Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
  • C09J133/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
  • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
  • H10F19/804—Materials of encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/80—Constructional details
  • H10K30/88—Passivation; Containers; Encapsulations
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2433/00—Presence of (meth)acrylic polymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2453/00—Presence of block copolymer

Definitions

• the present invention relates to adhesive photopolymerizable compositions used in the encapsulation of electronic and optoelectronic devices, in particular flexible electronic and optoelectronic devices, for example organic photovoltaic cells, in order to protect them against permeation by gases and humidity.
• Rigid electronic or optoelectronic devices can be of different types depending on the applications considered, such as display applications (for example OLEDs and QLEDs), photovoltaics (for example silicon-based semiconductors, CIGS, CDTEs, organic semi-conductors, semi-conductors of the Perovskite type) or sensors.
• display applications for example OLEDs and QLEDs
• photovoltaics for example silicon-based semiconductors, CIGS, CDTEs, organic semi-conductors, semi-conductors of the Perovskite type
• Flexible electronic or optoelectronic devices can be defined according to the same application examples but for semiconductor technologies compatible with the use of flexible substrates such as organic light-emitting diode (OLED) devices, organic photovoltaic cells (OPV) , amorphous silicon (a-Si) cells, CIGS, perovskite type semiconductors, organic transistors (OFET) or organic sensors using organic semiconductors.
• OLED organic light-emitting diode
• OCV organic photovoltaic cells
• a-Si amorphous silicon
• CIGS CIGS
• perovskite type semiconductors organic transistors
• OFET organic sensors using organic semiconductors.
• Electronic or optoelectronic devices are devices that are sensitive to multiple factors, for example, light, heat, oxygen (air), humidity, pressure, shock, etc. In order to ensure optimum efficiency and yield and to obtain satisfactory durability, they should therefore be protected and isolated from their environment. This protection must be all the more effective as the constituent materials are sensitive to the atmosphere, in particular to water and oxygen. This is particularly the case when using organic semiconductors, for example perovskite type semiconductors or CIGS semiconductors.
• Different encapsulation techniques have been implemented. These generally comprise the coating of the device with an adhesive composition to obtain a coated device, then the rolling of the coated device between two covers to obtain an encapsulated device.
• the choice of the adhesive composition and the caps will depend on the devices to be encapsulated.
• the electronic or optoelectronic modules obtained will have specific properties, in particular in terms of weight, thickness, transparency/opacity, rigidity/flexibility, permeation/gas tightness and liquids, impact resistance and/or durability/aging.
• two types of permeation can be observed, an orthogonal permeation at the level of the external surface of the covers between which the coated devices are inserted, and a lateral permeation at the level of the free edge of the adhesive within the coating material as well as at the interface of the two covers.
• the protection of the device against lateral permeation is ensured in particular by the adhesive or coating material, the effectiveness of which may depend on various factors, in particular its chemical formulation, its method of application, its thickness (proportional to the surface of exchange with the environment), its interface with the covers, its resistance to the constraints of use, etc.
• the properties of the adhesive must therefore be optimized to minimize or even eliminate lateral permeation, to ensure optimum efficiency and yield and to obtain satisfactory durability.
• Flexible photovoltaic cells e.g. organic cells, perovskite, CIGS, CDTE
• flexible photovoltaic cells represent a particularly interesting alternative to rigid silicon-based photovoltaic cells, in that they can be manufactured using continuous and high-speed processes (roll process roller) and may be suitable for applications requiring flexibility or conformability or low weight. They are also less fragile (use of flexible covers) and less susceptible to breakage.
• Flexible photovoltaic cells can for example be obtained by low-temperature printing of a thin active layer (organic material or perovskite with semi-conducting properties) deposited on a flexible polymeric support substrate.
• a thin active layer organic material or perovskite with semi-conducting properties
• the encapsulation of a flexible electronic or optoelectronic device can be achieved by means of a cover that is not very permeable to gases, in particular to water vapor and to oxygen, which must be at least as flexible as the device it protects so as not to become a factor limiting the bending of the latter, or that it must exhibit controlled flexibility when, for example, encapsulation is used to knowingly limit the radius of curvature of the device and to avoid its damage.
• the invention relates firstly to a photopolymerizable adhesive composition comprising, by weight per total weight of the photopolymerizable adhesive composition:
• the block copolymer is chosen from the group consisting of block copolymers comprising at least one M block and at least one B block; said block M designating a polymer block comprising at least 50% by weight of methyl methacrylate; and block B designating an elastomeric polymer block incompatible with block M, and whose glass transition temperature is less than 20°C.
• the (meth)acrylate monomer having a glass transition temperature of at least 85°C is selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, phenyl-methacrylate, isopropyl methacrylate, isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-ter-butylcyclohexyl methacrylate, dihydrodicyclopentadienyl acrylate and mixtures thereof.
• the alkoxysilane (meth)acrylate monomer is selected from the group consisting of trialkoxysilane (meth)acrylate monomers.
• the adhesive photopolymerizable composition further comprises at least one (meth)acrylate monomer having a glass transition temperature below 0°C, a methacrylic acid monomer, at least one urethane (meth)acrylate oligomer, at least one monofunctional reactive diluent and mixtures thereof.
• the (meth)acrylate monomer having a glass transition temperature below 0°C is selected from the group consisting of butyl acrylate, ethyl acrylate, acrylate propyl, hexyl acrylate, acrylate octyl acrylate, dodecyl acrylate, isopropyl acrylate, isobutyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, methacrylate d isodecyl, dodecyl methacrylate, 2-hydroxyethyl acrylate and mixtures thereof.
• the adhesive photopolymerizable composition is advantageously a single-component composition.
• the adhesive photopolymerizable composition has a glass transition temperature of at least 85°C, preferably at least 90°C, more preferably at least 100°C.
• the invention relates secondly to an adhesive product comprising the photopolymerizable adhesive composition as described opposite and an opaque container containing it.
• the invention relates to an adhesive obtained by the process comprising the following steps:
• the invention relates fourthly to an electronic or optoelectronic module comprising the assembly of a series of layers comprising, in this order:
• the flexible electronic or optoelectronic device is chosen from organic light-emitting diodes, organic photovoltaic cells, organic transistors, or organic sensors.
• the flexible electronic or optoelectronic device is a perovskite type device.
• the invention relates fifthly to a process for obtaining the module as described opposite, the process comprising the following steps:
• the invention relates sixthly to the use of the photopolymerizable adhesive composition as described opposite, or of the adhesive as described opposite, for the encapsulation of flexible electronic or optoelectronic devices.
• the photopolymerizable adhesive composition according to the present invention after application and photopolymerization, has entirely satisfactory, even excellent, properties, in particular adhesive, optical, thermal, electrical, barrier, elastic and resistance.
• the invention also has one or preferably more of the following advantages:
• Figure 1 corresponds to the photographs and to the corresponding images obtained after computer analysis of the modules tested in test 1.
• Figure 2 represents a graph concerning the speed of degradation according to the modules tested according to test 1.
• Figure 3 corresponds to the photographs of the modules tested in test 2.
• Figure 4 represents a graph concerning the percentage of transmission of the modules tested according to the wavelength (nm) according to test 3.
• flexible electronic or optoelectronic device (and the module obtained from it) is meant a device (a module) retaining its electronic conductive or semi-conductive properties even when bent with a very large radius of curvature. low without risk of buckling or delamination of electronic components.
• adheresive is meant the matrix/structure formed around the electronic or optoelectronic device by the photopolymerized adhesive composition.
• adhesive or “encapsulant” are used interchangeably herein.
• module is meant the assembly of the electronic or optoelectronic device coated with the polymerized adhesive composition and inserted between the two covers.
• Cross means the elements between which the coated electronic or optoelectronic device is laminated. Currently, this element may be referred to interchangeably as “support”, “plate” or “sheet”.
• photopolymerizable composition or “photocrosslinkable composition” is meant a composition for which the initiation (initiation) of the polymerization is triggered by exposure to electromagnetic radiation, in particular to ultraviolet (UV) radiation.
• electromagnetic radiation in particular to ultraviolet (UV) radiation.
• adhesive photopolymerizable composition is advantageously meant a composition developing adhesive properties when it is subjected to electromagnetic radiation, in particular to ultraviolet (UV) radiation, which initiates (initiates) the polymerization thereof.
• electromagnetic radiation in particular to ultraviolet (UV) radiation
• “monomer” is meant a molecule which can undergo polymerization.
• “monomer” when used to refer to a constituent of a polymer, it means the unit (or residue) derived from the monomer - or monomer unit/monomeric unit - by polymerization with at least one other monomer.
• polymerization we mean a process for transforming a single type of monomer or a mixture of different types of monomer into a polymer.
• polymer is meant a copolymer or a homopolymer.
• homopolymer is meant a polymer grouping together several identical monomer units.
• copolymer is meant a polymer combining at least two different types of monomer units (designated co-monomers).
• oligomer is meant a small polymer compound, obtained by polymerization of 2 and 30 monomers (comprising from 2 to 30 monomer units), that is to say whose degree of polymerization is between 2 and 30 .
• block copolymer is meant a polymer comprising one or more uninterrupted sequences of each of the distinct polymer species, the polymer sequences being chemically different from one another and being linked together by a covalent bond. These polymer sequences are also called polymer blocks.
• (meth)acrylic is meant any type of compound, polymer, monomer or oligomer, acrylic and/or methacrylic (or acrylate and/or methacrylate).
• (meth)acrylic acid means acrylic acid or methacrylic acid
• isobornyl (meth)acrylate means isobornyl acrylate or isobornyl methacrylate, etc.
• polymerization we mean a chemical process making it possible to link molecules together to form a three-dimensional network.
• initiator or “initiator” is meant a chemical species which reacts with a monomer to form an intermediate compound capable of successfully binding to a large number of other monomers to form a polymer or which reacts with polymers to initiate the process of molecular interconnection called polymerization.
• Tg is meant the glass transition temperature.
• the glass transition temperature can be measured by differential calorimetry (DSC), for example using the tangent at mid-height method measured between two inflection points located between the 3 rd heating cycle between 40 and 140°C.
• Root temperature means a temperature of approximately 20°C.
• substantially free of is meant a composition comprising less than 1%, preferably less than 0.1%, preferably less than 0.01%, preferably approximately 0%, of a compound, by weight per total weight of the composition.
• the present invention relates to an adhesive photopolymerizable composition.
• the composition comprises at least one block copolymer, preferably at least one (meth)acrylic block copolymer.
• the composition may comprise from 20 to 35%, preferably from 25 to 30%, of at least one block copolymer, by weight per total weight of the composition.
• the composition may comprise, for example, from 20 to 21%, alternatively from 21 to 22%, alternately 22 to 23%, alternately 23 to 24%, alternately 24 to 25%, alternately 25 to 26%, alternately 26 to 27%, alternately 27 to 28%, alternately 28 to 29%, alternately from 29 to 30%, alternatively from 30 to 31%, alternatively from 31 to 32%, alternatively from 32 to 33%, alternatively from 33 to 34%, alternatively from 34 to 35%, of at least one block copolymer, by weight per total weight of the composition.
• (meth)acrylic block copolymer is meant a (meth)acrylic block copolymer comprising 10% or less (for example from 0.1 to 10%), preferably 5% or less (for example from 0.1 to 5%) , of at least one non-(meth)acrylic monomer, by weight per total weight of the copolymer.
• the non-(meth)acrylic monomer can be chosen from the group consisting of butadiene, isoprene, styrene, vinylnaphthalene, a cyclosiloxane monomer, vinyl Ipyridine and their derivatives (for example ⁇ -methylstyrene or tert -butylstyrene).
• the block copolymer can be chosen from block copolymers comprising at least one M block and at least one B block, in particular block copolymers having the B-M diblock structure (or B-M diblock copolymer) or the M-B-M triblock structure (or triblock M-B-M), in which each block is linked to the other by means of a covalent bond or by an intermediate molecule linked to one of the blocks by a covalent bond and to the other block by another covalent bond.
• the block copolymer is preferably an M-B-M triblock copolymer.
• the block M designates a polymer block comprising at least 50% by weight of methyl methacrylate.
• the block M can designate a homopolymer block of polymethyl methacrylate (PMMA - 100% by weight of methyl methacrylate) or a block copolymer comprising at least 50% by weight of methyl methacrylate and 50% or less of another monomer, different from methyl methacrylate, by weight per total weight of block M.
• Block B designates an elastomeric polymer block incompatible with block M, and whose glass transition temperature (Tg) is lower than room temperature, preferentially lower than 0° C., preferentially lower than -20° C.
• Tg glass transition temperature
• the M block may consist of methyl methacrylate monomers.
• block M can comprise at least 50% (for example from 50 to 99.9%), preferably at least 75% (for example from 75 to 99.9%), of methyl methacrylate; and 50% or less (for example from 0.1 to 25%), preferably 25% or less (for example from 0.1 to 25%), of at least one other monomer other than methyl methacrylate, by weight per total weight of the block Mr.
• the other monomer, different from methyl methacrylate, constituting the block M, can be another (meth)acrylic monomer or a non-(meth)acrylic monomer.
• the non-(meth)acrylic monomer can be chosen from the group consisting of butadiene, isoprene, styrene, vinylnaphthalene, a cyclosiloxane monomer, vinylpyridine and their derivatives (for example ⁇ -methylstyrene or tert- butylstyrene).
• the other (meth)acrylic monomer can be selected from the group consisting of methyl acrylate, ethyl (meth)acrylate, (meth)acrylic acid, propyl (meth)acrylate, (meth)acrylate, )n-butyl acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, amides derived from (meth)acrylic acid (for example N,N-dimethylacrylamide), 2-methoxyethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, polyethylene glycol (PEG) (meth)acrylate ), in which the PEG group has a molar mass ranging from 400 to 10,000 g/mol, and mixtures thereof.
• PEG polyethylene glycol
• the elastomeric block B may consist of alkyl (meth)acrylate monomer.
• block B can comprise at least 95% (for example from 95 to 99.9%) of alkyl (meth)acrylate; and 5% or less (for example from 0.1 to 5%) of another monomer other than alkyl (meth)acrylate, by weight per total weight of block B.
• the other monomer, different from the alkyl (meth)acrylate can be chosen from the group consisting of butadiene, isoprene, styrene, vinylnaphthalene, a cyclosiloxane monomer, vinylpyridine and their derivatives (for example a-methylstyrene or tert-butylstyrene).
• the B-M diblock copolymer can have a number-average molar mass of between 10,000 and 500,000 g/mol, preferably between 20,000 and 200,000 g/mol.
• the B-M diblock copolymer may comprise a mass fraction (by weight per total weight of the copolymer) of between 5 and 95%, preferably between 15 and 85%, in block M; and between 5 and 95%, preferably between 15 and 85%, in block B.
• the two M blocks consist of the same monomers (or co-monomers) as the M block of the B-M diblock copolymer as described above.
• These two blocks M can be identical or different.
• these two blocks M can be different by their molar mass, but consist of the same monomers.
• the B block consists of the same monomers (or co-monomers) as the B block of the B-M diblock copolymer as described above.
• the M-B-M triblock copolymer may have a number-average molar mass of between 10,000 g/mol and 500,000 g/mol, preferably between 20,000 and 200,000 g/mol.
• the MBM triblock copolymer can comprise a mass fraction (by weight per total weight of the copolymer) of between 10 and 80%, preferentially between 15 and 70%, preferentially between 40 and 60%, in blocks M; and between 20 and 90%, preferentially between 30 and 85%, preferentially between 40 and 60%, in block B.
• An example of MBM triblock copolymer is a polymethylmethacrylate-poly(styrene-co-butylacrylate)-polymethylmethacrylate block copolymer.
• the block copolymers can be manufactured by controlled radical polymerization (PRC), for example according to the methods as described in PCT applications WO 96/24620 A and WO 00/71501 A1, or by anionic polymerization.
• PRC controlled radical polymerization
• One or less of the M and B blocks can be functionalized by means of one or more functions chosen from the group consisting of acid, amine, amide, epoxy, thiol functions, quaternary ammonium groups, chlorinated groups and fluorinated groups.
• Block copolymers are commercially available under the name Nanostrength® from Arkema.
• the composition comprises at least one (meth)acrylate monomer having a glass transition temperature (Tg) of at least 85°C.
• the composition may comprise from 45 to 75%, preferably from 45 to 70%, preferably from 45 to 65%, of at least one (meth)acrylate monomer having a glass transition temperature of at least 85° C., by weight by total weight of the composition.
• the composition may comprise, for example, from 45 to 46%, alternatively from 46 to 47%, alternatively from 47 to 48%, alternatively from 48 to 49%, alternatively from 49 to 50%, alternatively from 50 to 51%, alternatively from 51 to 52%, alternately from 52 to 53%, alternately from 53 to 54%, alternately from 54 to 55%, alternately from 55 to 56%, alternately from 56 to 57%, alternately from 57 to 58%, alternately from 58 to 59%, alternately 59 to 60%, alternately 60 to 61%, alternately 61 to 62%, alternately 62 to 63%, alternately 63 to 64%, alternately 64 to 65%, alternately 65 to 66%, alternately from 66 to 67%, alternately from 67 to 68%, alternately from
• the (meth)acrylate monomer having a glass transition temperature of at least 85°C can be chosen from the group consisting of methyl methacrylate, tert-butyl methacrylate, phenyl-methacrylate, isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-ter-butylcyclohexyl methacrylate, dihydrodicyclopentadienyl acrylate and mixtures thereof; preferentially, the (meth)acrylate monomer having a glass transition temperature of at least 85° C. is methyl methacrylate.
• the composition comprises at least one alkoxysilane (meth)acrylate monomer.
• the composition may comprise from 2 to 15%, preferably from 3 to 10%, preferably from 4 to 6%, of at least one alkoxysilane (meth)acrylate monomer, by weight per total weight of the composition.
• the composition may comprise, for example, from 2 to 3%, alternatively from 3 to 4%, alternatively from 4 to 5%, alternatively from 5 to 6%, alternatively from 6 to 7%, alternatively from 7 to 8%, alternatively from 8 to 9%, alternately from 9 to 10%, alternately from 10 to 11%, alternately from 11 to 12%, alternately from 12 to 13%, alternately from 13 to 14%, alternately from 14 to 15%, d at least one alkoxysilane (meth)acrylate monomer, by weight per total weight of the composition.
• the alkoxysilane (meth)acrylate monomer may be selected from the group consisting of trialkoxysilane (meth)acrylate monomers; preferably trimethoxysilane (meth)acrylate monomers; preferentially, the alkoxysilane (meth)acrylate monomer is chosen from the group consisting of 3-(trimethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, trimethoxysilyl acrylate, trimethoxysilyl acrylate and mixtures thereof; preferentially, the alkoxysilane (meth)acrylate monomer is trimethoxysilyl acrylate.
• Trimethoxysilane acrylate is commercially available under the name Silquest® A174 from Momentive®.
• the composition includes at least one photoinitiator.
• Any compound capable of initiating the photopolymerization of the adhesive composition in particular any compound capable of initiating the radical polymerization of urethane (meth)acrylate monomers and/or oligomers by irradiation with ultraviolet (UV) or visible light, to obtain the adhesive, can be used.
• UV ultraviolet
• the composition may comprise from 0.1 to 5%, preferentially from 0.5 to 4%, preferentially from 1 to 3%, of at least one photoinitiator, by weight per total weight of the composition.
• the composition may comprise, for example, from 0.1 to 1%, alternatively from 1 to 2%, alternatively from 2 to 3%, alternatively from 3 to 4%, alternatively from 4 to 5%, of at least one photoinitiator, in weight per total weight of the composition.
• the photoinitiator can be chosen from the group consisting of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, triethylbenzoyl-diphenylphosphine oxide, thioxanthen-9-one, 4,4-bis(diethylamino)benzophenone, 9 ,10-phenanthrene quione, benzoyltrimethylgermane, dibenzoyldiethylgermane, bis-(4-methoxybenzoyl)diethylgermanium and their mixtures; preferentially phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.
• a mixture may include, for example, benzophenone, ⁇ -hydroxyketone and triethylbenzoyl-diphenylphosphine oxide.
• Another mixture may include, for example, benzoyltrimethylgermane, dibenzoyldiethylgermane and bis-(4-methoxybenzoyl)diethylgermanium.
• Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide is commercially available under the name Irgacure® 819 from Ciba® Specialty Chemicals.
• the mixture comprising benzophenone, ⁇ -hydroyketone and triethylbenzoyl-diphenylphosphine oxide is commercially available under the name Esacure® KTO 46 from Lehvoss.
• the composition may comprise at least one (meth)acrylate monomer having a glass transition temperature (Tg) below 0°C.
• the composition comprises the mixture of a (meth)acrylate monomer having a glass transition temperature of at least 85°C and a (meth)acrylate monomer having a glass transition temperature below 0°C .
• the composition may comprise from 0 to 5% of at least one (meth)acrylate monomer having a glass transition temperature below 0° C., by weight per total weight of the composition. If present, the composition may comprise from 0.1 to 5% of at least one (meth)acrylate monomer having a glass transition temperature below 0°C, by weight per total weight of the composition.
• the composition may comprise, for example, from 0 to 1% (from 0.1 to 1%), alternatively from 1 to 2%, alternatively from 2 to 3%, alternatively from 3 to 4%, alternatively from 4 to 5%, d at least one (meth)acrylate monomer having a glass transition temperature below 0° C., by weight per total weight of the composition.
• the (meth)acrylate monomer having a glass transition temperature below 0°C can be chosen from the group consisting of butyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate , octyl acrylate, dodecyl acrylate, isopropyl acrylate, isobutyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate , isodecyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl acrylate and mixtures thereof; preferably butyl acrylate.
• the composition may be substantially free of (meth)acrylate monomers having a glass transition temperature (Tg) below 0°C.
• the composition may include a methacrylic acid monomer.
• the composition may comprise from 0 to 20% methacrylic acid, by weight per total weight of the composition. If present, the composition comprises from 1 to 16%, preferably from 3 to 12%, of methacrylic acid, by weight per total weight of the composition.
• the composition may comprise, for example, from 0 to 1%, alternatively from 1 to 2%, alternatively from 2 to 3%, alternatively from 3 to 4%, alternatively from 4 to 5%, alternatively from 5 to 6%, alternatively from 6 to 7%, alternately from 7 to 8%, alternately from 8 to 9%, alternately from 9 to 10%, alternately from 10 to 11%, alternately from 11 to 12%, alternately from 12 to 13%, alternately from 13 to 14%, alternately 14 to 15%, alternately 15 to 16%, alternately from 16 to 17%, alternatively from 17 to 18%, alternatively from 18 to 19%, alternatively from 19 to 20%, of methacrylic acid, by weight per total weight of the composition.
• the composition may comprise at least one urethane (meth)acrylate oligomer.
• the composition may comprise from 0 to 7% of at least one urethane (meth)acrylate oligomer, by weight per total weight of the composition. If present, the composition comprises from 0.1 to 7%, preferably from 3 to 6%, of at least one urethane (meth)acrylate oligomer, by weight per total weight of the composition.
• the composition may comprise, for example, from 0 to 1%, alternatively from 1 to 2%, alternatively from 2 to 3%, alternatively from 3 to 4%, alternatively from 4 to 5%, alternatively from 5 to 6%, alternatively from 6 to 7%, alternatively from 7 to 8%, alternatively from 8 to 9%, alternatively from 9 to 10%, of at least one urethane (meth)acrylate oligomer, by weight per total weight of the composition.
• the urethane (meth)acrylate oligomer can be chosen from aliphatic urethane diacrylate oligomers, preferably the urethane (meth)acrylate oligomer is aliphatic urethane diacrylate.
• composition may further comprise at least one monofunctional reactive diluent.
• the composition can comprise from 0 to 0.7% of at least one monofunctional reactive diluent, by weight per total weight of the composition. If present, the composition comprises from 0.1 to 0.7%, preferably from 0.3 to 0.7%, of at least one monofunctional reactive diluent, by weight per total weight of the composition.
• the monofunctional reactive diluent can be 2-(2-ethoxy-ethoxy)ethyl acrylate.
• the adhesive photopolymerizable composition is preferably a liquid composition.
• the composition may have a viscosity of 100 to 10,000 mPa.s, preferentially from 500 to 5,000 mPa.s, more preferentially from 1,000 to 2,500 mPa.s.
• the viscosity can be measured according to standard NF EN 12092 "Adhesives - Determination of viscosity" using a Brookfield DVIII Ultra viscometer (spindle: SC4-27, rotation: 20 revolutions/minute, temperature: 25° C.).
• the composition has a glass transition temperature, preferably of at least 85°C, preferably of at least 90°C, preferably of at least 100°C.
• composition may comprise (alternatively may consist of), by weight per total weight of the composition:
• composition may comprise (alternatively may consist of):
• At least one block copolymer preferably at least one (meth)acrylic block copolymer; preferably a (meth)acrylic block copolymer having an M-B-M triblock structure;
• At least one (meth)acrylate monomer having a glass transition temperature of at least 85°C preferably a monomer selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, phenyl-methacrylate, isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-ter-butylcyclohexyl methacrylate, dihydrodicyclopentadienyl acrylate and mixtures thereof; preferentially a monomer being methyl methacrylate;
• alkoxysilane (meth)acrylate monomer preferably a monomer chosen from the group consisting of trialkoxysilane (meth)acrylate monomers; preferably trimethoxysilane (meth)acrylate monomers; preferably 3-(trimethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, trimethoxysilyl acrylate, trimethoxysilyl acrylate and mixtures thereof; preferentially a monomer being trimethoxysilyl acrylate;
• a photoinitiator preferentially a photoinitiator chosen from the group consisting of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, triethylbenzoyl-diphenylphosphine oxide, thioxanthen-9-one, 4,4-bis(diethylamino)benzophenone, 9, 10-phenanthrene quione, benzoyltrimethylgermane, dibenzoyldiethylgermane, bis-(4-methoxybenzoyl)diethylgermanium and mixtures thereof; preferentially a photoinitiator being phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide;
• (meth)acrylate monomer having a glass transition temperature below 0° C.; preferably a monomer selected from the group consisting of butyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, isopropyl acrylate, isobutyl acrylate, isodecyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, isodecyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl and mixtures thereof; preferably a monomer being butyl acrylate;
• urethane (meth)acrylate oligomer optionally at least one urethane (meth)acrylate oligomer; preferably an oligomer chosen from aliphatic urethane diacrylate oligomers; preferentially an oligomer being aliphatic urethane diacrylate;
• diluent 2-(2-ethoxy-ethoxy)ethyl acrylate.
• the composition is a single-component composition, that is to say a ready-to-use composition.
• the composition is not a multi-component composition, that is to say a kit comprising at least two separately packaged components, which components are intended to be mixed together externally, just before application of the composition thus obtained.
• a one-component composition does not need to be prepared in the form of at least two separate components, which must be mixed just before use, in order to avoid premature polymerization.
• the single-component composition comprises at least one photoinitiator, making it possible to initiate the polymerization when the composition is exposed to light radiation, in particular ultraviolet (UV) radiation.
• UV radiation ultraviolet
• the composition must not be exposed to light.
• the present invention comprises an adhesive product.
• the adhesive product comprises the adhesive photopolymerizable composition as described above and an opaque container containing it.
• opaque container is meant a container whose walls do not allow light capable of activating the photoinitiator, in particular visible light and ultraviolet radiation (less than 600 nm), to pass.
• the opaque container can be any container capable of containing the composition and of retaining its properties, in particular the adhesive properties. The use of an opaque container makes it possible not to expose the composition to light (in particular to ultraviolet radiation) before use, that is to say during its storage and transport, and thus avoids any premature or untimely polymerization .
• the container can be chosen, for example, from the group consisting of a bottle or a tube.
• the present invention relates to an adhesive, in particular an adhesive obtained from the photopolymerizable adhesive composition as described above.
• adhesive or “photopolymerized adhesive composition” is meant the adhesive layer obtained by applying the photopolymerizable adhesive composition, by photopolymerizing the latter and optionally by shaping the adhesive thus obtained.
• the adhesive is obtained by the process comprising the following steps:
• the adhesive may take the form of a film.
• the application of the composition can be implemented by a conventional application technique, for example the following techniques: coating in a slot die (slot-die coating), coating by immersion (deep coating), inkjet printing , screen printing, deposition by centrifugation (spin coating), deposition by spraying (spray coating) or with a rigid knife applicator (doctor blade).
• the photopolymerization of the composition can be implemented by exposure to ultraviolet (UV) radiation and to visible light, in particular by the use of a UV lamp emitting in a range making it possible to activate the photoinitiator without being absorbed by the encapsulation cover.
• a suitable UV lamp can be, for example, a UV source of the Delolux® 03S system UV LED type.
• the light-curing can be implemented between 1 and 10 min.
• the optional shaping of the adhesive can be implemented, for example, by a thermoforming technique.
• the adhesive may have a thickness of 10 to 200 ⁇ m, preferentially from 10 to 100 ⁇ m, preferentially from 10 to 30 ⁇ m.
• the adhesive has a number of advantages, in particular for use at a temperature of at least 70° C., preferably at least 85° C., for example when the electronic or optoelectronic device is a photovoltaic cell or when the device must meet temperature test standards (automotive applications for example).
• the adhesive preferably has satisfactory adhesive properties, in particular to allow satisfactory cohesion between the electronic or optoelectronic device and the covers, even for flexible modules.
• the adhesive preferably has satisfactory optical properties, in particular satisfactory transparency, in particular to allow the transmission of light waves to the electronic or optoelectronic device and/or to limit diffraction, in particular when the device is a photovoltaic cell.
• the adhesive can have a transparency of 90% in transmission between 400 and 800nm. Transparency can be measured by UV-visible transmission spectrometry.
• the adhesive preferably has satisfactory electrical properties, in particular satisfactory electrical insulation properties, in particular to avoid any short circuit inside the module. Electrical insulation properties can be measured with ASTM D149.
• the adhesive preferably has satisfactory resistance, in particular to aging under ultraviolet radiation, to abrasion and/or to impact.
• the adhesive preferably exhibits satisfactory barrier properties, in particular barrier properties to water and to oxygen (air).
• the barrier properties can be measured with the ASTM F1249 standard with a water vapor transmission rate of less than 5 g.rrr 2 .d' 1 , preferably less than 2 g.rrr 2 .d ' 1 , for a thickness of 1 mm, at a temperature of 38° C. and a relative humidity of 85%.
• the adhesive preferably has satisfactory elastic properties.
• Elastic properties, especially flexibility, can be measured using a cylindrical mandrel bend tester, with the three or four point bending test method, or with tensile measurements.
• the present invention relates to a module, preferably a flexible module.
• the module corresponds to an encapsulated electronic or optoelectronic device.
• the module can be obtained by superimposing and assembling a series of layers.
• the series of layers can include, in this order:
• the electronic or optoelectronic device may itself comprise a semiconductor layer deposited on a support substrate.
• This series of layers can also comprise additional layers, in particular layers interposed between a cover and an adhesive, for example an additional layer improving the adhesion between the internal surface of a cover and a layer of adhesive composition, a surface treatment hood, etc.
• the electronic or optoelectronic device is preferably coated with the two adhesives, which overlap at their periphery, in order to form a tight seal.
• the coating of the electronic or optoelectronic device by the adhesives, and its encapsulation between the two covers, makes it possible to isolate it from its environment.
• the module thus obtained has satisfactory properties, making it possible to limit, or even prevent, both orthogonal permeation and lateral permeation, while retaining the flexibility properties of the electronic or optoelectronic device.
• the module can have a total thickness of 50 to 500 ⁇ m, preferentially from 50 to 300 ⁇ m, preferentially from 50 to 150 ⁇ m.
• the electronic or optoelectronic devices can be chosen from rigid, flexible devices or combinations thereof; preferably the devices are flexible devices; preferentially, the devices are chosen from organic light-emitting diodes, organic photovoltaic cells, organic transistors, transistors or organic sensors.
• the photovoltaic cells are perovskite type devices.
• the so-called halogenated perovskite material can comprise in its crystalline structure a metal (for example lead or tin), organic and inorganic cations (for example cesium, formamidinium and/or ammonium), halide anions (for example example boron or iodine).
• Perovskite-type devices are particularly suitable for photovoltaic applications. However, perovskite-type devices can present stability problems over time, due to their sensitivity to the atmosphere, in particular to water vapour.
• the covers can be identical or different.
• Hoods can be monolayer or multilayer.
• the covers can be flexible or rigid, preferably flexible.
• the module can have an orientation, for example in that it comprises a lower or rear cover (commonly referred to as a "rear face” or “backsheet” in English) and an upper or front cover (commonly referred to as a “front face” or “frontsheet” in English).
• the upper or front cover is preferably transparent and the lower or rear cover is preferably opaque.
• a cover can be a polymer cover.
• a cap may be an inorganic cap.
• a polymer cover can comprise at least one fluorinated polymeric layer obtained from at least one fluorinated polymer, for example poly(vinyl fluoride) (PVF), poly(vinylidene fluoride) (PVDF) and their mixture.
• fluorinated polymer for example poly(vinyl fluoride) (PVF), poly(vinylidene fluoride) (PVDF) and their mixture.
• a polymer cover can comprise at least one polymeric layer obtained from polyethylene terephthalate (PET) (or PET layer).
• PET polyethylene terephthalate
• a polymer cover can comprise at least one polymeric layer obtained from ethylene-vinyl acetate (EVA) (or EVA layer).
• EVA ethylene-vinyl acetate
• a monolayer cover can comprise a layer chosen from a fluorinated polymeric layer, a PET layer or an EVA layer.
• a multilayer cap can comprise at least two layers, preferably three layers, chosen from a fluorinated polymer layer, a PET layer, an EVA layer or combinations thereof.
• a three-layer cover can be a fluorinated polymer layer/PET layer/fluorinated polymer layer or fluorinated polymer layer/PET layer/EVA layer cover.
• the fluorinated polymeric layer, the PET layer, the EVA layer and their combinations, and the monolayer or multilayer covers obtained therefrom, are particularly suitable for use as a lower or rear cover.
• a cover can include at least one layer of glass.
• a cover can comprise at least one polymeric layer obtained from polymethyl methacrylate (PMMA) (or PMMA layer).
• PMMA polymethyl methacrylate
• the glass layer or the PMMA layer is particularly suitable for use as a top or front cover.
• a flexible cover particularly suitable for the encapsulation of flexible electronic or optoelectronic devices, in particular organic photovoltaic cells, for example devices of the perovskite type, is commercially available under the name 3M Ultra-Barrier Solar Film from 3M®.
• This cover is a laminated multilayer cover comprising a PET film, an inorganic barrier layer, a so-called PSA film (pressure sensitive adhesive or pressure-sensitive adhesive) and a fluoro-polymer film.
• PSA film pressure sensitive adhesive or pressure-sensitive adhesive
• the present invention relates to a method for obtaining the module as described above, the method comprising the following steps: - the supply of an electronic or optoelectronic device;
• the method may also comprise a step of irradiating the first cover and/or the second cover with ultraviolet-ozone radiation before the application step and/or the lamination step.
• the rigid modules are obtained by a technique by lamination (rolling) under vacuum temperature (designated “plate to plate” or “sheet to sheet” in English).
• the flexible modules are obtained by a roll-to-roll technique, as described for example in the article by S. Razza et al. entitled “Research Update: Large-area deposition, coating, printing, and processing techniques for the upscaling of perovskite solar cell technology”, APL Materials (2016) 4(9).
• This technique is particularly suitable for flexible electronic or optoelectronic devices; preferentially devices chosen from organic light-emitting diodes, organic photovoltaic cells, organic transistors, or organic sensors; preferentially devices of the perovskite type.
• the present invention relates to the use of the adhesive photopolymerizable composition as described above, and of the adhesive as described above obtained therefrom, for the encapsulation of electronic devices. or optoelectronics, in particular for the encapsulation of flexible electronic or optoelectronic devices, for example for the encapsulation of organic photovoltaic devices, in particular devices of the perovskite type.
• Block copolymer M-B-M triblock copolymer [polymethylmethacrylate-poly(styrene-co-butylacrylate)-polymethylmethacrylate block copolymer] (abbreviation: M-B-M)
• Alkoxysilane (meth)acrylate monomers trimethoxysilane acrylate (Silquest® A174 product from Momentive®) (abbreviation: A174)
• Photoinitiators phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure® 819 product from Ciba® Specialty Chemicals) (abbreviation: 1819), also available from Sigma-Aldrich
• AMA Methacrylic acid
• Urethane (meth)acrylate oligomers aliphatic urethane diacrylate in 10% 2-(2-ethoxy-ethoxy)ethyl acrylate (CN966H90® product from Sartomer) (abbreviation: CN966)
• the modules to be tested are commonly referred to as specimens.
• PK layer perovskite layer of formula Cso,o5FAo,95Pb(lo,88Bro,i2)3 with an area of 4x4 cm (16 cm 2 )
• Glass layer layer with an area of 5x5 cm (25 cm 2 )
• ITO layer indium oxide layer doped with tin
• Sn ⁇ 2 layer layer of tin dioxide
• the glass, ITO and/or SnO2 layers form the support substrate as such.
• Multilayer module 1 glass/ITO/SnO2/PK
• Multilayer module 2 glass/ITO/PK/ITO
• the SnO2 and/or PK layers are deposited by the spin coating technique.
• the upper ITO layer (module 2) is deposited by physical vapor deposition.
• the perovskite layers are deposited on the support substrate, with an overhang of 5 mm between the edge of the substrate and the perovskite layer.
• the modules are individually encapsulated between two glass covers having a thickness of 1.2 mm by means of the photopolymerizable compositions to be tested. Test methods
• the thermal and gas barrier properties of the tested modules were analyzed with a differential calorimetric analyzer (DSC).
• DSC differential calorimetric analyzer
• the measurements are carried out over three cooling-heating cycles ranging from -80 to 200°C at a rate of 10°C per minute.
• the glass transition temperature is measured on the third heating cycle with the tangent method at mid-height calculated between 40° and 140°C.
• the degradation rate (cm 2 /h) is determined with respect to the degradation of a perovskite layer.
• the degradation of the modules tested was assessed with the following method: the specimen as described above is placed in a climatic chamber at a temperature of 85°C and a relative humidity of 85% in accordance with the climatic conditions for testing the modules photovoltaic cells reported in the IEC 61615 standard method, in order to determine an algorithmic degradation rate parameter (cm 2 /h). See the article by E. Booker et al. entitled “Perovskite Test: A high throughput method to screen ambient encapsulation conditions”, Energy Technology (2020) 8(12).
• Photographic shots of the specimens are taken regularly, for example approximately every 48 hours, in order to evaluate the aging of the perovskite layers.
• the residual surface of the perovskite layers is determined, in order to calculate the rate of degradation of these layers (cm 2 /h) from a linear regression of the points between 12 cm 2 and 2 cm 2 .
• Areas having a thickness of 180 nm or less are considered to be degraded areas (black areas by algorithmic analysis) and areas having a thickness greater than 180 nm are considered to be intact areas (gray areas by algorithmic analysis).
• photopolymerizable adhesive compositions were prepared (see Table 1, proportions expressed as percentage by mass relative to the total weight of the photopolymerizable adhesive composition):
• compositions CExA and CExB are comparative compositions.
• composition Ex1 invention
• compositions CExA and CExB comparative
• Two series of tests are carried out with each composition.
• compositions differ in particular by the proportion of (meth)acrylate monomers having a glass transition temperature below 0° C. (in this case butyl acrylate), considering that they comprise an identical total proportion (53.55%) of monomers (meth)acrylates, that is to say the mixture of monomers having a glass transition temperature of at least 85°C and of (meth)acrylate monomers having a glass transition temperature below 0°C.
• composition ExA has a glass transition temperature of 86.2°C.
• the tested modules are photographed at regular intervals.
• the pictures are taken at Oh, 159h, 280h, 351h, 447h, 521h, 624h, 737h, 852h, 948h and 1091h, as illustrated in figure 1 (the first lines correspond to the photographs and the second lines correspond images after computer analysis).
• composition Ex1 demonstrates that the comparative compositions, comprising a high proportion of (meth)acrylate monomers having a glass transition temperature below 0° C., exhibit an insufficient glass transition temperature and a high degradation rate, which corresponds to a high lateral permeation rate.
• the modules tested according to the invention have a water vapor transmission rate of 2 g.mm.M′ 2 .d′ 1 , according to the method described in the article by A.Kovrov et al. entitled “Novel acrylic monomers for organic photovoltaics encapsulation”, Solar Energy Materials & Solar Cells (2020) 110210.
• compositions differ in particular by the proportion of block copolymer.
• the tested modules are photographed at regular intervals.
• the pictures are taken at Oh, 265h, 505h, 771h, 1002h, as shown in Figure 3 (each line corresponds to the photographs).
• the photoaging of the layers, and their possible yellowing is measured between 0 and 1600 h.
• the empty circles (white) correspond to the data relating to the commercial composition at 1600 h
• the solid circles (black) correspond to the data relating to the commercial composition at 0 h
• the empty triangles (white) correspond to the data relating to the Ex1 composition at 1600 h
• the solid triangles (black) correspond to the data relating to the Ex1 composition at 0 h

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Physics & Mathematics (AREA)
• Electromagnetism (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Electroluminescent Light Sources (AREA)
• Polymerisation Methods In General (AREA)
• Polymerization Catalysts (AREA)
• Graft Or Block Polymers (AREA)
• Polyurethanes Or Polyureas (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Sealing Material Composition (AREA)
• Photovoltaic Devices (AREA)

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• 2021
  • 2021-12-22 FR FR2114208A patent/FR3130824B1/fr active Active
• 2022
  • 2022-12-22 WO PCT/EP2022/087431 patent/WO2023118410A1/fr not_active Ceased
  • 2022-12-22 JP JP2024538048A patent/JP2025503489A/ja active Pending
  • 2022-12-22 US US18/723,324 patent/US20250066649A1/en active Pending
  • 2022-12-22 CN CN202280085514.4A patent/CN118696103A/zh active Pending
  • 2022-12-22 KR KR1020247024656A patent/KR20240134327A/ko active Pending
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