstand konnte abgehoben werden. Nun wurde die Menge des entfernten Methanols durch frisches Methanol ersetzt, der Ansatz für 10 Minuten wieder aufgerührt und für 12 h sedimentieren gelassen. Diese Waschprozedur wurde noch zweimal wiederholt bis die Leitfähigkeit des methanolischen Überstandes 3 mS/cm betrug. Nach vollständigem Entfernen des klaren methanolischen Überstandes wurde eine 34,8 Gew.- %-ige methanolische Zinkoxid Aufschlämmung erhalten. Beispiel 2:A total of 34.36 g portions of KOH (technical weight 90.22% by weight) were added. After stirring for 40 minutes, within 8 min. a solution of 290.00 g KOH (technical 90.22 wt .-%) in 660.00 g methanol was added. During the entire precipitation process, the reaction temperature was 60 ° C. After a maturation time of 35 min. the reaction mixture was cooled to room temperature by external ice cooling. The ZnO particles sedimented overnight and the saline supernatant could be removed. Now the amount of methanol removed was replaced by fresh methanol, the mixture was stirred again for 10 minutes and left to sediment for 12 h. This washing procedure was repeated two more times until the conductivity of the methanolic supernatant was 3 mS / cm. After the clear methanolic supernatant was completely removed, a 34.8% by weight methanolic zinc oxide slurry was obtained. Example 2:
28,7 g einer nach Beispiel 1 hergestellten nano-ZnO Aufschlämmung (34,8 Gew.-% ZnO, Leitfähigkeit der flüssigen Phase 3 mS/cm) wurden mit 71,3 g einer 4 gew.-%-igen Lösung von Triethanolamin in n-Butanol unter Rühren versetzt. Die28.7 g of a nano-ZnO slurry prepared according to Example 1 (34.8% by weight of ZnO, conductivity of the liquid phase 3 mS / cm) were mixed with 71.3 g of a 4% by weight solution of triethanolamine in n-Butanol mixed with stirring. The
UN-spektroskopische Charakterisierung lieferte ein Extinktionsverhältnis E35o/E oo von 109.UN spectroscopic characterization gave an extinction ratio E 35 o / E oo of 109.
Beispiel 3Example 3
71,6 g einer nach Beispiel 1 hergestellten nano-ZnO Aufschlämmung (34,8 Gew.-% ZnO, Leitfähigkeit der flüssigen Phase 3 mS/cm) wurde/? mit 28,4 g einer 4 gew.-%-igen Lösung von Triethanolamin in n-Butanol unter Rühren versetzt. Die UV-spektroskopische Charakterisierung lieferte ein Extinktionsverhältnis E35o/E 0o von 91.71.6 g of a nano-ZnO slurry produced according to Example 1 (34.8% by weight ZnO, conductivity of the liquid phase 3 mS / cm) was /? 28.4 g of a 4% strength by weight solution of triethanolamine in n-butanol are added with stirring. The UV spectroscopic characterization gave an extinction ratio E 35 o / E 0 o of 91.
Beispiel 4Example 4
Zur Verbesserung des Dispersionsgrades der Primärpartikel wurden nach den Bei- spielen 2 und 3 hergestellte Dispersionen durch je dreimalige Behandlung mit einemTo improve the degree of dispersion of the primary particles, dispersions prepared according to Examples 2 and 3 were each treated three times with a
Düsenstrahldispergator bei 1500 bar homogenisiert. Auf diese Weise konnte das Extinktionsverhältnis E350/E4QQ der Dispersion aus Beispiel 2 auf 250 und aus Beispiel- 3 auf 175 verbessert werden.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.
Beispiel 5Example 5
412,0 g einer analog zu Beispiel 1 hergestellten nano-ZnO Aufschlämmung (33,1 Gew.-% ZnO, Leitfähigkeit der flüssigen Phase 3 mS/cm) wurde mit 545,48 g einer 4 gew.-%-igen Lösung von Triethanolamin in n-Butanol unter Rühren versetzt. Anschließend wurden bei 50°C Wasserbadtemperatur und 100 mbar Druck 275,63 g412.0 g of a nano-ZnO slurry produced analogously to Example 1 (33.1% by weight of ZnO, conductivity of the liquid phase 3 mS / cm) was mixed with 545.48 g of a 4% by weight solution of triethanolamine added in n-butanol with stirring. Then at 50 ° C water bath temperature and 100 mbar pressure 275.63 g
Leichtsieder zur Entfernung des Methanols abdestilliert. Die UV-spektroskopische Charakterisierung lieferte ein Extinktionsverhältnis E35o/E400 von 100. Eine Hochdruckhomogenisierung mittels Düsenstrahldispergator (einmaliger Durchgang, 400 bar) führte zu einer Steigerung auf 199.Low boilers distilled off to remove the methanol. The UV spectroscopic Characterization gave an extinction ratio E 3 5o / E 400 of 100. A high-pressure homogenization by means of nozzle jet disperser (single passage 400 bar) led to an increase in the 199th
Beispiel 6:Example 6:
60 g Triethanolamin wurden mit 105,1 g einer analog zu Beispiel 1 hergestellten methanolischen Zinkoxid Aufschlämmung (37,1 Gew.-% ZnO, Leitfähigkeit der flüssigen Phase 3 mS/cm) unter Rühren gemischt. Das enthaltene Methanol wurde anschließend bei 50°C Wasserbadtemperatur im Rotationsverdampfer abdestilliert60 g of triethanolamine were mixed with 105.1 g of a methanolic zinc oxide slurry (37.1% by weight of ZnO, conductivity of the liquid phase 3 mS / cm) prepared analogously to Example 1 with stirring. The methanol contained was then distilled off at 50 ° C. water bath temperature in a rotary evaporator
(Vakuum 200 mbar), wobei ein transluzentes lagerstabiles Sol erhalten wurde. Die UV-spektroskopische Charakterisierung lieferte ein Extinktionsverhältnis E350/E oo von 117.(Vacuum 200 mbar), a translucent, storage-stable sol being obtained. The UV spectroscopic characterization gave an extinction ratio E 350 / E oo of 117.
Beispiel 7:Example 7:
100 g einer nach Beispiel 6 hergestellten Dispersion in Triethanolamin wurde mit 100 g n-Butanol unter Rühren gemischt, wobei ein 19,9 Gew.-%-iges transluzentes, lagerstabiles Sol erhalten wurde. Die UV-spektroskopische Charakterisierung lieferte ein Extinktionsverhältnis E350/E oo von 360.100 g of a dispersion in triethanolamine prepared according to Example 6 was mixed with 100 g of n-butanol with stirring, a 19.9% by weight translucent, storage-stable sol being obtained. The UV spectroscopic characterization provided an extinction ratio E 350 / E oo of 360.
Beispiel 8: Herstellung einer UV-Schutzformulierung mit nano-ZnOExample 8: Preparation of a UV protection formulation with nano-ZnO
Unter Rühren wurden 13,98 g oligomeres cyclo-{SiO(CH3)[(CH2CH2Si(CH3)- (OC2H5)2]} (D4-Diethoxid-Oligomer) in 50 g l-Methoxy-2-propanol vorgelegt undWith stirring, 13.98 g of oligomeric cyclo- {SiO (CH 3 ) [(CH 2 CH 2 Si (CH 3 ) - (OC 2 H 5 ) 2 ]} (D4-diethoxide oligomer) in 50 g of l-methoxy Submitted -2-propanol and
26,5 g Tetraethoxysilan und 0,1 g Verlaufshilfsmittels (Tegoglide® 410, Goldschmidt AG, Essen) zugegeben. Anschließend wurden 3,4 g 0,1 n p-Toluolsulfonsäure zugegeben und es wurde 30 min bei Raumtemperatur gerührt, bevor 38,87 g einer nach Beispiel 2 hergestellten und nach Beispiel 4 homogenisierten nano-Zinkoxid Dispersion (Menge entsprechend 10 g ZnO trocken) zugetropft wurde. Anschließend wird der Lack über einen Faltenfilter filtriert. Beispiel 9: Entfernen der Niedrigsieder aus der UV-Schutzformulierung aus Beispiel 826.5 g of tetraethoxysilane and 0.1 g of leveling agent (® Tegoglide 410, Goldschmidt AG, Essen) was added. 3.4 g of 0.1 n p-toluenesulfonic acid were then added and the mixture was stirred at room temperature for 30 minutes before 38.87 g of a nano-zinc oxide dispersion prepared according to Example 2 and homogenized according to Example 4 (amount corresponding to 10 g ZnO dry) was dropped. The varnish is then filtered through a pleated filter. Example 9: Removing the low boilers from the UV protection formulation from Example 8
Um die nach Beispiel 8 hergestellte UV-Schutzformulierung von niedrigsiedenden toxischen Bestandteilen wie Methanol zu befreien, wurden 60 g n-Butanol zugesetzt und anschließend wurden bei 50°C Wasserbadtemperatur und 200 mbar Druck 60 g Leichtsieder abdestilliert.In order to free the low-boiling toxic constituents such as methanol from the UV protection formulation prepared according to Example 8, 60 g of n-butanol were added and then 60 g of low boilers were distilled off at 50 ° C. water bath temperature and 200 mbar pressure.
Beispiel 10: Herstellung einer weiteren UV-Schutzformulierung mit nano-ZnOExample 10: Production of a further UV protection formulation with nano-ZnO
Zu einer Mischung aus 18,9 g D4-Diethoxid-Oligomer, 26,6 g Tetraethoxysilan und 35,6 g l-Methoxy-2-propanol wurden unter Rühren 3,6 g einer 0,1 n, wässrigen p- Toluolsulfonsäurelösung gegeben. Nach 60 Minuten Rühren wurden dann 57,8 g eines nano-ZnO-Sols, hergestellt wie in Beispiel 5 beschrieben, zugegeben und nach3.6 g of a 0.1N aqueous solution of p-toluenesulfonic acid were added to a mixture of 18.9 g of D4-diethoxide oligomer, 26.6 g of tetraethoxysilane and 35.6 g of l-methoxy-2-propanol with stirring. After stirring for 60 minutes, 57.8 g of a nano-ZnO sol, prepared as described in Example 5, were then added and after
15 Minuten Rühren schließlich noch 15,0 g mit Acetessigsäure komplexierten Alu- miniumtributylats in l-Methoxy-2-propanol (hergestellt durch Zugabe von 4,28 g Acetessigsäureethylester zu einer Mischung aus 8,1 g und 2,63 g l-Methoxy-2-propanol unter Rühren). Es wurde eine UV-Schutzformulierung mit 35 Gew.-% nano-ZnO, berechnet auf die Feststoffe, erhalten.Finally, 15.0 g of 15.0 g of aluminum tributylate complexed with acetoacetic acid in 1-methoxy-2-propanol (prepared by adding 4.28 g of ethyl acetoacetate to a mixture of 8.1 g) for 15 minutes and 2.63 g of l-methoxy-2-propanol with stirring). A UV protective formulation with 35% by weight of nano-ZnO, calculated on the solids, was obtained.
Beispiel 11: Herstellung von UV-Schutzbeschichtungen auf Glas und Polycar- bonatExample 11: Production of UV protective coatings on glass and polycarbonate
Die nach Beispiel 10 hergestellte UV-Schutzformulierung wurde durch SchleudernThe UV protection formulation prepared according to Example 10 was spun
(maximale Drehzahl 500 U/min, 20 Sekunden Haltezeit) auf wie beschrieben mit einem Haftvermittler versehene Polycarbonat-Platten appliziert. Nach der Aushärtung, 60 Minuten bei 125°C, wurde ein optisch einwandfreier und gut haftender Film erhalten. Zur Messung der UV-/VIS-Absorptionsspektren wurde die nach Beispiel 10 hergestellte UV-Schutzformulierung ebenfalls auf Glas appliziert, wobei der Auftrag durch Schleudern bei 4 verschiedenen maximalen Drehzahlen erfolgt (200, 400, 600 und 800 U/min). Auf diese Weise wurden nach der Aushärtung (60 min bei 125°C) 4 Glasplatten mit unterschiedlichen Schichtdicken erhalten.(maximum speed 500 rpm, 20 seconds holding time) applied to polycarbonate plates provided with an adhesion promoter as described. After curing, 60 minutes at 125 ° C, an optically perfect and well adhering film was obtained. To measure the UV / VIS absorption spectra, the 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.).
Wie den Absorptionsspektren zu entnehmen ist (siehe Figur 1), gewähren die so hergestellten Beschichtungen unterhalb von ca. 375 nm einen - hervorragenden UV- Schutz (hohe Extinktion und scharfe Extinktionskante) und weisen im Bereich des sichtbaren Lichts keinerlei Streuung oder Absorption auf.As can be seen from the absorption spectra (see FIG. 1), 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.
Beispiel 12: Herstellung einer UN-Schutzbeschichtung mit nano-ZnO in organischem BinderExample 12: Production of a UN protective coating with nano-ZnO in organic binder
40,42 g eines hydroxylgruppenhaltigen Polyaciylats mit einem OH-Gehalt nach DIΝ40.42 g of a hydroxyl-containing polyaciylate with an OH content according to DIΝ
53240/2 von 3,2 + 0,4 Gew.-% und einem Äquivalentgewicht von 530 g/mol (Desmophen® A 665 (70 Gew.-%-ig in Butylacetat), Bayer AG) wurden in 11,41 g einer l:l-Mischung aus l-Methoxypropylacetat-2 und Solvent Νaphtha 100 (höhersiedendes Aromatengemisch, Exxon Chemie GmbH, Hamburg) gelöst und anschließend unter Rühren mit einem aliphatischen, vernetzenden Einbrennurethanharz mit einem blockierten ΝCO-Gehalt von 10,5 Gew.-% und einem Äquivalentgewicht von ca. 400 g/mol (Desmodur® VP LS 2253 (75 Gew.-%-ig in l-Methoxypropylacetat-2 und Solvent Νaphtha 100 (8:17), Bayer AG) versetzt. Dann wurden je.0,49 g Baysilone® OL17 (10 Gew.-%-ig in Xylol) (GE Bayer Silicones, Leverkusen) und Modaflow® (1 Gew.-% in Xylol), (Solutia Germany GmbH, Mainz) als Verlaufshilfsmittel sowie53240/2 of 3.2 + 0.4 wt .-% and an equivalent weight of 530 g / mol (Desmophen ® A 665 (70 wt .-% in butyl acetate), Bayer AG) were in 11.41 g 1: 1 mixture of 1-methoxypropylacetate-2 and solvent Νaphtha 100 (higher-boiling aromatic mixture, Exxon Chemie GmbH, Hamburg) dissolved and then with stirring with an aliphatic, crosslinking stoving urethane resin with a blocked ΝCO content of 10.5% by weight and an equivalent weight of about 400 g / mol (Desmodur ® VP LS 2253 (75 wt .-% - solution in l-methoxypropyl-2 and Solvent Νaphtha 100 (8:17), Bayer AG) were then added je.0. , 49 g 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
4,9 g Dibutylzinndilaurat zugesetzt. Nach 30 minütigem Rühren wurden 103,4 g einer 20,3 Gew.-%-igen ZnO-Dispersion in Butanol/TEA (96:4) (hergestellt nach Beispiel 5) zugegeben und weitere 10 min gerührt.4.9 g of dibutyltin dilaurate were added. After stirring for 30 minutes, 103.4 g of a 20.3% by weight ZnO dispersion in butanol / TEA (96: 4) (prepared according to Example 5) were added and the mixture was stirred for a further 10 minutes.
Anschließend wurde das applikationsfertige Beschichtungssystem als lagerstabileThen the ready-to-use coating system became stable in storage
Flüssigkeit erhalten. Beispiel 13: Herstellung von UV-Schutzbeschichtungen auf Glas und Polycar- bonatGet liquid. Example 13: Production of UV protective coatings on glass and polycarbonate
Die nach Beispiel 12 hergestellte UV-Schutzformulierung wurde durch Schleudern (maximale Drehzahl 1500 U/min , 20 Sekunden Haltezeit) auf wie beschrieben mit einem Haftvermittler versehene Polycarbonat-Platten appliziert. Nach der Aushärtung, 60 Minuten bei 130°C, würde ein optisch einwandfreier und gut haftender Film erhalten.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.
Zur Messung des UV-/VIS-Abso tionsspektrums wurde die nach Beispiel 12 hergestellte UV-Schutzformulierung ebenfalls auf Glas appliziert, wobei der Auftrag durch Schleudern erfolgte (maximale Drehzahlen 1000 U/min, 20 Sekunden Haltezeit). Nach Aushärtung (60 min bei 130°C) wurde ein optisch einwandfreier und gut haftender Film erhalten.To measure the UV / VIS absorption spectrum, 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.
Wie dem Absorptionsspektrum zu entnehmen ist (siehe Figur 2), gewährt die so hergestellte Beschichtung unterhalb von ca. 375 nm einen hervorragenden UV-Schutz (hohe Extinktion und scharfe Extinktionskante) und weist im Bereich des sichtbaren Lichts keinerlei Streuung oder Absorption auf. As can be seen from the absorption spectrum (see FIG. 2), 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.

Claims

Patentansprttche: Patentansprttche:
1. Wasser- und halogenfreie Dispersion enthaltend prfmärpartikulär redispergierte Zinkoxidteilchen mit einem Durchmesser zwischen 1 und 200 nm und Aminoalkohole.1. Water-free and halogen-free dispersion containing test oxide-redispersed zinc oxide particles with a diameter between 1 and 200 nm and amino alcohols.
2. Dispersion nach Anspruch 1 dadurch gekennzeichnet, dass zusätzlich halogenfreie organische Lösemittel enthalten sind.2. Dispersion according to claim 1, characterized in that halogen-free organic solvents are additionally contained.
3. Ein Verfahren zur Herstellung der Zinkoxid-Dispersionen nach Anspruch 1 bei dem primärpartikulär redispergierbare Zinkoxidteilchen unter Rühren in Aminoalkohole oder amino alkoholhaltige, wasserfreie organische Lösemittel gegeben werden.3. A process for the preparation of the zinc oxide dispersions according to claim 1 in which the primary particulate redispersible zinc oxide particles are added with stirring to amino alcohols or amino alcohol-containing, anhydrous organic solvents.
4. Formteile und Überzüge hergestellt unter Verwendung der Dispersionen nach4. Molded parts and coatings produced using the dispersions
Anspruch 1. Claim 1.
EP03798155A 2002-09-23 2003-09-10 Zinc-oxide dispersions in anhydrous dispersion media that are devoid of halogen Withdrawn EP1546266A1 (en)

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DE10244212A DE10244212A1 (en) 2002-09-23 2002-09-23 Water- and halogen free dispersion, useful for the production of transparent UV-protective coatings, comprises redispersable primary particle zinc oxide particles having a diameter of 1-200 nm and aminoalcohols
DE10244212 2002-09-23
PCT/EP2003/010024 WO2004029161A1 (en) 2002-09-23 2003-09-10 Zinc-oxide dispersions in anhydrous dispersion media that are devoid of halogen

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