WO1996009348A2 - Polymer composition, a method of producing the same and a use therefor - Google Patents
Polymer composition, a method of producing the same and a use therefor Download PDFInfo
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- WO1996009348A2 WO1996009348A2 PCT/EP1995/003577 EP9503577W WO9609348A2 WO 1996009348 A2 WO1996009348 A2 WO 1996009348A2 EP 9503577 W EP9503577 W EP 9503577W WO 9609348 A2 WO9609348 A2 WO 9609348A2
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- Prior art keywords
- composition according
- polymer composition
- zinc oxide
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- films
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- 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
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
Definitions
- the invention relates to a polymeric composition with pesticide-resistant and light-stable properties, a process for its preparation and use as a film for greenhouses. Another object of the invention is a film which is produced from the polymeric composition.
- HALS Hlingerd Amine Light Stabilizers
- UV-light-absorbing substances such as benzophenone or benzotriazole.
- LDPE low density polyethylene
- ethylene-vinyl acetate copolymers are generally used alone or in combination with low density polyethylene or linear low density polyethylene (LLDPE).
- LLDPE linear low density polyethylene
- the films for greenhouses can be produced as single-layer or co-extruded multilayer films.
- the technical object of the invention is therefore to provide a composition which, despite its zinc oxide content, enables the production of a transparent film and in which the decomposition of the alkylated amines by pesticides is not possible.
- a polymeric composition with pesticide-resistant and light-stable properties which, in addition to the commonly used polyethylene resin and / or ethylene-vinyl acetate copolymer and the alkylated amine as light stabilizer, contains micronized zinc oxide particles with a particle diameter of 10 to 200 nm.
- the polymeric composition contains an ethylene-vinyl acetate copolymer in combination with low density polyethylene or linear low density polyethylene.
- An alkylated amine of the formulas I or II is preferably used as the light stabilizer. These are so-called HALS (Hlingerd Amin Light Stabilizers).
- the micronized zinc oxide particles particularly preferably have a particle diameter of 20 to 60 nm and can be used in amounts of 0.01 to 1% by weight.
- the alkylated amines are used in amounts of 0.1 to 2% by weight.
- the polymeric composition according to the invention can furthermore contain customary antioxidants, antiblocking agents, inorganic, infrared-shielding fillers and anti-thawing agents.
- the antioxidants are added to improve the thermal stability of the polymer.
- the antiblocking agents are added to make it easier to unfold the folded film.
- the infrared shielding fillers are said to reduce heat loss during the night in the greenhouses. Natural kaolins or natural silicon oxides are generally used for this. Anti-thaw agents are added to reduce moisture condensation, which reduces the translucency of these transparent films. In general, high molecular weight fatty acid esters are used for this.
- Another object of the invention is a method for producing the polymeric composition, wherein the individual components are mixed, heated, melted and granulated after cooling.
- the polymeric compositions according to the invention can also be produced in highly concentrated form as a granulated masterbatch, which is then processed with the addition of further polymeric base materials.
- Rose films in greenhouses can be improved with the films produced in a conventional manner from the polymer composition according to the invention, since the
- Plants can be better protected from the "Botrytis” rose disease.
- the growth of the pests causing this disease is stimulated by UV light with a wavelength of 370 nm. UV light in particular However, this wavelength is absorbed by the zinc oxide particles in the film according to the invention.
- a single-layer film with a diameter of 180 ⁇ m was produced from low-density polyethylene with a melt index of 0.3 and various proportions of micronized zinc oxide with a diameter of 60 nm and alkylated amines.
- the commercial products from Ciba-Geigy Chimassorb 944 (Formula I) and Chimassorb 119 (Formula II) were used as amines.
- Resistance to pesticides was measured by spraying the known pesticide "permethrin" onto the samples once a month. The samples were then exposed to a Xenotest 1200 (2) (UV tester from Hanau). This is a test in which the samples are exposed to the annual UV radiation within a short time. This allows the aging process of the film to be simulated in a short time.
- the residual elongation at break was then determined as a measure of the degree of aging of the film. The results are given in kLy (kiloLangley) up to 50% residual expansion.
- the samples sprayed with "permethrin” and unsprayed were treated in a separate device to prevent contamination. A 1% emulsion of "permethrin” in ethanol / hexane (ratio 9: 1) was used.
- the Xenotest was set to 70 ° C operating temperature in the device (black panel temperature) and a rela tive air humidity of 60%. The samples were fixed on plexiglass. Table 1 shows the composition of the films produced, Table 2 shows the results of the measurements for the films assembled according to Table 1.
- Zinc stearate was used as a processing aid.
- Coextruded multilayer films with a diameter of 180 ⁇ m were produced, which essentially consist of an ethylene-vinyl acetate copolymer with a
- Layer A is a base resin of low density polyethylene that
- Layer B is a base resin of ethylene-vinyl acetate copolymer with a vinyl acetate content of 12% by weight.
- Layer C is identical to layer B.
- anti-thaw agents and infrared absorbing additives are added as follows (all figures in% by weight):
- Table 3 shows the composition of the individual films.
- Table 4 shows the properties.
- Zinc stearate was added as a processing aid.
- the films which have micronized zinc oxide with a diameter of 60 nm have excellent properties with regard to light transmission and also maintain stability when treated with pesticides. As a result, they are superior to films that contain zinc oxide with a diameter of 1 ⁇ m and also to films that do not contain zinc oxide at all.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Greenhouses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Polymere Zusammensetzung, Verfahren zu ihrer Herstellung und eine Verwendung Polymer composition, process for its preparation and its use
Gegenstand der Erfindung ist eine polymere Zusammensetzung mit pestizidresistenten und lichtstabilen Eigenschaften, ein Verfahren zu ihrer Herstellung sowie eine Verwendung als Folie für Gewächshäuser. Ein weiterer Gegenstand der Erfindung ist eine Folie, die aus der polymeren Zusammensetzung hergestellt wird. The invention relates to a polymeric composition with pesticide-resistant and light-stable properties, a process for its preparation and use as a film for greenhouses. Another object of the invention is a film which is produced from the polymeric composition.
Folien, die in Gewächshäusern verwendet werden, müssen im allgemeinen gut geschützt sein gegen Licht- und UV-Einstrahlung sowie gegen die Einwirkungen von in den Gewächshäusern verwendeten Pestiziden. Daher werden im allgemeinen derartige Folien durch das Hinzufügen von alkylierten Aminverbindungen insbesondere sogenannten HALS- Verbindungen (HALS = Hindred Amin Light Stabilizers) in Kombination mit UV-Licht absorbierenden Substanzen, wie Benzophenon oder Benzotriazol behandelt. Als Basisharz für derartige Folien werden im allgemeinen Polyethylen niedriger Dichte (LDPE), Ethylen-Vinylacetat-Copolymere allein oder in Kombination mit Polyethylen niedriger Dichte oder linearem Polyethylen niedriger Dichte (LLDPE) verwendet. Die Folien für Gewächshäuser können als Einschicht- oder koextrudierte Mehrschichtfolien hergestellt werden. Films used in greenhouses generally have to be well protected against light and UV radiation and against the effects of pesticides used in the greenhouses. Therefore, films of this type are generally treated by adding alkylated amine compounds, in particular so-called HALS compounds (HALS = Hindred Amine Light Stabilizers) in combination with UV-light-absorbing substances, such as benzophenone or benzotriazole. As the base resin for such films, low density polyethylene (LDPE), ethylene-vinyl acetate copolymers are generally used alone or in combination with low density polyethylene or linear low density polyethylene (LLDPE). The films for greenhouses can be produced as single-layer or co-extruded multilayer films.
Aus dem Stand der Technik ist bekannt, daß Folien, die mit alkylierten Aminverbindungen gegen UV- und Lichteinwirkung geschützt werden, den Nachteil aufweisen, daß sich allmählich diese Schutzwirkung verringert. Es ist vermutet worden, daß dieser Effekt dadurch auftritt, daß die alkylierten Amine mit den in den Gewächshäusern verwendeten Pestiziden reagieren und so ihren UV-stabilisierenden Effekt verlieren, was eine beschleunigte Zersetzung der Folien zur Folge hat. Es ist weiterhin bekannt, daß auch Zinkoxid mit einem Teilchendurchmesser von 1 bis 3 μm einen UV-absorbierenden Effekt besitzt, dadurch daß es UV-Strahlung nicht durchläßt. Es ist weiterhin auch bekannt, daß Zinkoxid bei der Herstellung von Polyolefinen als Neutralisator für halogenhaltige Katalysatoren verwendet wird. Trotz dieser positiven Eigenschaften wurde Zinkoxid bisher nicht in transparenten Folien für Treibhäuser verwendet, weil man davon ausgegangen ist, daß das Hinzufügen von Zinkoxid die Folien lichtundurchlässig macht, so daß sie für den Einsatz in Gewächshäusern nicht mehr geeignet sind. It is known from the prior art that films which are protected against the action of UV and light with alkylated amine compounds have the disadvantage that this protective action is gradually reduced. It has been suspected that this effect occurs because the alkylated amines react with the pesticides used in the greenhouses and thus lose their UV-stabilizing effect, which results in an accelerated decomposition of the films. It is also known that zinc oxide with a particle diameter of 1 to 3 μm also has a UV-absorbing effect in that it does not transmit UV radiation. It is also known that zinc oxide is used as a neutralizer for halogen-containing catalysts in the production of polyolefins. Despite these positive properties, zinc oxide has not previously been used in transparent films for greenhouses, because it has been assumed that the addition of zinc oxide makes the films opaque, so that they are no longer suitable for use in greenhouses.
Die technische Aufgabe der Erfindung liegt daher darin, eine Zusammensetzung zur Verfügung zu stellen, die trotz ihres Gehaltes an Zinkoxid die Herstellung einer transparenten Folie ermöglicht und bei der die Zersetzung der alkylierten Amine durch Pestizide nicht möglich ist. The technical object of the invention is therefore to provide a composition which, despite its zinc oxide content, enables the production of a transparent film and in which the decomposition of the alkylated amines by pesticides is not possible.
Diese Aufgabe wird durch eine polymere Zusammensetzung mit pestizidresistenten und lichtstabilen Eigenschaften gelöst, die neben dem üblicherweise verwendeten Polyethylenharz und/oder Ethylen-Vinylacetat-Copolymer und dem alkylierten Amin als Lichtstabilisierungsmittel mikronisierte Zinkoxidpartikel mit einem Teilchendurchmesser von 10 bis 200 nm enthält. This object is achieved by a polymeric composition with pesticide-resistant and light-stable properties which, in addition to the commonly used polyethylene resin and / or ethylene-vinyl acetate copolymer and the alkylated amine as light stabilizer, contains micronized zinc oxide particles with a particle diameter of 10 to 200 nm.
Überraschenderweise wurde nämlich gefunden, daß bei Verwendung von mikronisierten Zinkoxidpartikeln mit einem Teilchendurchmesser von 10 und 200 nm transparente Folien hergestellt werden können, die sich von denen, die kein Zinkoxid enthalten, in ihrer Transparenz fast nicht unterscheiden lassen. In der polymeren Zusammensetzung wirkt das Zinkoxid dieser Korngröße trotz des geringen Durchmessers noch ausreichend als Barriere für UV-Licht bis zu einer Wellenlänge von 390 nm und ist andererseits ein hervorragendes Stabilisierungsmittel gegen Pestizide, die Halogen enthalten. Durch diese Maßnahmen wird eine Zerset zung der alkylierten Amine verhindert. Aufgrund der Teil- chendurchmesser des mikronisierten Zinkoxids bleiben die aus der erfindungsgemäßen polymeren Zusammensetzung hergestellten Folien weiterhin transparent. Surprisingly, it has been found that when using micronized zinc oxide particles with a particle diameter of 10 and 200 nm, transparent films can be produced which are almost indistinguishable in their transparency from those which do not contain zinc oxide. In the polymeric composition, the zinc oxide of this grain size, despite the small diameter, still acts sufficiently as a barrier for UV light up to a wavelength of 390 nm and is also an excellent stabilizer against pesticides that contain halogen. Through these measures, a decomposition Prevention of alkylated amines prevented. Because of the particle diameter of the micronized zinc oxide, the films produced from the polymeric composition according to the invention remain transparent.
In einer bevorzugten Ausführungsform enthält die polymere Zusammensetzung ein Ethylen-Vinylacetat-Copolymer in Kombination mit Polyethylen niedriger Dichte oder linearem Polyethylen niedriger Dichte. Als Lichtstabilisierungsmittel wird bevorzugt ein alkyliertes Amin der Formeln I oder II verwendet. Es handelt sich dabei um sogenannte HALS (Hindred Amin Light Stabilizers). In a preferred embodiment, the polymeric composition contains an ethylene-vinyl acetate copolymer in combination with low density polyethylene or linear low density polyethylene. An alkylated amine of the formulas I or II is preferably used as the light stabilizer. These are so-called HALS (Hindred Amin Light Stabilizers).
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung der polymeren Zusammensetzung, wobei die einzelnen Komponenten gemischt, erhitzt, geschmolzen und nach dem Abkühlen granuliert werden. So können die polymeren Zusammensetzungen gemäß der Erfindung beispielsweise auch in hochkonzentrierter Form als granuliertes Masterbatch hergestellt werden, das dann unter Hinzufugung weiterer polymerer Grundmaterialien verarbeitet wird. Another object of the invention is a method for producing the polymeric composition, wherein the individual components are mixed, heated, melted and granulated after cooling. For example, the polymeric compositions according to the invention can also be produced in highly concentrated form as a granulated masterbatch, which is then processed with the addition of further polymeric base materials.
Mit den aus der erfindungsgemäßen Polymerzusammensetzungin üblicher Weise hergestellte Folien können Rosenkultivierungen in Treibhäusern verbessert werden, da die Rose films in greenhouses can be improved with the films produced in a conventional manner from the polymer composition according to the invention, since the
Pflanzen besser vor der Rosenkrankheit "Botrytis" geschützt werden können. Das Wachstum der diese Krankheit verursachenden Schädlinge wird durch UV-Licht einer Wellenlänge von 370 nm stimuliert. Gerade das UV-Licht die- ser Wellenlänge wird jedoch durch die Zinkoxidpartikel in der erfindungsgemäßen Folie absorbiert. Plants can be better protected from the "Botrytis" rose disease. The growth of the pests causing this disease is stimulated by UV light with a wavelength of 370 nm. UV light in particular However, this wavelength is absorbed by the zinc oxide particles in the film according to the invention.
Die folgenden Beispiele sollen die Erfindung näher erläutern. The following examples are intended to explain the invention in more detail.
Beispiele Examples
Beispiele 1 bis 3, Vergleichsbeispiele 1 bis 4 Examples 1 to 3, Comparative Examples 1 to 4
Es wurde eine einschichtige Folie mit einem Durchmesser von 180 μm aus Polyethylen niedriger Dichte mit einem Schmelzindex von 0,3 und verschiedenen Anteilen an mikronisiertem Zinkoxid mit einem Durchmesser von 60 nm und alkylierten Aminen hergestellt. Als Amine wurden die Handelsprodukte der Fa. Ciba-Geigy Chimassorb 944 (Formel I) und Chimassorb 119 (Formel II) verwendet. Die Resistenz gegen Pestizide wurde gemessen, indem einmal pro Monat das bekannte Pestizid "Permethrin" auf die Proben gesprüht wurde. Die Proben wurden dann einem Xenotest 1200 (2) (UV-Prüfgerät der Fa. Hanau) ausgesetzt. Hierbei handelt es sich um einen Test, bei dem die Proben innerhalb kurzer Zeit der jährlichen UV-Strahlung ausgesetzt werden. Damit läßt sich der Alterungsprozeß der Folie in kurzer Zeit simulieren. A single-layer film with a diameter of 180 μm was produced from low-density polyethylene with a melt index of 0.3 and various proportions of micronized zinc oxide with a diameter of 60 nm and alkylated amines. The commercial products from Ciba-Geigy Chimassorb 944 (Formula I) and Chimassorb 119 (Formula II) were used as amines. Resistance to pesticides was measured by spraying the known pesticide "permethrin" onto the samples once a month. The samples were then exposed to a Xenotest 1200 (2) (UV tester from Hanau). This is a test in which the samples are exposed to the annual UV radiation within a short time. This allows the aging process of the film to be simulated in a short time.
Die Restreißdehnung wurde dann als Maß für den Alterungs- grad der Folie ermittelt. Die Ergebnisse werden angegeben in kLy (kiloLangley) bis zu 50 %iger restlicher Ausdeh- nung. Die mit "Permethrin" besprühten und unbesprühten Proben wurden in einer getrennten Vorrichtung behandelt, um eine Kontamination zu verhindern. Es wurde eine 1 %ige Emulsion von "Permethrin" in Ethanol/Hexan (Verhältnis 9:1) verwendet. Der Xenotest wurde auf 70 °C Betriebstemperatur im Gerät (black panel temperature) und eine rela tiven Luftfeuchtigkeit von 60 % eingestellt. Die Proben wurden auf Plexiglas fixiert. Tabelle 1 zeigt die Zusammensetzung der hergestellten Folien, Tabelle 2 zeigt die Ergebnisse der Messungen bei den gemäß Tabelle 1 zusammengesetzten Folien. The residual elongation at break was then determined as a measure of the degree of aging of the film. The results are given in kLy (kiloLangley) up to 50% residual expansion. The samples sprayed with "permethrin" and unsprayed were treated in a separate device to prevent contamination. A 1% emulsion of "permethrin" in ethanol / hexane (ratio 9: 1) was used. The Xenotest was set to 70 ° C operating temperature in the device (black panel temperature) and a rela tive air humidity of 60%. The samples were fixed on plexiglass. Table 1 shows the composition of the films produced, Table 2 shows the results of the measurements for the films assembled according to Table 1.
1 mikronisiertes ZnO 1 micronized ZnO
2 handelsübliches ZnO 2 commercial ZnO
3 Zinkstearat wurde als Prozeßhilfsmittel verwendet. 3 Zinc stearate was used as a processing aid.
V = Verleichsbeispiel B = Beispiel V = comparative example B = example
Alle Angaben in Gew% . All figures in% by weight.
V = Vergleichsbeispiel B = Beispiel V = comparative example B = example
Aus den Tabellen ist ersichtlich, daß bei Folien, die mikronisiertes Zinkoxid enthalten, zwischen besprühten und nicht besprühten Proben nur ein geringer Unterschied bezüglich der Restreißdehnung besteht im Vergleich zu Folien, die kein mikronisiertes Zinkoxid enthalten. Hier zeigen die mit Pestizid behandelten Folien eine erheblich geringere Restreißdehnung als die unbehandelten Folien. Bei den Folien, die Zinkoxid des Teilchendurchmessers 60 nm enthalten, fällt weiterhin auf, daß diese eine gute Lichtdurchlässigkeit und eine gute Absorption für UV- Strahlung einer Wellenlänge von 370 nm besitzen und dadurch der Folie für Gewächshäuser optimale Eigenschaften verleihen. Beispiele 4 und 5, Vergleichsbeispiele 5 bis 8 From the tables it can be seen that in films which contain micronized zinc oxide, there is only a slight difference in the elongation at break between sprayed and non-sprayed samples compared to films which do not contain micronized zinc oxide. Here the films treated with pesticide show a significantly lower elongation at break than the untreated films. In the films containing zinc oxide with a particle diameter of 60 nm, it is also noticeable that they have good light transmission and good absorption for UV radiation of a wavelength of 370 nm and thus give the film optimal properties for greenhouses. Examples 4 and 5, Comparative Examples 5 to 8
Es wurden koextrudierte Mehrschichtfolien eines Durchmessers von 180 um hergestellt, die im wesentlichen bestehen aus Ethylen-Vinylacetat-Copolymer mit einer Coextruded multilayer films with a diameter of 180 μm were produced, which essentially consist of an ethylene-vinyl acetate copolymer with a
Schichtkonfiguration von A = 1:4, B = 2:4 und C = 1:4. In allen drei Schichten wird mikronisiertes Zinkoxid und das Lichtstabilisierungsmittel hinzugefügt. Die Schicht A ist ein Basisharz von Polyethylen niedriger Dichte, die Layer configuration of A = 1: 4, B = 2: 4 and C = 1: 4. Micronized zinc oxide and the light stabilizer are added in all three layers. Layer A is a base resin of low density polyethylene that
Schicht B ist ein Basisharz von Ethylen-Vinylacetat-Copolymer mit einem Anteil an Vinylacetat von 12 Gew% . Die Schicht C ist identisch zur Schicht B. Weiterhin werden hinzugefügt Antitaumittel und infrarot absorbierende Additive wie folgt (alle Angaben in Gew%): Layer B is a base resin of ethylene-vinyl acetate copolymer with a vinyl acetate content of 12% by weight. Layer C is identical to layer B. Furthermore, anti-thaw agents and infrared absorbing additives are added as follows (all figures in% by weight):
Schicht A Antitaumittel 0,5 % Layer A antifreeze 0.5%
IR-absorbierendes Mittel 1 % IR absorbing agent 1%
Schicht B Antitaumitel 3,0 % Layer B anti-thaw agent 3.0%
IR-absorbierendes Mittel 5 % IR absorbent 5%
Schicht C Antitaumittel 1,0 % Layer C antifreeze 1.0%
IR-absorbierendes Mittel 2 % IR absorbing agent 2%
Aus Tabelle 3 ist die Zusammensetzung der einzelnen Folien zu entnehmen. Tabelle 4 zeigt die Eigenschaften. Table 3 shows the composition of the individual films. Table 4 shows the properties.
Alle Angaben in Gew%. All figures in% by weight.
1 mikronisiertes ZnO 1 micronized ZnO
2 handelsübliches ZnO 2 commercial ZnO
3 Zinkstearat wurde als Prozeßhilfsmittel zugegeben. 3 Zinc stearate was added as a processing aid.
Aus den Tabellen 3 und 4 kann ersehen werden, daß insbesondere die Folien, die mikronisiertes Zinkoxid eines Durchmessers von 60 nm besitzen, hervorragende Eigenschaften bezüglich der Lichtdurchlässigkeit besitzen und darüber hinaus auch bei Behandlung mit Pestiziden ihre Stabilität behalten. Sie sind dadurch solchen Folien, die Zinkoxid eines Durchmessers von 1 μm enthalten, überlegen und ebenfalls solchen, die gar kein Zinkoxid enthalten. It can be seen from Tables 3 and 4 that, in particular, the films which have micronized zinc oxide with a diameter of 60 nm have excellent properties with regard to light transmission and also maintain stability when treated with pesticides. As a result, they are superior to films that contain zinc oxide with a diameter of 1 μm and also to films that do not contain zinc oxide at all.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95933360A EP0729489A1 (en) | 1994-09-16 | 1995-09-12 | Polymer composition, a method of producing the same and a use therefor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944433018 DE4433018C1 (en) | 1994-09-16 | 1994-09-16 | Polymer composition, process for its preparation and its use |
| DEP4433018.9 | 1994-09-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1996009348A2 true WO1996009348A2 (en) | 1996-03-28 |
| WO1996009348A3 WO1996009348A3 (en) | 1996-06-20 |
Family
ID=6528384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1995/003577 WO1996009348A2 (en) | 1994-09-16 | 1995-09-12 | Polymer composition, a method of producing the same and a use therefor |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0729489A1 (en) |
| DE (1) | DE4433018C1 (en) |
| WO (1) | WO1996009348A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000050504A1 (en) * | 1999-02-23 | 2000-08-31 | Bayer Aktiengesellschaft | Plastic composites containing metal oxides |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1066840B1 (en) | 2000-04-28 | 2004-12-29 | Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica | Ventricular assist device |
| US6337362B1 (en) * | 2000-06-12 | 2002-01-08 | Elementis Specialties, Inc. | Ultraviolet resistant pre-mix compositions and articles using such compositions |
| EP1609816A1 (en) * | 2004-06-25 | 2005-12-28 | A. Schulman Plastics | Masterbatch Composition containing nano scalar zinc oxide for the production of transparent polyolefin films with UV-barrier properties |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6216356A (en) * | 1985-07-05 | 1987-01-24 | テイカ株式会社 | Functional synthetic resin film |
| IT1215455B (en) * | 1987-05-05 | 1990-02-14 | Ciba Geigy Spa | STABILIZING COMPOSITION FOR POLYETHYLENE INCLUDING COMPOUNDS CONTAINING PIPERIDINIC GROUPS AND METALLIC COMPOUNDS |
| EP0429731A1 (en) * | 1989-12-01 | 1991-06-05 | At Plastics Inc. | Composition for use in films |
| US5352725A (en) * | 1991-09-27 | 1994-10-04 | Kerr-Mcgee Chemical Corporation | Attenuation of polymer substrate degradation due to ultraviolet radiation |
| IT1269953B (en) * | 1994-06-27 | 1997-04-16 | Ciba Geigy Spa | POLYOLEFIN FILMS OR OLEFINE COPOLYMERS WITH IMPROVED LIGHT STABILITY AND INSECTICIDE RESISTANCE |
-
1994
- 1994-09-16 DE DE19944433018 patent/DE4433018C1/en not_active Expired - Fee Related
-
1995
- 1995-09-12 WO PCT/EP1995/003577 patent/WO1996009348A2/en not_active Application Discontinuation
- 1995-09-12 EP EP95933360A patent/EP0729489A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000050504A1 (en) * | 1999-02-23 | 2000-08-31 | Bayer Aktiengesellschaft | Plastic composites containing metal oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0729489A1 (en) | 1996-09-04 |
| DE4433018C1 (en) | 1996-04-25 |
| WO1996009348A3 (en) | 1996-06-20 |
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