WO2011033232A1 - Masterbatch composition useful in photovoltaic modules - Google Patents

Masterbatch composition useful in photovoltaic modules Download PDF

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Publication number
WO2011033232A1
WO2011033232A1 PCT/FR2010/051937 FR2010051937W WO2011033232A1 WO 2011033232 A1 WO2011033232 A1 WO 2011033232A1 FR 2010051937 W FR2010051937 W FR 2010051937W WO 2011033232 A1 WO2011033232 A1 WO 2011033232A1
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WIPO (PCT)
Prior art keywords
peroxide
composition
copolymer
tert
ethylperhexanoate
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PCT/FR2010/051937
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French (fr)
Inventor
Laurent Keromnes
Samuel Devisme
Catherine Corfias-Zuccalli
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Arkema France
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Publication date
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Publication of WO2011033232A1 publication Critical patent/WO2011033232A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the invention relates to a thermoplastic composition comprising an organic peroxide, its method of manufacture and the use of this composition for crosslinking polymers.
  • the subject of the invention is the use of this composition for the crosslinking of film encapsulating photovoltaic cells.
  • Organic peroxides are commonly used for the crosslinking of thermoplastic resins or elastomers, these resins and elastomers being grouped together in the present description under the term "polymers".
  • a peroxide is generally mixed with the polymer to be crosslinked in a first step, then a second polymer forming step is carried out and a third crosslinking step, for example by a heat treatment.
  • EP 2003701 and EP 1 164167 disclose compositions based on a copolymer of ethylene and vinyl acetate and a conventional peroxide.
  • the peroxides can be in liquid or solid form.
  • they are mixed at high temperature, that is to say a temperature above the softening point of the polymer, for example by extrusion or kneading; the peroxides are then usually in a liquid form.
  • a first problem is that the peroxides in this liquid form are difficult to mix with the polymer and a phenomenon of demixion of the peroxide can be observed.
  • a long mixing time at high temperature is necessary to allow the mixing of the peroxide in the polymer.
  • porous fillers such as silica or talc.
  • these porous peroxide-bearing fillers are mixed with the polymer, they are difficult to distribute uniformly and rapidly in the polymer; the use of these porous fillers can also reduce certain properties of the polymer, such as its transparency.
  • compositions comprising an additional polymer and peroxides in high concentration, which are well known to those skilled in the art under the name "masterbatch”. "Master batch”).
  • the photovoltaic modules comprise light-sensitive cells, called “photovoltaic cells", which are capable of converting light into current.
  • These cells are protected from their environment (moisture, oxygen, etc.) by protective layers which are usually made of glass or polymer.
  • protective layers which are usually made of glass or polymer.
  • One or more layers of encapsulant allow to adhere the cells to the protective layers.
  • the encapsulant must perfectly match the shape of the space existing between the cells and the other layers of protection of the module and this in order to avoid the presence of air which limits the efficiency of the photovoltaic module.
  • This encapsulant is generally a composition comprising an encapsulating polymer, generally a copolymer of ethylene and vinyl acetate, which is crosslinked with an organic peroxide.
  • the various constituent layers of the panel are assembled (cells, encapsulant layer (s) comprising peroxide, protective layers) and the panel thus assembled undergoes a firing step allowing the crosslinking of the encapsulant layer.
  • encapsulant layer comprising peroxide, protective layers
  • compositions according to the formulation of this document include:
  • the invention relates precisely to a new composition, useful as a masterbatch, which makes it possible to solve at least one of the above disadvantages.
  • composition (I) comprises:
  • the mass quantity of peroxide solution (b) being in the range of 5 to 30% relative to the total weight of the composition (I).
  • This novel composition can be advantageously used as a masterbatch for the crosslinking of polymer encapsulating in photovoltaic panels.
  • the crosslinking is fast and the introduction of the peroxide in the form of masterbatch makes it possible to improve the transparency of the encapsulating polymer.
  • the introduction of organic peroxide by a masterbatch is easier than the direct introduction of liquid or solid peroxide into the encapsulating polymer.
  • the polar-functional ethylenic monomer comprises from 3 to 20 carbon atoms, preferably from 4 to 8 atoms.
  • the polar-bearing ethylenic monomer is chosen from vinyl esters of saturated carboxylic acid, unsaturated carboxylic acids of carbon or (meth) acrylic acid esters of unsaturated carboxylic acid.
  • the ethylenic monomer may be chosen from vinyl acetate and methyl, ethyl or butyl (meth) acrylates. Most preferably, it is vinyl acetate.
  • the copolymer (a) comprises from 10 to 60% by weight of ethylenic monomer carrying a polar function relative to the total weight of the copolymer, preferably from 25 to 45% by weight.
  • the dispersion of the peroxide is improved when the copolymer comprises this range of ethylenic monomer.
  • the mass quantity of peroxide included in the composition (I) is in the range of 7 to 16%.
  • the peroxide (b) is tert-butyl 2-ethylperhexanoate.
  • the invention also relates to a method of manufacturing a composition (I) according to the invention comprising:
  • An advantage of this process is that the phenomenon of premature crosslinking of the composition is even more limited and that the manufacturing process is simple.
  • the temperature of the second process step is lower than the softening temperature of the copolymer, which is measured in the present application by the method is described in ASTM E 28-99 (2004), better known under the name "Ring and Bail”.
  • the copolymer is in the form of particles having an average volume of 1 to 1000 mm 3 , preferably 3 to 120 mm 3 .
  • the composition (I) is obtained directly in the form of particles without the need to reform particles. It can then easily be used as a masterbatch. By using particles having this particular volume, the uptake of the peroxide by the copolymer is excellent and there is little agglomeration between the particles.
  • Another subject of the invention is a composition obtained by the process according to the invention.
  • Another subject of the invention is a film comprising a mixture of the thermoplastic composition (I) and a second polymer chosen from polyolefins.
  • This film can be advantageously used as a film encapsulating photovoltaic cells.
  • the mass quantity of composition (I) relative to the total mass of the film is 3 to 30%, preferably 8 to 25%.
  • the invention also relates to a method of manufacturing a photovoltaic module comprising the steps:
  • the composition according to the invention to form the encapsulant film of the invention, the efficiency of the photovoltaic panel manufacturing processes is rapid and the encapsulant layer retains a high transparency, which allows to obtain a photovoltaic panel with a very good performance.
  • composition (I) produced by the process according to the invention comprises a copolymer (a) and an organic peroxide solution (b).
  • the copolymer (a) is a copolymer of ethylene and an ethylenic monomer carrying a polar function.
  • ethylenic monomer is understood to mean a monomer comprising an unsaturation capable of reacting with ethylene in a radical process.
  • polar function is meant a function having a dipole moment, such as amine, alcohol, urethane, acid or ester functions.
  • the polar function is an acid function or an ester function.
  • the polar-functional ethylenic monomer preferably comprises from 3 to 20 carbon atoms, preferentially from 4 to 8 carbon atoms.
  • copolymer (a) By way of example of copolymer (a), mention may be made of copolymers of ethylene and of a vinyl ester of carboxylic acid, copolymers of ethylene with an unsaturated carboxylic acid or copolymers of ethylene and of an alkyl acrylate and or methacrylates, grouped together in the present application under the term (meth) acrylate.
  • the ethylenic monomer may be chosen from vinyl acetate and methyl, ethyl or butyl (meth) acrylates.
  • the quantity by mass of ethylenic monomer relative to the total weight of the copolymer (a) can be in the range of from 1 to 70%, advantageously from 10 to 60% and preferably from 20 to 45%.
  • the amounts of the various monomers present in the copolymer (a) can be measured by infrared spectroscopy using the ISO8985 (1998) standard.
  • the softening temperature of the copolymer can be measured by ASTM Standard E 28-99 (2004).
  • the so-called radical polymerization processes usually operating at pressures between 200 and 2500 bar, may be used. These processes are carried out industrially using two main types of reactors: an autoclave type reactor or a tubular type reactor. These polymerization processes known to those skilled in the art and can be used for example the methods described in documents FR2498609, FR256941 1 and FR2569412. Those skilled in the art know in what proportions to use each of the monomers to obtain the copolymer (a) used in the invention.
  • copolymers are marketed by the applicant under the trademark EVATANE® and LOTRYL®.
  • the copolymer may also include additives or inorganic fillers.
  • additives or inorganic fillers mention may be made of plasticizers, antioxidants or anti-ozone agents, antistatic agents, coloring materials, pigments, optical brighteners, heat stabilizers, light stabilizers and flame retardants. .
  • Coupling agents may be advantageously added in order to improve the adhesion power on another support of the composition (I) or the polymer to be crosslinked. It can be organic, mineral and more preferably semi-mineral semi-organic. Among these, mention may be made of titanates or organic silanes, for example monoalkyl titanates, trichlorosilanes and trialkoxysilanes.
  • fillers there may be mentioned clay, silica, talc, carbonates such as calcium carbonate, silicates such as sodium silicate.
  • the copolymer (a) is in the form of "particles", that is to say that pieces of polymer can have any type of geometry, for example, spherical, spheroidal or cylindrical.
  • the volume of a particle is advantageously in the range from 1 to 1000 mm 3 , preferably from 3 to 120 mm 3 . In these preferred volume ranges, excellent peroxide uptake is achieved while having little agglomeration of particles. Preferably, at least 90% by weight of these particles have a volume included in these preferred ranges of volume.
  • the organic peroxide solution (b) comprises at least one organic peroxide optionally with an organic solvent thereof.
  • solvents of the alkane, aromatic, alkene, halogenated or alcohol type are used.
  • the solvent molecules comprise from 1 to 12 carbon atoms.
  • a solvent mention may be made of decane, dodecane, 2,4,4-trimethylpentene, ⁇ -methylstyrene, trichlorethylene, toluene, benzene, ethylbenzene and (1-methylethylenyl). benzene, 2-ethylhexanol, isopropanol, t-butyl alcohol or acetone.
  • the amount of solvent is less than or equal to 25% of the total mass of the organic peroxide solution (b), or even less than or equal to 10%.
  • the solvent used is preferably not a solvent of the copolymer, especially when the amount of solvent in the peroxide solution is greater than 20% by weight.
  • solvent of the copolymer is meant a polymer concentration greater than or equal to 0.05 g per ml of solvent when 1 g of copolymer per ml of solvent is brought into contact for one hour at 23 ° C.
  • the composition (I) produced by the process according to the invention comprises a mass quantity of peroxide in the range from 5 to 30%, for example from 7 to 16%.
  • the manufacturing method according to the invention comprises the following steps: a first step of contacting the peroxide solution (b) with the copolymer (a); ⁇ a second step of total absorption of the peroxide solution (b) with the copolymer (a);
  • thermoplastic composition recovery stage (!) ⁇
  • the first contacting step can be carried out in any type of container.
  • the container may be left open or closed after contacting.
  • the container can be closed tightly or not.
  • the container is sealed and is equipped with a valve.
  • the solution (b) of peroxide is brought into contact with the copolymer (a) by pouring it directly onto the particles or by a drip system or by a spraying system such as a spray.
  • the second step is a stirring absorption step of the peroxide solution (b) with the copolymer (a). This is a total absorption.
  • total absorption is meant that the remaining volume solution (b) not absorbed in the container after the absorption step is less than 5%, preferably less than 2%, most preferably less than 1%.
  • the absorption step is carried out at a temperature at which the solution (b) remains liquid, that is to say at a temperature greater than or equal to the melting temperature of the peroxide when it is used without solvent.
  • the absorption temperature it is advantageous for the absorption temperature to be lower than the softening temperature of the copolymer (a) measured according to the ASTM E 28-99 (2004) standard.
  • the duration of the absorption is at least until the complete absorption of the peroxide.
  • the absorption time is generally in the range of 10 to 600 minutes, preferably 20 to 240 minutes.
  • the absorption step is carried out with stirring.
  • This stirring can be carried out by any stirring system, such as for example a system with pale, helical, screw or ultrasonic or in a rotary type device or drum, such as a dryer.
  • Several peroxide solution (b) can be contacted with the copolymer (a), i.e., the process can comprise at least 2 peroxide injections.
  • the first and second steps of the process according to the invention can also be carried out simultaneously by putting the solution of peroxide (b) in continuous contact with the copolymer (a), for example by means of a drip system or again by a spraying system such as a spray.
  • thermoplastic composition (I) is recovered in the form of copolymer particles comprising peroxide.
  • a step of drying the particles recovered during the third step for example in an oven or any other type of dryer. This is carried out at a temperature below the decomposition temperature of the peroxide of the composition (I).
  • thermoplastic composition (I) can be used to crosslink a useful polymer as encapsulant in the photovoltaic modules.
  • encapsulating polymers include polyolefins such as copolymers (a) of ethylene and a polar functional ethylenic monomer described above.
  • the copolymer (a) is a copolymer of ethylene and vinyl acetate and the polymer to be crosslinked is a copolymer of ethylene and vinyl acetate.
  • the encapsulating polymer In order to crosslink the encapsulating polymer, it is generally mixed in a first step with the composition (I) of the invention, and then, in a second shaping step, the encapsulating film which is cross-linked in a third stage is shaped. .
  • thermoplastic processing tools such as extruders or mixers. It can be mixed at a temperature below the degradation temperature of the peroxide (b).
  • the second forming step is carried out at a temperature below the degradation temperature of the peroxide (b).
  • Any type of apparatus for shaping such as presses, injectors or calenders can be used. It is also possible to perform the shaping simultaneously with the first step, for example by extrusion of film by placing a flat die at the end of the extruder.
  • the third step is generally carried out at a temperature above the degradation temperature of the peroxide.
  • a first layer of lower encapsulant, photovoltaic sensors, a second upper encapsulant layer and then an upper protective layer are successively placed on a rear protection layer. These different layers are assembled to form the module and then performs the third crosslinking step.
  • compositions can be used to crosslink the encapsulants of all types of photovoltaic modules and are obviously not limited to those presented in this description.
  • thermoplastic composition (I) is advantageously used to crosslink polymers for the manufacture of transparent encapsulants.
  • a part or a film is transparent when it has a level of disorder (in English "Haze") less than or equal to 20%, for example less than or equal to 10%.
  • the cloudiness level of the film is evaluated according to the ASTM D1003 standard, on a film of 500 ⁇ thickness of the composition which constitutes the part or the film, and for at least one wavelength of the visible range (from 380 to 780 nm), for example 500 nm.

Abstract

The present invention relates to a composition that is useful as masterbatch and includes a copolymer (a), made of ethylene and an ethylene monomer and having a polar function, and at least one organic peroxide solution (b) that is selected from among tert-Butyl 2-ethylperhexanoate, tert-Amyl 2-ethylperhexanoate, and dilauroyl peroxide, the amount by weight of the peroxide solution (b) ranging from 5% to 30% of the total weight of the composition (I). The invention also relates to the use of said masterbatch for the crosslinking of a photovoltaic cell encapsulant.

Description

COMPOSITION MELANGE-MAITRE UTILE DANS LES MODULES  MIXING-MASTER COMPOSITION USEFUL IN MODULES
PHOTOVOLTAIQUES  PHOTOVOLTAIQUES
Domaine de l'invention Field of the invention
L'invention a pour objet une composition thermoplastique comprenant un peroxyde organique, son procédé de fabrication et l'utilisation de cette composition pour réticuler des polymères. En particulier, l'invention a pour objet l'utilisation de cette composition pour la réticulation de film encapsulant des cellules photovoltaïques. The invention relates to a thermoplastic composition comprising an organic peroxide, its method of manufacture and the use of this composition for crosslinking polymers. In particular, the subject of the invention is the use of this composition for the crosslinking of film encapsulating photovoltaic cells.
Etat de l'art State of the art
Les peroxydes organiques sont couramment utilisés pour la réticulation des résines thermoplastiques ou des élastomères, ces résines et élastomères étant regroupés dans la présente description sous le terme « polymères ». Pour réticuler un polymère, un peroxyde est généralement mélangé au polymère à réticuler dans une première étape, puis on réalise une seconde étape de mise en forme du polymère et une troisième étape de réticulation, par exemple par un traitement thermique. A titre d'exemples, on connaît par les documents EP 2003701 et EP 1 164167 qui divulguent des compositions à base d'un copolymère d'éthylène et d'acétate de vinyle ainsi qu'un peroxyde classique. Organic peroxides are commonly used for the crosslinking of thermoplastic resins or elastomers, these resins and elastomers being grouped together in the present description under the term "polymers". To crosslink a polymer, a peroxide is generally mixed with the polymer to be crosslinked in a first step, then a second polymer forming step is carried out and a third crosslinking step, for example by a heat treatment. By way of example, EP 2003701 and EP 1 164167 disclose compositions based on a copolymer of ethylene and vinyl acetate and a conventional peroxide.
A température ambiante, les peroxydes peuvent être sous forme liquide ou solide. Lorsque les peroxydes sont mélangés à ces polymères, ils sont mélangés à haute température, c'est-à-dire une température supérieure au point de ramollissement du polymère, par exemple par extrusion ou malaxage ; les peroxydes sont alors généralement sous une forme liquide. At room temperature, the peroxides can be in liquid or solid form. When the peroxides are mixed with these polymers, they are mixed at high temperature, that is to say a temperature above the softening point of the polymer, for example by extrusion or kneading; the peroxides are then usually in a liquid form.
Un premier problème est que les peroxydes sous cette forme liquide sont difficiles à mélanger avec le polymère et on peut observer un phénomène de demixion du peroxyde. De plus, une longue durée de mélange à haute température est nécessaire afin de permettre le mélange du peroxyde dans le polymère. On peut alors observer un phénomène de réticulation dès cette étape, c'est-à-dire une réticulation prématurée du polymère avant sa mise en forme. Ce phénomène diminue la transparence du polymère réticulé. A first problem is that the peroxides in this liquid form are difficult to mix with the polymer and a phenomenon of demixion of the peroxide can be observed. In addition, a long mixing time at high temperature is necessary to allow the mixing of the peroxide in the polymer. We can then observe a crosslinking phenomenon at this stage, that is to say a premature crosslinking of the polymer before shaping. This phenomenon decreases the transparency of the crosslinked polymer.
Pour limiter ces problèmes, on peut incorporer à température ambiante le peroxyde sous forme liquide préalablement dans des charges poreuses tels que la silice ou le talc. Cependant, lorsque ces charges poreuses portant le peroxyde sont mélangées avec le polymère, elles sont difficiles à répartir uniformément et rapidement dans le polymère ; l'utilisation de ces charges poreuses peut également diminuer certaines propriétés du polymère, comme par exemple sa transparence.  To limit these problems, can be incorporated at room temperature liquid form of peroxide previously in porous fillers such as silica or talc. However, when these porous peroxide-bearing fillers are mixed with the polymer, they are difficult to distribute uniformly and rapidly in the polymer; the use of these porous fillers can also reduce certain properties of the polymer, such as its transparency.
Afin de faciliter le mélange des peroxydes avec le polymère à réticuler, on peut également utiliser des compositions comprenant un polymère additionnel et des peroxydes en concentration élevée, bien connues de l'homme du métier sous le nom de « mélange-maître » (en anglais « master batch »).  In order to facilitate the mixing of the peroxides with the polymer to be crosslinked, it is also possible to use compositions comprising an additional polymer and peroxides in high concentration, which are well known to those skilled in the art under the name "masterbatch". "Master batch").
Par ailleurs, les modules photovoltaïques comprennent des cellules sensibles à la lumière, dite « cellules photovoltaïques », qui sont capables de transformer la lumière en courant. Ces cellules sont protégées de leur environnement (humidité, oxygène, etc ..) par des couches de protection qui sont généralement en verre ou en polymère. Une ou plusieurs couches d'encapsulant permettent de faire adhérer les cellules aux couches de protection. L'encapsulant doit épouser parfaitement la forme de l'espace existant entre les cellules et les autres couches de protection du module et ceci afin d'éviter la présence d'air qui limite le rendement du module photovoltaïque. Cet encapsulant est généralement une composition comprenant un polymère encapsulant, généralement un copolymère d'éthylène et d'acétate de vinyle, qui est réticulé par un peroxyde organique. Les différentes couches constitutives du panneau sont assemblées (cellules, couche(s) d'encapsulant comprenant le peroxyde, couches de protection) et le panneau ainsi assemblé subit une étape de cuisson permettant la réticulation de la couche d'encapsulant. On peut se référer par exemple au Handbook of Photovoltaic Science and Engineering, Wiley, 2003 qui décrit le fonctionnement et la constitution des modules photovoltaïques. In addition, the photovoltaic modules comprise light-sensitive cells, called "photovoltaic cells", which are capable of converting light into current. These cells are protected from their environment (moisture, oxygen, etc.) by protective layers which are usually made of glass or polymer. One or more layers of encapsulant allow to adhere the cells to the protective layers. The encapsulant must perfectly match the shape of the space existing between the cells and the other layers of protection of the module and this in order to avoid the presence of air which limits the efficiency of the photovoltaic module. This encapsulant is generally a composition comprising an encapsulating polymer, generally a copolymer of ethylene and vinyl acetate, which is crosslinked with an organic peroxide. The various constituent layers of the panel are assembled (cells, encapsulant layer (s) comprising peroxide, protective layers) and the panel thus assembled undergoes a firing step allowing the crosslinking of the encapsulant layer. One can refer for example to the Handbook of Photovoltaic Science and Engineering, Wiley, 2003 which describes the operation and constitution of photovoltaic modules.
Par ailleurs, un des problèmes rencontrés par l'industrie de fabrication des modules photovoltaïques est que cette étape de cuisson diminue le rendement du procédé de fabrication des modules.  In addition, one of the problems encountered by the photovoltaic module manufacturing industry is that this firing step decreases the efficiency of the module manufacturing process.
Il est donc nécessaire de trouver de nouvelles compositions permettant d'améliorer les rendements des procédés de fabrication des modules photovoltaïques.  It is therefore necessary to find new compositions for improving the yields of photovoltaic module manufacturing processes.
On connaît également le document KR 2009-035971 qui divulgue une composition comprenant : Document KR 2009-035971 is also known which discloses a composition comprising:
- 100 parties en poids d'un copolymère d'éthylène et d'acétate de vinyle, 100 parts by weight of a copolymer of ethylene and of vinyl acetate,
- 0,01 à 5 parties en poids d'un agent de réticulation, 0.01 to 5 parts by weight of a crosslinking agent,
- 0,01 à 5 parties en poids d'un adhésif réactif, 0.01 to 5 parts by weight of a reactive adhesive,
- 0,01 à 5 parties en poids d'au moins deux peroxydes.  0.01 to 5 parts by weight of at least two peroxides.
Les deux exemples de formulation d'une composition selon la formulation de ce document comprennent :  The two examples of formulation of a composition according to the formulation of this document include:
- 1000 parties en poids du copolymère d'éthylène et d'acétate de vinyle, - 0,5 partie en poids d'un agent de réticulation,  1000 parts by weight of the copolymer of ethylene and of vinyl acetate, 0.5 part by weight of a crosslinking agent,
- 2 parties en poids de silane,  2 parts by weight of silane,
- respectivement 0,47 et 0,42 partie en poids de n-butyl-4,4-bis(t- butylperoxy)valerate, et  0.47 and 0.42 parts by weight, respectively, of n-butyl-4,4-bis (t-butylperoxy) valerate, and
- respectivement 0,03 et 0,08 partie en poids de t-butylperoxy-2- ethylhexanoate.  0.03 and 0.08 parts by weight of t-butylperoxy-2-ethylhexanoate, respectively.
Il existe également un besoin de trouver une nouvelle composition permettant de limiter le phénomène de réticulation prématuré afin d'améliorer le rendement des cellules photovoltaïques. There is also a need to find a new composition to limit the phenomenon of premature crosslinking in order to improve the efficiency of the photovoltaic cells.
Résumé de l'invention L'invention porte justement sur une nouvelle composition, utile comme mélange-maître, qui permet de résoudre au moins un des inconvénients ci- dessus. Summary of the invention The invention relates precisely to a new composition, useful as a masterbatch, which makes it possible to solve at least one of the above disadvantages.
Cette composition (I) comprend :  This composition (I) comprises:
- un copolymère (a) d'éthylène et d'un monomère éthylénique portant une fonction polaire ;  a copolymer (a) of ethylene and an ethylenic monomer carrying a polar function;
■ et au moins une solution (b) de peroxyde organique choisi parmi le 2- éthylperhexanoate de tert-butyle, le 2-éthylperhexanoate de tert-amyle et le peroxyde de dilauroyle ; ■ and at least one solution (b) organic peroxide selected from 2- éthylperhexanoate tert-butyl, 2-tert-amyl éthylperhexanoate and dilauroyl peroxide;
la quantité massique de solution de peroxyde (b) étant comprise dans la gamme allant de 5 à 30% par rapport au poids total de la composition (I). the mass quantity of peroxide solution (b) being in the range of 5 to 30% relative to the total weight of the composition (I).
Cette nouvelle composition peut être avantageusement utilisée en tant que mélange-maître pour la réticulation de polymère encapsulant dans les panneaux photovoltaïques. This novel composition can be advantageously used as a masterbatch for the crosslinking of polymer encapsulating in photovoltaic panels.
En effet, la réticulation est rapide et le fait d'introduire le peroxyde sous forme de mélange-maître permet d'améliorer la transparence du polymère encapsulant. De plus, l'introduction de peroxyde organique par un mélange- maître est plus aisée que l'introduction directe de peroxyde liquide ou solide dans le polymère encapsulant.  Indeed, the crosslinking is fast and the introduction of the peroxide in the form of masterbatch makes it possible to improve the transparency of the encapsulating polymer. In addition, the introduction of organic peroxide by a masterbatch is easier than the direct introduction of liquid or solid peroxide into the encapsulating polymer.
Préférentiellement, le monomère éthylénique portant une fonction polaire comprend de 3 à 20 atomes de carbone, préférentiellement de 4 à 8 atomes. Avantageusement, le monomère éthylénique portant une fonction polaire est choisi parmi les esters vinyliques d'acide carboxylique saturé, les acides carboxyliques insaturés de carbone ou les esters (méth)acryliques d'acide carboxylique insaturé. Preferably, the polar-functional ethylenic monomer comprises from 3 to 20 carbon atoms, preferably from 4 to 8 atoms. Advantageously, the polar-bearing ethylenic monomer is chosen from vinyl esters of saturated carboxylic acid, unsaturated carboxylic acids of carbon or (meth) acrylic acid esters of unsaturated carboxylic acid.
De préférence, le monomère éthylénique peut être choisi parmi l'acétate de vinyle et les (méth)acrylates de méthyle, d'éthyle ou de butyle. Tout préférentiellement, il s'agit de l'acétate de vinyle. Avantageusement, le copolymère (a) comprend de 10 à 60% en masse de monomère éthylénique portant une fonction polaire par rapport à la masse totale du copolymère, préférentiellement de 25 à 45% en masse. Preferably, the ethylenic monomer may be chosen from vinyl acetate and methyl, ethyl or butyl (meth) acrylates. Most preferably, it is vinyl acetate. Advantageously, the copolymer (a) comprises from 10 to 60% by weight of ethylenic monomer carrying a polar function relative to the total weight of the copolymer, preferably from 25 to 45% by weight.
La dispersion du peroxyde est améliorée lorsque le copolymère comprend cette gamme de monomère éthylénique. The dispersion of the peroxide is improved when the copolymer comprises this range of ethylenic monomer.
Selon un mode, la quantité massique de peroxyde comprise dans la composition (I) est comprise dans la gamme allant de 7 à 16%. Préférentiellement, le peroxyde (b) est le 2-éthylperhexanoate de tert-butyle. According to one mode, the mass quantity of peroxide included in the composition (I) is in the range of 7 to 16%. Preferably, the peroxide (b) is tert-butyl 2-ethylperhexanoate.
L'invention porte également sur un procédé de fabrication d'une composition (I) selon l'invention comprenant : The invention also relates to a method of manufacturing a composition (I) according to the invention comprising:
■ une première étape de mise en contact de la solution de peroxyde (b) choisi parmi le 2-éthylperhexanoate de tert-butyle, le 2- éthylperhexanoate de tert-amyle et le peroxyde de dilauroyle avec le copolymère (a) ; ■ a first step of contacting the peroxide solution (b) selected from 2-éthylperhexanoate tert-butyl 2- éthylperhexanoate tert-amyl and dilauroyl peroxide with the copolymer (a);
■ une seconde étape d'absorption totale de la solution de peroxyde (b) par le copolymère (a) sous agitation ; ■ a second step of total absorption of the peroxide solution (b) with the copolymer (a) with stirring;
■ une troisième étape de récupération de la composition (I).  A third step of recovering the composition (I).
Un avantage de ce procédé est que le phénomène de réticulation prématuré de la composition est encore plus limité et que le procédé de fabrication est simple.  An advantage of this process is that the phenomenon of premature crosslinking of the composition is even more limited and that the manufacturing process is simple.
Selon un mode avantageux, la température de la seconde étape du procédé est inférieure à la température de ramollissement du copolymère, qui est mesuré dans la présente demande par la méthode est décrite dans la norme ASTM E 28-99(2004), mieux connue sous le nom « Ring and Bail ». According to an advantageous embodiment, the temperature of the second process step is lower than the softening temperature of the copolymer, which is measured in the present application by the method is described in ASTM E 28-99 (2004), better known under the name "Ring and Bail".
Selon un premier mode avantageux, le copolymère est sous forme de particules ayant un volume moyen de 1 à 1000 mm3, préférentiellement de 3 à 120 mm3. Dans ce cas, on obtient directement la composition (I) sous forme de particules sans avoir besoin de reformer des particules. Il peut alors facilement être utilisé comme mélange-maître. En utilisant des particules ayant ce volume particulier, l'absorption du peroxyde par le copolymère est excellente et on observe peu d'agglomération entre les particules. Selon une version du procédé de fabrication de la composition de l'invention, il existe plusieurs mises en contact ou une mise en contact continue de la solution de peroxyde (b) avec le copolymère (a), c'est-à-dire qu'il y a plusieurs injections ou une injection continue de la solution de peroxyde (b) lors du procédé. According to a first advantageous embodiment, the copolymer is in the form of particles having an average volume of 1 to 1000 mm 3 , preferably 3 to 120 mm 3 . In this case, the composition (I) is obtained directly in the form of particles without the need to reform particles. It can then easily be used as a masterbatch. By using particles having this particular volume, the uptake of the peroxide by the copolymer is excellent and there is little agglomeration between the particles. According to one version of the process for producing the composition of the invention, there are several contacts or a continuous contact of the peroxide solution (b) with the copolymer (a), that is to say that There are several injections or continuous injection of the peroxide solution (b) during the process.
Un autre objet de l'invention est une composition obtenue par le procédé selon l'invention. Another subject of the invention is a composition obtained by the process according to the invention.
Un autre objet de l'invention est un film comprenant un mélange de la composition thermoplastique (I) et d'un second polymère choisi parmi les polyoléfines. Ce film peut être avantageusement utilisé en tant que film encapsulant de cellules photovoltaïques. Another subject of the invention is a film comprising a mixture of the thermoplastic composition (I) and a second polymer chosen from polyolefins. This film can be advantageously used as a film encapsulating photovoltaic cells.
Avantageusement, la quantité massique de composition (I) par rapport à la masse totale du film est de 3 à 30%, préférentiellement de 8 à 25%. Advantageously, the mass quantity of composition (I) relative to the total mass of the film is 3 to 30%, preferably 8 to 25%.
L'invention porte également sur un procédé de fabrication d'un module photovoltaïque comprenant les étapes : The invention also relates to a method of manufacturing a photovoltaic module comprising the steps:
■ d'assemblage des couches de cellules photovoltaïques, de films encapsulant et de couches protectrices, au moins un des films encapsulant étant un film selon l'invention ; ■ assembling layers of photovoltaic cells, encapsulating films and protective layers, at least one encapsulating film being a film according to the invention;
■ de cuisson du module, préférentiellement à une température supérieure ou égale à la température de dégradation du peroxyde (b). En utilisant la composition selon l'invention pour former le film encapsulant de l'invention, le rendement des procédés de fabrication des panneaux photovoltaïques est rapide et la couche d'encapsulant conserve une transparence élevée, ce qui permet d'obtenir un panneau photovoltaïque présentant un très bon rendement. ■ cooking module, preferably at a temperature greater than or equal to the degradation temperature of the peroxide (b). By using the composition according to the invention to form the encapsulant film of the invention, the efficiency of the photovoltaic panel manufacturing processes is rapid and the encapsulant layer retains a high transparency, which allows to obtain a photovoltaic panel with a very good performance.
Description détaillée de l'invention Detailed description of the invention
La composition (I) fabriquée par le procédé selon l'invention comprend un copolymère (a) et une solution de peroxyde organique (b). The composition (I) produced by the process according to the invention comprises a copolymer (a) and an organic peroxide solution (b).
Le copolymère (a) est un copolymère d'éthylène et d'un monomère éthylénique portant une fonction polaire. The copolymer (a) is a copolymer of ethylene and an ethylenic monomer carrying a polar function.
On entend par monomère éthylénique, un monomère comprenant une insaturation susceptible de réagir avec l'éthylène dans un procédé par voie radicalaire. The term "ethylenic monomer" is understood to mean a monomer comprising an unsaturation capable of reacting with ethylene in a radical process.
Par fonction polaire, on entend une fonction présentant un moment dipolaire, tel que les fonctions aminé, alcool, uréthane, acide ou ester. Préférentiel lement, la fonction polaire est une fonction acide ou une fonction ester.  By polar function is meant a function having a dipole moment, such as amine, alcohol, urethane, acid or ester functions. Preferentially, the polar function is an acid function or an ester function.
Le monomère éthylénique portant une fonction polaire comprend préférentiellement de 3 à 20 atomes de carbone, préférentiellement de 4 à 8 atomes de carbone.  The polar-functional ethylenic monomer preferably comprises from 3 to 20 carbon atoms, preferentially from 4 to 8 carbon atoms.
A titre d'exemple de copolymère (a), on peut citer les copolymères d'éthylène et d'un ester vinylique d'acide carboxylique, les copolymères d'éthylène et d'un acide carboxylique insaturé ou encore les copolymères d'éthylène et d'un acrylate et ou d'un méthacrylates d'alkyle, regroupés dans la présente demande sous le terme (méth)acrylate d'alkyle. Avantageusement, le monomère éthylénique peut être choisi parmi l'acétate de vinyle et les (méth)acrylates de méthyle, d'éthyle ou de butyle.  By way of example of copolymer (a), mention may be made of copolymers of ethylene and of a vinyl ester of carboxylic acid, copolymers of ethylene with an unsaturated carboxylic acid or copolymers of ethylene and of an alkyl acrylate and or methacrylates, grouped together in the present application under the term (meth) acrylate. Advantageously, the ethylenic monomer may be chosen from vinyl acetate and methyl, ethyl or butyl (meth) acrylates.
La quantité massique en monomère éthylénique par rapport à la masse totale du copolymère (a) peut être comprise dans la gamme allant de 1 à 70%, avantageusement de 10 à 60% et préférentiellement de 20 à 45%.  The quantity by mass of ethylenic monomer relative to the total weight of the copolymer (a) can be in the range of from 1 to 70%, advantageously from 10 to 60% and preferably from 20 to 45%.
Selon l'invention, les quantités des différents monomères présents dans le copolymère (a) peuvent être mesurées par spectroscopie infrarouge en utilisant la norme ISO8985 (1998). La température de ramollissement du copolymère peut être mesurée par la Norme ASTM E 28-99(2004). On peut utiliser les procédés dits de polymérisation radicalaire fonctionnant habituellement à des pressions entre 200 et 2 500 bars. Ces procédés sont mis en oeuvre industriellement en utilisant deux types principaux de réacteurs : un réacteur de type autoclave ou un réacteur de type tubulaire. Ces procédés de polymérisation connus de l'homme du métier et on peut utiliser par exemple les procédés décrits dans les documents FR2498609, FR256941 1 et FR2569412. L'homme du métier sait dans quelles proportions utiliser chacun des monomères pour obtenir le copolymère (a) utilisé dans l'invention. According to the invention, the amounts of the various monomers present in the copolymer (a) can be measured by infrared spectroscopy using the ISO8985 (1998) standard. The softening temperature of the copolymer can be measured by ASTM Standard E 28-99 (2004). The so-called radical polymerization processes, usually operating at pressures between 200 and 2500 bar, may be used. These processes are carried out industrially using two main types of reactors: an autoclave type reactor or a tubular type reactor. These polymerization processes known to those skilled in the art and can be used for example the methods described in documents FR2498609, FR256941 1 and FR2569412. Those skilled in the art know in what proportions to use each of the monomers to obtain the copolymer (a) used in the invention.
Ces copolymères sont commercialisés par la demanderesse sous la marque EVATANE® et LOTRYL®. These copolymers are marketed by the applicant under the trademark EVATANE® and LOTRYL®.
Le copolymère peut comprendre également des additifs ou des charges inorganiques. A titre d'exemple d'additif, on peut citer les plastifiants, les antioxydants ou agents anti-ozone, les agents antistatiques, les matériaux colorants, les pigments, les azurants optiques, les stabilisants thermiques, les stabilisants lumière, les retardateurs de flamme. The copolymer may also include additives or inorganic fillers. By way of example of an additive, mention may be made of plasticizers, antioxidants or anti-ozone agents, antistatic agents, coloring materials, pigments, optical brighteners, heat stabilizers, light stabilizers and flame retardants. .
Des agents de couplage peuvent être avantageusement ajoutés afin d'améliorer le pouvoir d'adhérence sur un autre support de la composition (I) ou du polymère à réticuler. Il peut être organique, minéral et plus préférentiellement semi-minéral semi-organique. Parmi ceux-ci, on peut citer les titanates ou les silanes organiques, comme par exemple les monoalkyl titanates, les trichlorosilanes et les trialkoxysilanes.  Coupling agents may be advantageously added in order to improve the adhesion power on another support of the composition (I) or the polymer to be crosslinked. It can be organic, mineral and more preferably semi-mineral semi-organic. Among these, mention may be made of titanates or organic silanes, for example monoalkyl titanates, trichlorosilanes and trialkoxysilanes.
A titre de charges, on peut citer l'argile, la silice, le talc, les carbonates comme le carbonate de calcium, les silicates comme le silicate de sodium.  As fillers, there may be mentioned clay, silica, talc, carbonates such as calcium carbonate, silicates such as sodium silicate.
Le copolymère (a) est sous forme de « particules », c'est-à-dire que de morceaux de polymère pouvant avoir tout type de géométrie, par exemple, sphérique, sphéroïdale ou cylindrique. Le volume d'une particule est avantageusement compris dans la gamme allant de 1 à 1000 mm3, préférentiellement de 3 à 120 mm3. Dans ces gammes préférées de volume, on obtient une excellente absorption du peroxyde tout en ayant peu d'agglomération des particules. Préférentiellement, au moins 90% en masse de ces particules ont un volume compris dans ces gammes préférées de volume. The copolymer (a) is in the form of "particles", that is to say that pieces of polymer can have any type of geometry, for example, spherical, spheroidal or cylindrical. The volume of a particle is advantageously in the range from 1 to 1000 mm 3 , preferably from 3 to 120 mm 3 . In these preferred volume ranges, excellent peroxide uptake is achieved while having little agglomeration of particles. Preferably, at least 90% by weight of these particles have a volume included in these preferred ranges of volume.
La solution (b) de peroxyde organique comprend au moins un peroxyde organique avec éventuellement un solvant organique de celui-ci. The organic peroxide solution (b) comprises at least one organic peroxide optionally with an organic solvent thereof.
On peut utiliser tout type de solvant miscible avec le peroxyde. Par exemple, on utilise des solvants de type alcane, aromatique, alcène, halogéné ou alcool. Préférentiellement les molécules de solvant comprennent de 1 à 12 atomes de carbone. A titre d'exemple de solvant, on peut citer le décane, le dodécane, le 2,4,4-triméthylepentène, le α-méthylestyrène, le trichloroéthylène, le toluène, le benzène, l'éthylebenzène, le (l -méthylethenyl)benzène, 2-éthylehexanol, l'isopropanol, l'alcool de t-butyle ou l'acétone.  Any type of solvent miscible with peroxide can be used. For example, solvents of the alkane, aromatic, alkene, halogenated or alcohol type are used. Preferably, the solvent molecules comprise from 1 to 12 carbon atoms. As an example of a solvent, mention may be made of decane, dodecane, 2,4,4-trimethylpentene, α-methylstyrene, trichlorethylene, toluene, benzene, ethylbenzene and (1-methylethylenyl). benzene, 2-ethylhexanol, isopropanol, t-butyl alcohol or acetone.
On peut utiliser également un mélange de solvants, par exemple un mélange des solvants listés ci-dessus.  It is also possible to use a mixture of solvents, for example a mixture of the solvents listed above.
Préférentiellement, la quantité de solvant est inférieure ou égale à 25% de la masse totale de la solution de peroxyde organique (b), voire inférieure ou égale à 10%. Preferably, the amount of solvent is less than or equal to 25% of the total mass of the organic peroxide solution (b), or even less than or equal to 10%.
Le solvant utilisé n'est préférentiellement pas un solvant du copolymère, tout particulièrement lorsque la quantité de solvant dans la solution de peroxyde est supérieure à 20% en masse. Par solvant du copolymère, on entend une concentration en polymère supérieure ou égale à 0,05g par mL de solvant lorsqu'on met en contact pendant une heure à 23°C 1 g de copolymère par mL de solvant. La composition (I) fabriquée par le procédé selon l'invention comprend une quantité massique de peroxyde comprise dans la gamme allant de 5 à 30%, par exemple de 7 à 16%.  The solvent used is preferably not a solvent of the copolymer, especially when the amount of solvent in the peroxide solution is greater than 20% by weight. By solvent of the copolymer is meant a polymer concentration greater than or equal to 0.05 g per ml of solvent when 1 g of copolymer per ml of solvent is brought into contact for one hour at 23 ° C. The composition (I) produced by the process according to the invention comprises a mass quantity of peroxide in the range from 5 to 30%, for example from 7 to 16%.
Le procédé de fabrication selon l'invention comporte les étapes suivantes : ■ une première étape de mise en contact de la solution de peroxyde (b) avec le copolymère (a) ; ■ une seconde étape d'absorption totale de la solution de peroxyde (b) par le copolymère (a) ; The manufacturing method according to the invention comprises the following steps: a first step of contacting the peroxide solution (b) with the copolymer (a); ■ a second step of total absorption of the peroxide solution (b) with the copolymer (a);
■ une troisième étape de récupération de la composition thermoplastique (!)■ ■ a third of the thermoplastic composition recovery stage (!) ■
La première étape de mise en contact peut être réalisée dans tout type de récipient. Le récipient peut être laissé ouvert ou être clos après la mise en contact. Le récipient peut être fermé de manière étanche ou non. Préférentiellement, le récipient est fermé de manière étanche et est équipé d'une soupape. The first contacting step can be carried out in any type of container. The container may be left open or closed after contacting. The container can be closed tightly or not. Preferably, the container is sealed and is equipped with a valve.
La solution (b) de peroxyde est mise en contact avec le copolymère (a) en le versant directement sur les particules ou par un système de goutte à goutte ou encore par un système de pulvérisation tel qu'un spray. La seconde étape est une étape d'absorption sous agitation de la solution de peroxyde (b) par le copolymère (a). Il s'agit d'une absorption totale. Par « absorption totale », on entend que le volume restant se solution (b) non absorbée dans le récipient après l'étape d'absorption est inférieur à 5%, préférentiellement inférieur à 2%, tout préférentiellement inférieur à 1 %.  The solution (b) of peroxide is brought into contact with the copolymer (a) by pouring it directly onto the particles or by a drip system or by a spraying system such as a spray. The second step is a stirring absorption step of the peroxide solution (b) with the copolymer (a). This is a total absorption. By "total absorption" is meant that the remaining volume solution (b) not absorbed in the container after the absorption step is less than 5%, preferably less than 2%, most preferably less than 1%.
L'étape d'absorption est réalisée à une température à laquelle la solution (b) reste liquide, c'est-à-dire à une température supérieure ou égale à la température de fusion du peroxyde lorsque celui-ci est utilisé sans solvant. Il est cependant avantageux que la température d'absorption soit inférieure à la température de ramollissement du copolymère (a) mesurée selon la norme ASTM E 28-99(2004). The absorption step is carried out at a temperature at which the solution (b) remains liquid, that is to say at a temperature greater than or equal to the melting temperature of the peroxide when it is used without solvent. However, it is advantageous for the absorption temperature to be lower than the softening temperature of the copolymer (a) measured according to the ASTM E 28-99 (2004) standard.
La durée de l'absorption est au moins jusqu'à l'absorption complète du peroxyde. La durée d'absorption est généralement comprise dans la gamme allant de 10 à 600 minutes, préférentiellement de 20 à 240 minutes.  The duration of the absorption is at least until the complete absorption of the peroxide. The absorption time is generally in the range of 10 to 600 minutes, preferably 20 to 240 minutes.
L'étape d'absorption est réalisée sous agitation. Cette agitation peut être réalisée par tout système d'agitation, comme par exemple un système à pâle, à hélice, à vis ou à ultrasons ou dans un dispositif de type rotatif ou à tambour, tel qu'un sécheur. On peut effectuer plusieurs mises en contact de solution de peroxyde (b) avec le copolymère (a), c'est-à-dire que le procédé peut comprendre au moins 2 injections de peroxyde. On peut également réaliser de manière simultanée la première et la seconde étape du procédé selon l'invention en mettant en contact de manière continue la solution de peroxyde (b) avec le copolymère (a), par exemple par un système de goutte à goutte ou encore par un système de pulvérisation tel qu'un spray. The absorption step is carried out with stirring. This stirring can be carried out by any stirring system, such as for example a system with pale, helical, screw or ultrasonic or in a rotary type device or drum, such as a dryer. Several peroxide solution (b) can be contacted with the copolymer (a), i.e., the process can comprise at least 2 peroxide injections. The first and second steps of the process according to the invention can also be carried out simultaneously by putting the solution of peroxide (b) in continuous contact with the copolymer (a), for example by means of a drip system or again by a spraying system such as a spray.
Lors de la troisième étape du procédé, on récupère la composition thermoplastique (I) sous forme de particules de copolymère comprenant le peroxyde. In the third step of the process, the thermoplastic composition (I) is recovered in the form of copolymer particles comprising peroxide.
De manière optionnelle, on peut réaliser une étape de séchage des particules récupérées lors de la troisième étape, par exemple dans une étuve ou tout autre type de sécheur. Celle-ci est réalisée à une température inférieure à la température de décomposition du peroxyde de la composition (I).  Optionally, it is possible to carry out a step of drying the particles recovered during the third step, for example in an oven or any other type of dryer. This is carried out at a temperature below the decomposition temperature of the peroxide of the composition (I).
La composition thermoplastique (I) peut être utilisée pour réticuler un polymère utile comme encapsulant dans les modules photovoltaïques. A titre d'exemple de polymères encapsulants, on peut citer les polyoléfines telles que les copolymères (a) d'éthylène et d'un monomère éthylénique portant une fonction polaire décrits ci-dessus. The thermoplastic composition (I) can be used to crosslink a useful polymer as encapsulant in the photovoltaic modules. As an example of encapsulating polymers include polyolefins such as copolymers (a) of ethylene and a polar functional ethylenic monomer described above.
Selon un mode de réalisation, le copolymère (a) est un copolymère d'éthylène et d'acétate de vinyle et le polymère à réticuler est un copolymère d'éthylène et d'acétate de vinyle.  According to one embodiment, the copolymer (a) is a copolymer of ethylene and vinyl acetate and the polymer to be crosslinked is a copolymer of ethylene and vinyl acetate.
Pour réticuler le polymère encapsulant, on le mélange généralement dans une première étape avec la composition (I) de l'invention, puis on met en forme dans une seconde étape de mise en forme le film encapsulant que l'on réticule dans une troisième étape. In order to crosslink the encapsulating polymer, it is generally mixed in a first step with the composition (I) of the invention, and then, in a second shaping step, the encapsulating film which is cross-linked in a third stage is shaped. .
Lors de la première étape, on utilise les techniques classiques de mélange, en particulier dans les outils de mise en œuvre des thermoplastiques, tels que les extrudeuses ou les mélangeurs. On peut mélanger à une température inférieure à la température de dégradation du peroxyde (b). On réalise la seconde étape de mise en forme à une température inférieure à la température de dégradation du peroxyde (b). On peut utiliser tout type d'appareillage permettant la mise en forme tels que les presses, les injecteurs ou les calandreurs. On peut également réaliser la mise en forme simultanément avec la première étape, par exemple par extrusion de film en plaçant une filière plate en bout de l'extrudeuse. In the first step, conventional mixing techniques are used, in particular in thermoplastic processing tools, such as extruders or mixers. It can be mixed at a temperature below the degradation temperature of the peroxide (b). The second forming step is carried out at a temperature below the degradation temperature of the peroxide (b). Any type of apparatus for shaping such as presses, injectors or calenders can be used. It is also possible to perform the shaping simultaneously with the first step, for example by extrusion of film by placing a flat die at the end of the extruder.
La troisième étape est généralement réalisée à une température supérieure à la température de dégradation du peroxyde.  The third step is generally carried out at a temperature above the degradation temperature of the peroxide.
Dans le cas particulier d'un panneau photovoltaïque, on place successivement sur une couche de protection arrière, une première couche d'encapsulant inférieure, des capteurs photovoltaïques, une seconde couche d'encapsulant supérieure puis une couche protectrice supérieure. Ces différentes couches sont assemblées pour former le module et on effectue ensuite la troisième étape de réticulation.  In the particular case of a photovoltaic panel, a first layer of lower encapsulant, photovoltaic sensors, a second upper encapsulant layer and then an upper protective layer are successively placed on a rear protection layer. These different layers are assembled to form the module and then performs the third crosslinking step.
II est précisé que les compositions peuvent être utilisées pour réticuler les encapsulants de tous types de modules photovoltaïques et ne sont bien évidemment pas limités à ceux présentés dans cette description. It is specified that the compositions can be used to crosslink the encapsulants of all types of photovoltaic modules and are obviously not limited to those presented in this description.
La composition thermoplastique (I) est avantageusement utilisée pour réticuler des polymères pour la fabrication d'encapsulants transparents. The thermoplastic composition (I) is advantageously used to crosslink polymers for the manufacture of transparent encapsulants.
Selon l'invention, une pièce ou un film est transparent lorsqu'elle présente un niveau de trouble (en anglais « Haze ») inférieur ou égal à 20%, par exemple inférieur ou égal à 10%. Le niveau de trouble du film est évalué selon la norme ASTM D1003, sur un film de 500 μιτι d'épaisseur de la composition qui constitue la pièce ou le film, et pour au moins une longueur d'onde du domaine visible (de 380 à 780 nm), par exemple 500 nm.  According to the invention, a part or a film is transparent when it has a level of disorder (in English "Haze") less than or equal to 20%, for example less than or equal to 10%. The cloudiness level of the film is evaluated according to the ASTM D1003 standard, on a film of 500 μιτι thickness of the composition which constitutes the part or the film, and for at least one wavelength of the visible range (from 380 to 780 nm), for example 500 nm.

Claims

REVENDICATIONS Composition (I) comprenant : CLAIMS Composition (I) comprising:
- un copolymère (a) d'éthylène et d'un monomère éthylénique portant une fonction polaire ; - a copolymer (a) of ethylene and an ethylenic monomer carrying a polar function;
■ et au moins une solution (b) de peroxyde organique choisi parmi le 2- éthylperhexanoate de tert-butyle, le 2-éthylperhexanoate de tert- amyle et le peroxyde de dilauroyle ; ■ and at least one solution (b) of organic peroxide chosen from tert-butyl 2-ethylperhexanoate, tert-amyl 2-ethylperhexanoate and dilauroyl peroxide;
la quantité massique de solution de peroxyde (b) étant comprise dans la gamme allant de 5 à 30% par rapport au poids total de la composition (I). the mass quantity of peroxide solution (b) being in the range going from 5 to 30% relative to the total weight of the composition (I).
Composition selon la revendication 1 dans laquelle le monomère éthylénique portant une fonction polaire comprend de 3 à 20 atomes de carbone, préférentiellement de 4 à 8 atomes. Composition according to claim 1 in which the ethylenic monomer carrying a polar function comprises from 3 to 20 carbon atoms, preferably from 4 to 8 atoms.
Composition selon l'une des revendications précédentes dans laquelle le monomère éthylénique peut être choisi parmi l'acétate de vinyle et les (méth)acrylates de méthyle, d'éthyle ou de butyle. Composition according to one of the preceding claims in which the ethylenic monomer can be chosen from vinyl acetate and methyl, ethyl or butyl (meth)acrylates.
Composition selon l'une des revendications précédentes dans laquelle le copolymère (a) comprend de 10 à 60% en masse de monomère éthylénique portant une fonction polaire par rapport à la masse totale du copolymère, préférentiellement de 25 à 45% en masse. Composition according to one of the preceding claims in which the copolymer (a) comprises from 10 to 60% by mass of ethylenic monomer carrying a polar function relative to the total mass of the copolymer, preferably from 25 to 45% by mass.
Composition selon l'une des revendications précédentes dans laquelle la quantité massique de peroxyde comprise dans la composition (I) est comprise dans la gamme allant de 7 à 16%. Composition according to one of the preceding claims in which the mass quantity of peroxide included in composition (I) is included in the range from 7 to 16%.
Composition selon l'une des revendications précédentes dans laquelle le peroxyde (b) est le 2-éthylperhexanoate de tert-butyle. Composition according to one of the preceding claims in which the peroxide (b) is tert-butyl 2-ethylperhexanoate.
Procédé de fabrication d'une composition (I) selon l'une des revendications précédentes comprenant : Process for manufacturing a composition (I) according to one of the preceding claims comprising:
a. une première étape de mise en contact de la solution de peroxyde (b) choisi parmi le 2-éthylperhexanoate de tert-butyle, le 2- éthylperhexanoate de tert-amyle et le peroxyde de dilauroyle avec le copolymère (a) ; has. a first step of bringing the peroxide solution (b) chosen from tert-butyl 2-ethylperhexanoate, tert-amyl 2-ethylperhexanoate and dilauroyl peroxide into contact with the copolymer (a);
b. une seconde étape d'absorption totale de la solution de peroxyde (b) par le copolymère (a) sous agitation ; b. a second step of total absorption of the peroxide solution (b) by the copolymer (a) with stirring;
c. une troisième étape de récupération de la composition (I). vs. a third step of recovering the composition (I).
Film comprenant une composition selon l'une des revendications 1 à 6 ou obtenue selon le procédé selon la revendication 7 et un polymère encapsulant choisi parmi les polyoléfines. Film comprising a composition according to one of claims 1 to 6 or obtained according to the process according to claim 7 and an encapsulating polymer chosen from polyolefins.
Utilisation du film selon la revendication précédente comme film encapsulant de cellules photovoltaïques. Use of the film according to the preceding claim as an encapsulating film for photovoltaic cells.
10. Procédé de fabrication d'un module photovoltaïque comprenant les étapes : 10. Process for manufacturing a photovoltaic module comprising the steps:
■ d'assemblage des couches de cellules photovoltaïques, de films encapsulant et de couches protectrices, au moins un des films encapsulant étant un film selon la revendication 9 ; ■ assembly of layers of photovoltaic cells, encapsulating films and protective layers, at least one of the encapsulating films being a film according to claim 9;
■ de cuisson du module, préférentiellement à une température supérieure ou égale à la température de dégradation du peroxyde (b). ■ cooking the module, preferably at a temperature greater than or equal to the peroxide degradation temperature (b).
PCT/FR2010/051937 2009-09-21 2010-09-17 Masterbatch composition useful in photovoltaic modules WO2011033232A1 (en)

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FR0904502A FR2950352A1 (en) 2009-09-21 2009-09-21 MIXER-MASTER COMPOSITION USEFUL IN PHOTOVOLTAIC MODULES
FR0904502 2009-09-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015189508A1 (en) 2014-06-13 2015-12-17 Arkema France Organic solvent for peroxides

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2498609A1 (en) 1981-01-27 1982-07-30 Charbonnages Ste Chimique TERPOLYMERS OF ETHYLENE, PROCESS FOR THEIR MANUFACTURE AND THEIR APPLICATION TO THE MANUFACTURE OF FILMS
FR2569412A1 (en) 1984-08-23 1986-02-28 Charbonnages Ste Chimique NOVEL PROCESS FOR THE PRODUCTION OF ETHYLENE RADICAL TERPOLYMERS AND ETHYLENE RADICAL COPOLYMERS
FR2569411A1 (en) 1984-08-23 1986-02-28 Charbonnages Ste Chimique NOVEL PROCESS FOR THE PRODUCTION OF ETHYLENE RADICAL TERPOLYMERS AND ETHYLENE RADICAL COPOLYMERS
EP1164167A1 (en) 1999-11-01 2001-12-19 Bridgestone Corporation Sealing composition and sealing method
EP2003701A1 (en) 2006-04-05 2008-12-17 Bridgestone Corporation Sealing film for solar cell and solar cell using such sealing film
KR20090035971A (en) 2007-10-08 2009-04-13 주식회사 진흥공업 Eva sheet for photo voltaic module using two or more peroxides and process for preparing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2498609A1 (en) 1981-01-27 1982-07-30 Charbonnages Ste Chimique TERPOLYMERS OF ETHYLENE, PROCESS FOR THEIR MANUFACTURE AND THEIR APPLICATION TO THE MANUFACTURE OF FILMS
FR2569412A1 (en) 1984-08-23 1986-02-28 Charbonnages Ste Chimique NOVEL PROCESS FOR THE PRODUCTION OF ETHYLENE RADICAL TERPOLYMERS AND ETHYLENE RADICAL COPOLYMERS
FR2569411A1 (en) 1984-08-23 1986-02-28 Charbonnages Ste Chimique NOVEL PROCESS FOR THE PRODUCTION OF ETHYLENE RADICAL TERPOLYMERS AND ETHYLENE RADICAL COPOLYMERS
EP1164167A1 (en) 1999-11-01 2001-12-19 Bridgestone Corporation Sealing composition and sealing method
EP2003701A1 (en) 2006-04-05 2008-12-17 Bridgestone Corporation Sealing film for solar cell and solar cell using such sealing film
KR20090035971A (en) 2007-10-08 2009-04-13 주식회사 진흥공업 Eva sheet for photo voltaic module using two or more peroxides and process for preparing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Handbook of Photovoltaic Science and Engineering", 2003, WILEY
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 17 April 2009 (2009-04-17), KIM, GI HYEONG: "Preparation of EVA films for solar cells", XP002577693, Database accession no. 2009:457137 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015189508A1 (en) 2014-06-13 2015-12-17 Arkema France Organic solvent for peroxides
FR3022251A1 (en) * 2014-06-13 2015-12-18 Arkema France ORGANIC SOLVENT FOR PEROXIDES

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