WO2007063240A1 - Fluorescent covering films for greenhouses - Google Patents

Fluorescent covering films for greenhouses Download PDF

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Publication number
WO2007063240A1
WO2007063240A1 PCT/FR2006/051224 FR2006051224W WO2007063240A1 WO 2007063240 A1 WO2007063240 A1 WO 2007063240A1 FR 2006051224 W FR2006051224 W FR 2006051224W WO 2007063240 A1 WO2007063240 A1 WO 2007063240A1
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Prior art keywords
material according
nature
diffusing
ppm
mineral
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PCT/FR2006/051224
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French (fr)
Inventor
Gérard Pichon
Loïc Baralon
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Societe D'extrusion Du Polyethylene A. Barbier & Cie
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Publication of WO2007063240A1 publication Critical patent/WO2007063240A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Definitions

  • the present invention relates to a polyolefin polymer material capable of transforming light, combining inorganic molecules with fluorescent properties and mineral fillers capable of diffusing light.
  • Such a material can therefore be advantageously used in the manufacture of greenhouse cover films.
  • lamps especially high-voltage sodium lamps.
  • inorganic molecules having fluorescence properties in particular complexes of organo-metallic and / or metallic oxides of rare earths and / or other metals, in particular of Europium, Terbium, Yttrium, Vanadium , Zirconium or Barium, have been used successfully for this application.
  • Such molecules are for example described in EP-A-1,035,160 and FR-A-2,846,663.
  • a material according to the invention comprises a polymeric matrix and at least one fluorescent additive. It is further characterized by the presence in the matrix of at least one mineral filler of diffusing nature.
  • filler is intended to mean inorganic molecules having light scattering properties.
  • these fillers are advantageously chosen from the group comprising fillers based on calcium carbonate (CaCO 3 ) - in particular chalks, calcites or marbles -, kaolins, talcs, silica aluminates including
  • such molecules are used in the field of plastics, in particular in the manufacture of greenhouse films, for their ability to homogenize the distribution of light rays.
  • the mineral fillers with a diffusing nature are those based on calcium carbonate (CaCO 3 ), advantageously comprising at least 90% of CaCO 3 .
  • Typical compounds within this definition are chalks, calcites and marbles. Chalks are particularly preferred.
  • such charges have a mean diameter (D50) of between 1 and 6 ⁇ m.
  • these diffusing-type mineral fillers represent from 1000 to 100,000 ppm (parts per million by weight) of the polymeric matrix.
  • Particularly suitable polymers for the manufacture of the materials according to the invention are polyolefins, in particular LDPE (low density polyethylene) and copolymers EVA (ethylene vinyl acetate), EBA (ethylene butyl acetate) or EMA (ethylene acetate). methyl).
  • LDPE low density polyethylene
  • EVA ethylene vinyl acetate
  • EBA ethylene butyl acetate
  • EMA ethylene acetate
  • the molecules having fluorescence properties the molecules of inorganic nature are advantageously used for the reasons mentioned above. In practice, it is essentially complexes of organometallic oxides and / or rare earth metal and / or other metals, especially Europium, Terbium, Yttrium, Vanadium, Zirconium or barium.
  • These molecules can be characterized by variable re-emission domains. Thus they can re-emit only in the red, which is favorable to the growth of plants, but also in the blue corresponding to wavelengths having an impact on plant differentiation.
  • the fluorescent additive is advantageously incorporated into the polymer matrix at a level of 500 to 10,000 ppm.
  • the amount of fluorescent additive to be added is therefore less than or equal to 4000 ppm, more advantageously less than or equal to 1000 ppm.
  • Fluorescent additive mixtures of different types may also be used.
  • Light stabilizers modified amine type HALS (Hindered Amine Light Stabilizers) or nickel chelate salt type, thus give the polymer matrix resistance to degradation by UV.
  • modified amine type HALS Hindered Amine Light Stabilizers
  • nickel chelate salt type thus give the polymer matrix resistance to degradation by UV.
  • anti-drops also called “anti-fog”
  • anti-fog additives “anti-drops”, also called “anti-fog”
  • Both the fluorescent additive and the mineral filler of diffusing nature are generally in the form of inert and stable powders. Their incorporation into the polymer matrix can therefore be done by kneading these powders with the molten polymer using a double screw or a co-kneader to form a "compound".
  • This mixture can be used for the production of a film, for example by the extrusion blow molding technique.
  • the at least two components fluorescent additive and diffusing filler are distributed homogeneously in the polymer matrix.
  • the incorporation of the fluorescent additive and the mineral filler can also be carried out directly during the extrusion operation of the film.
  • the powders should be introduced via a masterbatch (powder concentrate pre-dispersed in a polymer, compatible with the polyolefin matrix used for the production of the film).
  • masterbatch powder concentrate pre-dispersed in a polymer, compatible with the polyolefin matrix used for the production of the film.
  • the at least two components fluorescent additive and diffusing filler
  • the fluorescent additive (s) and the mineral filler (s) with a diffusing nature are thus homogeneously distributed in the polymer matrix.
  • a material according to the invention is more particularly intended for the manufacture of blankets or greenhouse walls.
  • the term "greenhouse” should be understood here in a broad sense as any plastic shelter used in agriculture or horticulture for the protection and development of crops. Examples include greenhouses, large tunnels, small tunnels or flat tarpaulins.
  • a material according to the invention is advantageously in the form of a continuous film typically having a thickness of between 10 and 500 ⁇ m, preferably between 50 and 250 ⁇ m.
  • Such a film also has the characteristic of being transparent, even if the presence of the mineral charges diffusing nature can cause the appearance of a slight haze ("haze") without consequence.
  • EH 1 The intensity of the signal emitted by the sample according to the invention (ECH 1) is significantly higher than that emitted by the sample of the prior art (ECH 2), although the normal content of Ksanta Red is 20%. weaker. This is the consequence of the introduction of the diffusing mineral CaCO3 (chalk). This increase in luminous intensity emitted is easily verifiable under WOOD light, both in back-diffusion mode and in transmission mode.
  • the material according to the invention is therefore characterized by a very clear improvement in the retransmission in the visible.
  • the presence of diffusing charges is also accompanied by a significant increase in the temperature inside the greenhouse, compared to prior art greenhouse plastics containing only fluorescent additives.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Soil Sciences (AREA)
  • Environmental Sciences (AREA)
  • Protection Of Plants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Greenhouses (AREA)

Abstract

The invention relates to a material comprising a polymeric matrix, at least one fluorescent additive and at least one mineral filler of scattering character. This material is intended for covering greenhouses in the agricultural or horticultural field.

Description

FILMS DE COUVERTURE DE SERRE FLUORESCENTS FLUORESCENT GREENHOUSE COVER FILMS
Domaine techniqueTechnical area
L'invention concerne un matériau à base de polymère de type polyoléfine apte à transformer la lumière, associant des molécules inorganiques possédant des propriétés de fluorescence et des charges minérales aptes à diffuser la lumière.The present invention relates to a polyolefin polymer material capable of transforming light, combining inorganic molecules with fluorescent properties and mineral fillers capable of diffusing light.
En raison de la présence des molécules inorganiques possédant des propriétés de fluorescence, un tel matériau absorbe et convertit les radiations UV solaires, à l'origine de la dégradation des matières plastiques, en radiations de longueur d'onde dans le domaine du visible, pouvant favoriser la croissance des végétaux.Due to the presence of inorganic molecules with fluorescent properties, such a material absorbs and converts solar UV radiation, the cause of plastic degradation, into visible wavelength promote plant growth.
Un tel matériau peut donc être avantageusement utilisé dans la fabrication des films de couverture de serre.Such a material can therefore be advantageously used in the manufacture of greenhouse cover films.
Etat de la techniqueState of the art
L'impact de la lumière sur les plantes a été largement étudié. Une des principales fonctions de la lumière est de jouer le rôle de source d'énergie dans le processus de photosynthèse, favorisant ainsi la croissance des plantes. En fait, seule la partie visible de la lumière, plus précisément les radiations correspondant à la lumièreThe impact of light on plants has been widely studied. One of the main functions of light is to act as a source of energy in the process of photosynthesis, thus promoting the growth of plants. In fact, only the visible part of the light, more precisely the radiations corresponding to the light
(βb te (g- 1£ θfl fapα'tag fe -750 nm)), et en particulier la lumière rouge, sont utiles à la plante. Cette fraction représente à peine la moitié du rayonnement solaire. En outre dans le cas de culture en serre, la couverture et l'infrastructure de la serre jouent le rôle d'écran de sorte que le facteur de transmission n'est que de 60 à 80%.(βb te (g-1 θfl fapα'tag fe -750 nm)), and in particular the red light, are useful to the plant. This fraction represents barely half of the solar radiation. Moreover, in the case of greenhouse cultivation, the cover and the infrastructure of the greenhouse play the role of screen so that the transmission factor is only 60 to 80%.
Pour apporter un appoint de lumière aux cultures en serre, il a été envisagé de les éclairer artificiellement, à l'aide de lampes, en particulier des lampes à vapeur de sodium haute tension. Toutefois, il faut assurer un éclairage de forte intensité, appliqué la majeure partie du temps, et qui doit être capable d'éclairer de manière homogène toutes les parties de la plante. On constate que les contraintes techniques, énergétiques et financières pour de telles lampes sont importantes.To add light to greenhouse crops, it has been envisaged to light them artificially, using lamps, especially high-voltage sodium lamps. However, it is necessary to ensure a lighting of strong intensity, applied most of the time, and which must be able to illuminate in a homogeneous all parts of the plant. It is noted that the technical, energy and financial constraints for such lamps are important.
Alternativement, il a été proposé d'intégrer dans les couvertures de serres, des molécules présentant des propriétés de luminescence, et plus particulièrement de fluorescence c'est-à-dire, pour ce qui concerne le film plastique de couverture de serre, capables d'absorber des rayonnements ultraviolets (UV) et de réémettre de la lumière dans le visible, plus précisément dans le bleu ou le rouge.Alternatively, it has been proposed to integrate in greenhouse covers, molecules having luminescence properties, and more particularly fluorescence that is to say, with regard to the plastic film greenhouse cover, capable of absorb ultraviolet (UV) radiation and re-emit light in the visible, specifically in blue or red.
Dans le passé, certains films fluorescents à base de PVC ont été mis au point et commercialisés. Toutefois, l'utilisation de ce type de films ne s'est pas développée pour des raisons de performances mécaniques, d'environnement et de coût.In the past, some fluorescent PVC-based films have been developed and marketed. However, the use of this type of film has not developed for reasons of mechanical performance, environment and cost.
Concernant les films de serre à base de polyoléfines, il a tout d'abord été tenté d'utiliser des molécules organiques fluorescentes, connues et utilisées par ailleurs. Toutefois, il s'est avéré que ces molécules étaient peu adaptées car leur émission fluorescente disparaissait après quelques mois, alors que la durée de vie préconisée pour les films de serre est de l'ordre de 3 à 5 ans.As regards the polyolefin-based greenhouse films, it was first of all attempted to use fluorescent organic molecules known and used elsewhere. However, it turned out that these molecules were unsuitable because their fluorescent emission disappeared after a few months, while the recommended lifetime for greenhouse films is of the order of 3 to 5 years.
En revanche, des molécules inorganiques possédant des propriétés de fluorescence, notamment des complexes d'oxydes organo-métalliques et/ou métalliques de terres rares et/ou d'autres métaux, notamment d'Europium, de Terbium, d'Yttrium, de Vanadium, de Zirconium ou de Barium, ont été utilisées avec succès pour cette application. De telles molécules sont par exemple décrites dans les documents EP-A-I 035 160 et FR- A-2 846 663.On the other hand, inorganic molecules having fluorescence properties, in particular complexes of organo-metallic and / or metallic oxides of rare earths and / or other metals, in particular of Europium, Terbium, Yttrium, Vanadium , Zirconium or Barium, have been used successfully for this application. Such molecules are for example described in EP-A-1,035,160 and FR-A-2,846,663.
Ces additifs fluorescents ont toutefois un coût très élevé, ce qui majore fortement le prix au mètre carré du film de couverture de serre. II existe donc un besoin évident de développer des matériaux destinés à la couverture des serres, présentant des niveaux de réémission satisfaisants tout en possédant un coût de production modéré.These fluorescent additives however have a very high cost, which strongly increases the price per square meter of the greenhouse cover film. There is therefore a clear need to develop materials for greenhouse cover with satisfactory retransmission levels while having a moderate cost of production.
5 Description de l'inventionDescription of the invention
De manière classique, un matériau selon l'invention comprend une matrice polymérique et au moins un additif fluorescent. Il se caractérise en outre par la présence dans la matrice d'au moins une charge minérale à caractère diffusant.In a conventional manner, a material according to the invention comprises a polymeric matrix and at least one fluorescent additive. It is further characterized by the presence in the matrix of at least one mineral filler of diffusing nature.
10 On entend par le terme "charge minérale à caractère diffusant", des molécules inorganiques possédant des propriétés de diffusion de la lumière. Dans le cadre de l'invention, ces charges sont avantageusement choisies dans le groupe comprenant les charges à base de carbonate de calcium (CaCO3) - notamment les craies, les calcites ou les marbres -, les kaolins, les talcs, les silico-aluminates notamment deThe term "diffusing mineral filler" is intended to mean inorganic molecules having light scattering properties. In the context of the invention, these fillers are advantageously chosen from the group comprising fillers based on calcium carbonate (CaCO 3 ) - in particular chalks, calcites or marbles -, kaolins, talcs, silica aluminates including
15 potassium, ou les silices.Potassium, or silicas.
De manière connue, de telles molécules sont utilisées dans le domaine des matières plastiques, en particulier dans la fabrication des films pour serre, pour leur capacité à homogénéiser la répartition des rayonnements lumineux àIn a known manner, such molecules are used in the field of plastics, in particular in the manufacture of greenhouse films, for their ability to homogenize the distribution of light rays.
20 l'intérieur de la serre sur une surface donnée et à rendre l'irradiation lumineuse moins directe. Le second effet procuré par l'adjonction de telles charges est un effet thermique. De fait, l'incorporation de ce type d'additifs au sein d'une matrice polyoléfinique lui confère la capacité de mieux retenir les radiations20 inside the greenhouse on a given surface and make the light irradiation less direct. The second effect provided by the addition of such charges is a thermal effect. In fact, the incorporation of this type of additive into a polyolefinic matrix gives it the ability to better retain radiation.
( gl garfii fc= 7 à 20 microns) réémises par le sol durant la nuit. En(gl garfii fc = 7 to 20 microns) re-emitted by the soil during the night. In
25 pratique, cela permet de maintenir la chaleur à l'intérieur de la serre.In practice, this keeps the heat inside the greenhouse.
De manière surprenante, il a été montré, dans le cadre de l'invention, que ces charges minérales à caractère diffusant potentialisaient la réémission dans le visible des rayonnements UV absorbés par les additifs fluorescents. Sans vouloir être lié à une quelconque théorie, il peut être avancé que les particules de ces charges ont pour effet de diffuser la lumière incidente et ainsi de provoquer une augmentation du chemin optique au sein du matériau, d'où une probabilité accrue de conversion des photons UV en photons visibles par les molécules à propriétés fluorescentes.Surprisingly, it has been shown, in the context of the invention, that these mineral fillers with a diffusing nature potentiate the visible re-emission of the UV radiation absorbed by the fluorescent additives. Without wishing to be bound by any theory, it can be argued that the particles of these charges have the effect of diffusing the incident light and thus causing an increase in the optical path within the material, hence an increased probability of conversion of UV photons in photons visible by molecules with fluorescent properties.
De manière très avantageuse, les charges minérales à caractère diffusant sont celles à base de carbonate de calcium (CaCO3), comprenant avantageusement au moins 90% de CaCO3. Des composés classiques répondant à cette définition sont les craies, les calcites et les marbres. Les craies sont particulièrement préférées. Dans un mode de réalisation privilégiée, de telles charges présentent un diamètre moyen (D50) compris entre 1 et 6 μm.Very advantageously, the mineral fillers with a diffusing nature are those based on calcium carbonate (CaCO 3 ), advantageously comprising at least 90% of CaCO 3 . Typical compounds within this definition are chalks, calcites and marbles. Chalks are particularly preferred. In a preferred embodiment, such charges have a mean diameter (D50) of between 1 and 6 μm.
En effet, il s'avère que dans la cadre de l'invention, ce type de charges donne des résultats particulièrement satisfaisants. Outre leur fort pouvoir diffusant, les charges à base de carbonate de calcium ne perturbent pas la transmission globale de la lumière visible. En outre, c'est une matière première économique, disponible et facile à formuler.Indeed, it turns out that in the context of the invention, this type of charges gives particularly satisfactory results. In addition to their high diffusing power, calcium carbonate-based fillers do not disturb the overall transmission of visible light. In addition, it is an economic raw material, available and easy to formulate.
Avantageusement, ces charges minérales à caractère diffusant représentent de 1000 à 100 000 ppm (partie par million en poids) de la matrice polymérique.Advantageously, these diffusing-type mineral fillers represent from 1000 to 100,000 ppm (parts per million by weight) of the polymeric matrix.
Des mélanges de charges minérales à caractère diffusant de nature différente peuvent également être envisagés.Mixtures of mineral fillers with diffuse nature of different nature can also be envisaged.
Des polymères particulièrement adaptés à la fabrication des matériaux selon l'invention sont les polyoléfines, en particulier le PEBD (polyéthylène basse densité) et les copolymères EVA (éthylène acétate de vinyle), EBA (éthylène acétate de butyle) ou EMA (éthylène acétate de méthyle). Concernant les molécules possédant des propriétés de fluorescence, les molécules de nature inorganique sont avantageusement utilisées pour les raisons mentionnées ci-dessus. En pratique, il s'agit essentiellement de complexes d'oxydes organo-métalliques et/ou métalliques de terres rares et/ou d'autres métaux, notamment d'Europium, de Terbium, d'Yttrium, de Vanadium, de Zirconium ou de Barium.Particularly suitable polymers for the manufacture of the materials according to the invention are polyolefins, in particular LDPE (low density polyethylene) and copolymers EVA (ethylene vinyl acetate), EBA (ethylene butyl acetate) or EMA (ethylene acetate). methyl). As regards the molecules having fluorescence properties, the molecules of inorganic nature are advantageously used for the reasons mentioned above. In practice, it is essentially complexes of organometallic oxides and / or rare earth metal and / or other metals, especially Europium, Terbium, Yttrium, Vanadium, Zirconium or barium.
Ces molécules peuvent se caractériser par des domaines de réémission variables. Ainsi elles peuvent réémettre uniquement dans le rouge, ce qui est favorable à la croissance des végétaux, mais aussi dans le bleu correspondant à des longueurs d'onde ayant un impact sur la différentiation végétale.These molecules can be characterized by variable re-emission domains. Thus they can re-emit only in the red, which is favorable to the growth of plants, but also in the blue corresponding to wavelengths having an impact on plant differentiation.
De tels produits sont actuellement commercialisés, notamment l'additif Ksanta Red (société RANITA) émettant dans le rouge qui s'avère tout à fait adapté à la mise en œuvre de l'invention.Such products are currently marketed, including the additive Ksanta Red (company RANITA) emitting in the red which is quite suitable for the implementation of the invention.
De manière usuelle, l'additif fluorescent est avantageusement incorporé à la matrice polymérique à hauteur de 500 à 10 000 ppm. Toutefois, dans l'usage antérieur, pour avoir un niveau de réémission satisfaisant, il était recommandé d'ajouter au moins 1 000, voire au moins 4 000 ppm. Dans le cadre de l'invention, et en raison de la présence des charges minérales à caractère diffusant, il est possible de diminuer la quantité d'additif fluorescent d'au moins 30 à 50% pour obtenir un niveau de réémission équivalent. La quantité d'additif fluorescent à ajouter est donc inférieure ou égale à 4 000 ppm, encore plus avantageusement inférieure ou égale à 1 000 ppm.Usually, the fluorescent additive is advantageously incorporated into the polymer matrix at a level of 500 to 10,000 ppm. However, in previous use, to have a satisfactory level of retransmission, it was recommended to add at least 1000, or even at least 4000 ppm. In the context of the invention, and because of the presence of the diffusing nature fillers, it is possible to reduce the amount of fluorescent additive by at least 30 to 50% to obtain an equivalent level of retransmission. The amount of fluorescent additive to be added is therefore less than or equal to 4000 ppm, more advantageously less than or equal to 1000 ppm.
Des mélanges d'additifs fluorescents de nature différente peuvent également être utilisés.Fluorescent additive mixtures of different types may also be used.
D'autres molécules peuvent en outre être ajoutées à la matrice polymérique additionnée de l'additif fluorescent et de la charge diffusante. Des stabilisants lumière, de type aminé modifiée HALS (Hindered Aminé Light Stabilizers) ou du type sel chélate de Nickel, confèrent ainsi à la matrice polymérique une résistance à la dégradation par les UV.In addition, other molecules may be added to the polymeric matrix supplemented with the fluorescent additive and the diffusing charge. Light stabilizers, modified amine type HALS (Hindered Amine Light Stabilizers) or nickel chelate salt type, thus give the polymer matrix resistance to degradation by UV.
Par ailleurs, des additifs "anti-gouttes", aussi nommés "antibuée", ont la propriété de migrer à la surface de la matrice polymère, réduisant sa tension de surface et inhibant ainsi la formation de gouttelettes d'eau de condensation.Moreover, additives "anti-drops", also called "anti-fog", have the property of migrating to the surface of the polymer matrix, reducing its surface tension and thus inhibiting the formation of condensation water droplets.
Aussi bien l'additif fluorescent que la charge minérale à caractère diffusant se présentent généralement sous forme de poudres inertes et stables. Leur incorporation dans la matrice polymérique peut donc se faire en malaxant ces poudres avec le polymère fondu à l'aide d'une double vis ou d'un co-malaxeur pour former un "compound".Both the fluorescent additive and the mineral filler of diffusing nature are generally in the form of inert and stable powders. Their incorporation into the polymer matrix can therefore be done by kneading these powders with the molten polymer using a double screw or a co-kneader to form a "compound".
Ce mélange peut servir à la réalisation d'un film, par exemple par la technique d'extrusion soufflage. Selon ce protocole, les au moins deux composants (additif fluorescent et charge minérale à caractère diffusant) sont répartis de manière homogène dans la matrice polymérique.This mixture can be used for the production of a film, for example by the extrusion blow molding technique. According to this protocol, the at least two components (fluorescent additive and diffusing filler) are distributed homogeneously in the polymer matrix.
L'incorporation de l'additif fluorescent et de la charge minérale peut également être réalisée directement lors de l'opération d'extrusion du film. Dans ce cas, il convient que les poudres soient introduites via un mélange-maître (concentré de poudres pré-dispersées dans un polymère, compatible avec la matrice poly- oléfinique utilisé pour la fabrication du film). Ceci permet également de garantir que les au moins deux composants (additif fluorescent et charge minérale à caractère diffusant) soient répartis de manière homogène dans la matrice polymérique. Dans le cadre de l'invention, le(s) additif(s) fluorescent(s) et la ou les charge(s) minérale(s) à caractère diffusant sont donc distribués de manière homogène dans la matrice polymérique.The incorporation of the fluorescent additive and the mineral filler can also be carried out directly during the extrusion operation of the film. In this case, the powders should be introduced via a masterbatch (powder concentrate pre-dispersed in a polymer, compatible with the polyolefin matrix used for the production of the film). This also makes it possible to guarantee that the at least two components (fluorescent additive and diffusing filler) are distributed homogeneously in the polymer matrix. In the context of the invention, the fluorescent additive (s) and the mineral filler (s) with a diffusing nature are thus homogeneously distributed in the polymer matrix.
Un matériau selon l'invention est plus particulièrement destiné à la fabrication de couvertures ou de parois de serre. Le terme "serre" doit être compris ici au sens large comme tout abri en plastique utilisé dans l'agriculture ou l'horticulture pour la protection et le développement des cultures. A titre d'exemples, il peut s'agir de serres, de grands tunnels, de petits tunnels ou de bâches à plat.A material according to the invention is more particularly intended for the manufacture of blankets or greenhouse walls. The term "greenhouse" should be understood here in a broad sense as any plastic shelter used in agriculture or horticulture for the protection and development of crops. Examples include greenhouses, large tunnels, small tunnels or flat tarpaulins.
Dans cette application, un matériau selon l'invention se présente avantageusement sous la forme d'un film continu ayant typiquement une épaisseur comprise entre 10 et 500 μm, préférentiellement entre 50 et 250 μm.In this application, a material according to the invention is advantageously in the form of a continuous film typically having a thickness of between 10 and 500 μm, preferably between 50 and 250 μm.
Un tel film présente en outre comme caractéristique d'être transparent, même si la présence des charges minérales à caractère diffusant peut entraîner l'apparition d'une léger trouble ("haze") sans conséquence.Such a film also has the characteristic of being transparent, even if the presence of the mineral charges diffusing nature can cause the appearance of a slight haze ("haze") without consequence.
Exemple de réalisationExample of realization
L'invention et les avantages qui en découlent ressortiront mieux de l'exemple de réalisation qui suit. Cet exemple n'a toutefois aucune portée limitative.The invention and the advantages thereof will become more apparent from the following exemplary embodiment. This example, however, has no limiting scope.
EXEMPLE 1EXAMPLE 1
Protocole expérimental :Experimental protocol :
• Mode de transformation : Sur une ligne d'extrusion-soufflage, les additifs (Charge minérale diffusante, Additif minéral fluorescent et Agent anti UV) ont tous été incorporés séparément à la matrice polymère, sous forme de mélange- maître, lors de l'opération d'extrusion en film. • Température d'extrusion : 2000C• Transformation mode: On an extrusion blow-molding line, the additives (Diffuse Mineral Charge, Fluorescent Mineral Additive and UV Agent) were all incorporated separately into the polymer matrix, in the form of a masterbatch, at the time of application. film extrusion operation. • Extrusion temperature: 200 0 C
• Epaisseur du film : 200 μm• Thickness of the film: 200 μm
Formulation :Formulation:
Figure imgf000009_0001
Figure imgf000009_0001
Résultats :Results:
Figure imgf000009_0002
Figure imgf000009_0002
• Propriété émissive mesurée sur un microspectrofluomètre HITACHI OLYMPUS (avec pré exposition en enceinte vieillissement accéléré aux UV SEPAP 12/24 pendant 16 heures et analyse statistique des mesures faites par le spectrofluomètre).• Emission property measured on a HITACHI OLYMPUS microspectrofluometer (with pre-exposure in SEPAP 12/24 accelerated aging chamber for 16 hours and statistical analysis of the measurements made by the spectrofluorometer).
L'intensité du signal émis par l'échantillon selon l'invention (ECH 1) est significativement plus intense que celui émis par l'échantillon de l'art antérieur (ECH 2), bien que la teneur normale en Ksanta Red soit 20% plus faible. Ceci est la conséquence de l'introduction de la charge minérale diffusante CaCO3 (craie). Cette augmentation d'intensité lumineuse émise est aisément vérifiable sous lumière de WOOD, aussi bien en mode rétro-diffusion qu'en mode de transmission.The intensity of the signal emitted by the sample according to the invention (ECH 1) is significantly higher than that emitted by the sample of the prior art (ECH 2), although the normal content of Ksanta Red is 20%. weaker. This is the consequence of the introduction of the diffusing mineral CaCO3 (chalk). This increase in luminous intensity emitted is easily verifiable under WOOD light, both in back-diffusion mode and in transmission mode.
Le matériau selon l'invention se caractérise donc par une amélioration très nette de la réémission dans le visible. La présence des charges à caractère diffusant s'accompagne également d'une augmentation sensible de la température à l'intérieur de la serre, par rapport aux plastiques de serre de l'art antérieur contenant uniquement des additifs fluorescents. The material according to the invention is therefore characterized by a very clear improvement in the retransmission in the visible. The presence of diffusing charges is also accompanied by a significant increase in the temperature inside the greenhouse, compared to prior art greenhouse plastics containing only fluorescent additives.

Claims

REVENDICATIONS
1/ Matériau comprenant une matrice polymérique dans laquelle sont distribués de manière homogène au moins un additif fluorescent de nature minérale et au moins une charge minérale à caractère diffusant caractérisé en ce que la charge minérale à caractère diffusant est choisi dans le groupe comprenant les charges à base de carbonate de calcium, les kaolins, les talcs, les silico-aluminates et/ou les silices .1 / material comprising a polymer matrix in which at least one fluorescent additive of mineral nature and at least one mineral filler of diffusing nature are homogeneously distributed, characterized in that the mineral filler with a diffusing nature is chosen from the group comprising the fillers base of calcium carbonate, kaolins, talcs, silico-aluminates and / or silicas.
2/ Matériau selon la revendication 1, caractérisé en ce que la charge minérale à caractère diffusant est une charges à base de carbonate de calcium, avantageusement choisie parmi les craies, les calcites ou les marbres.2 / material according to claim 1, characterized in that the mineral filler diffusing nature is a calcium carbonate based filler, preferably selected from chalks, calcites or marbles.
3/ Matériau selon la revendication 1 ou 2, caractérisé en ce que la matrice polymérique est constituée de polymères choisis dans la famille des polyoléfines, en particulier le PEBD, l'EVA, l'EBA ou l'EMA.3 / material according to claim 1 or 2, characterized in that the polymeric matrix consists of polymers selected from the family of polyolefins, in particular LDPE, EVA, EBA or EMA.
4/ Matériau selon l'une des revendications précédentes, caractérisé en ce que l'additif fluorescent de nature minérale est un complexe d'oxydes organo- métalliques et/ou métalliques de terres rares et/ou d'autres métaux, notamment d'Europium, de Terbium, d'Yttrium, de Vanadium, de Zirconium ou de Barium.4 / material according to one of the preceding claims, characterized in that the fluorescent additive of inorganic nature is a complex of organometallic oxides and / or metal rare earth and / or other metals, especially Europium , Terbium, Yttrium, Vanadium, Zirconium or Barium.
5/ Matériau selon l'une des revendications précédentes, caractérisé en ce que l'additif fluorescent de nature minérale est ajouté à hauteur de 500 à 10 000 ppm, préférentiellement dans une quantité inférieure ou égale à 4 000 ppm, encore plus avantageusement inférieure ou égale à 1 000 ppm.5 / material according to one of the preceding claims, characterized in that the fluorescent additive of mineral nature is added at a level of 500 to 10,000 ppm, preferably in an amount of less than or equal to 4000 ppm, even more advantageously less or equal to 1000 ppm.
6/ Matériau selon l'une des revendications précédentes, caractérisé en ce que la charge minérale à caractère diffusant est ajoutée à hauteur de 1 000 à 100 000 ppm. 11 Matériau selon l'une des revendications précédentes, caractérisé en ce qu'il comprend en outre des agents de résistance à la dégradation par les UV.6 / material according to one of the preceding claims, characterized in that the mineral filler of diffusing nature is added at 1000 to 100 000 ppm. 11 Material according to one of the preceding claims, characterized in that it further comprises agents for resistance to degradation by UV.
8/ Matériau selon l'une des revendications précédentes, caractérisé en ce que le matériau se présente sous la forme d'un film d'épaisseur comprise entre 10 et 500 μm, préférentiellement entre 50 et 250 μm.8 / material according to one of the preceding claims, characterized in that the material is in the form of a film thickness between 10 and 500 microns, preferably between 50 and 250 microns.
9/ Matériau selon l'une des revendications précédentes, caractérisé en ce qu'il est transparent.9 / material according to one of the preceding claims, characterized in that it is transparent.
10/ Couverture ou paroi de serre comprenant un matériau selon les revendications l à 9. 10 / Cover or greenhouse wall comprising a material according to claims 1 to 9.
PCT/FR2006/051224 2005-11-29 2006-11-24 Fluorescent covering films for greenhouses WO2007063240A1 (en)

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CN109206716A (en) * 2018-09-10 2019-01-15 海南自立环保科技有限公司 The masterbatch and its manufacturing method for promoting crop yield, can control degradation speed

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