Photopolymerizable adhesive composition for encapsulating electronic or optoelectronic devices

Abstract

The present invention relates to a photopolymerizable adhesive composition comprising, in terms of total weight of the photopolymerizable adhesive composition, at least one block copolymer, preferably a (meth)acrylic block copolymer, at least one (meth)acrylate monomer having a glass transition temperature (Tg) of at least 85°C of the homopolymer obtained after polymerization, at least one alkoxysilane (meth)acrylate monomer, 1 to 15% by weight of a filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay, and at least one photoinitiator.

Description

[Technical Field]

[0001] The present invention relates to a photopolymerizable adhesive composition used for sealing electronic and optoelectronic devices, particularly flexible electronic and optoelectronic devices such as organic photocells, for the purpose of protecting them from gas and moisture penetration. [Background technology]

[0002] There are various types of electronic or optoelectronic devices, including rigid or flexible electronic or optoelectronic devices. Rigid electronic or optoelectronic devices can have different properties depending on the application under consideration, such as display applications (e.g., OLED and QLED), photovoltaics (e.g., silicon-based semiconductors, CIGS, CDTE, organic semiconductors, perovskite semiconductors), or sensors.

[0003] Flexible electronic and optoelectronic devices can be defined by the same application examples, but they refer to semiconductor technologies suitable for use with flexible substrates, such as organic light-emitting diode (OLED) devices, organic photovoltaics (OPVs), amorphous silicon batteries (a-Si), CIGS, perovskite semiconductors, organic transistors (OFETs), or organic sensors using organic semiconductors.

[0004] Electronic or optoelectronic devices are sensitive to multiple factors, including light, heat, oxygen (air), moisture, pressure, and shock. To ensure optimal efficiency and performance and achieve satisfactory durability, these devices must be protected and isolated from their environment. This protection needs to be even more effective because the constituent materials are sensitive to the atmosphere, particularly water and oxygen. This is especially true when using organic semiconductors such as perovskite or CIGS semiconductors.

[0005] Various sealing techniques are employed. These typically involve coating a device with an adhesive composition to obtain a sealed device, and then laminating the sealed device between two covers to obtain another sealed device. The choice of adhesive composition and cover depends on the device being sealed. Furthermore, depending on the composition and cover used, the resulting electronic or optoelectronic module will have characteristics, particularly in terms of weight, thickness, transparency / opacity, rigidity / flexibility, permeability / sealability to gases and liquids, impact resistance, and / or durability / aging.

[0006] Due to the layered arrangement, two types of penetration are observed: orthogonal penetration on the outer surface of the cover sandwiching the sealed device, and lateral penetration at the free end of the adhesive within the sealant and at the interface between the two covers.

[0007] Protecting devices from lateral penetration is particularly ensured by adhesives or sealants, and the effectiveness of these adhesives or sealants can depend on various factors, including their chemical composition, application method, thickness (proportional to the surface area exposed to the environment), interface with the cover, and resistance to usage conditions. Therefore, the properties of the adhesive must be optimized to minimize, or even eliminate, lateral penetration, thereby ensuring optimal efficiency and performance and achieving satisfactory durability.

[0008] Flexible photocells (e.g., organic, perovskite, CIGS, CDTE cells) are a particularly interesting alternative to rigid silicon photocells because they can be manufactured using continuous and high-speed processes (roll-to-roll methods) and are suitable for applications requiring flexibility, conformability, or lightweight design. They are also less prone to breakage and damage (due to the use of flexible covers).

[0009] Flexible photocells can be obtained, for example, by printing a thin active layer (an organic or perovskite material with semiconductor properties) deposited on a flexible polymer support substrate at low temperatures.

[0010] The encapsulation of flexible electronics or optoelectronic devices is achieved by a cover with low permeability to gases, especially water vapor and oxygen, which needs to have at least the same degree of flexibility as the device, so as not to be a factor limiting the bending of the device to be protected, or, if intentionally used, for example, to limit the bending radius of the device to prevent damage to the device, it needs to have controlled flexibility.

[0011] Therefore, there is an urgent need to provide an adhesive composition that enables the production of electronic or optoelectronic modules with satisfactory properties, especially adhesion, optical properties, thermal properties, electrical properties, gas and moisture barrier properties, elasticity and satisfactory resistance properties. There is also a need to provide an adhesive composition suitable for encapsulating flexible electronics or optoelectronic devices. Furthermore, there is a need to provide an adhesive composition that enables the production of electronic or optoelectronic modules with suppressed light degradation over time (e.g., yellowing). There is also a need to provide an adhesive composition that enables the production of electronic or optoelectronic modules with suppressed lateral gas and water penetration over time while maintaining good light transmission in the electronic or optoelectronic devices. There is also a need to provide an adhesive composition that guarantees optimal efficiency and performance as well as satisfactory durability.

Summary of the Invention

[0012] The present application mainly relates to a photopolymerizable adhesive composition, which comprises, based on the total weight of the photopolymerizable adhesive composition, at least one block copolymer, preferably a (meth)acrylic block copolymer, and at least one (meth)acrylate monomer having a glass transition temperature (Tg) of at least 85 °C of the homopolymer obtained after polymerization, and at least one alkoxysilane (meth)acrylate monomer, and 1 to 15% by weight of a filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay, and at least one photoinitiator. Preferably, the composition of the present invention is, with respect to the total weight of the photopolymerizable adhesive composition, 10-60% by weight, preferably 10-50% by weight, preferably 20-40% by weight, preferably 20-35% by weight, more preferably 25-35% by weight of at least one block copolymer, preferably a (meth)acrylic block copolymer, and 30-80% by weight, preferably 40-75% by weight, preferably 45-75% by weight, preferably 45-60% by weight, more preferably 45-55% by weight of at least one (meth)acrylate monomer, the homopolymer obtained after polymerization having a glass transition temperature (Tg) of at least 85°C. At least one alkoxysilane (meth)acrylate monomer in an amount of 1-20% by weight, preferably 2-15% by weight, preferably 3-10% by weight, preferably 4-6% by weight, A filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay in an amount of 1 to 15% by weight, preferably 1 to 12% by weight, more preferably 1 to 10% by weight, and more preferably 1.5 to 10% by weight, It comprises 0.1 to 5% by weight, preferably 0.5 to 4% by weight, preferably 1 to 3.5% by weight, and preferably 1 to 3% by weight of at least one photoinitiator.

[0013] Preferably, in the composition according to the present invention, the filler is -Type A zeolite, preferably 3A or 4A, -N + Organically modified clay containing quaternary ammonium ions of type R1R2R3R4, S + Organically modified clay containing R1R2R3 type sulfonium ions, P + Organically modified clay having R1R2R3R4 type phosphonium ions, wherein R1 to R4 are the same or different, and are composed of hydrogen, substituted or unsubstituted C1 to C25 alkyl groups, substituted or unsubstituted phenyl groups, substituted or unsubstituted benzyl groups, substituted or unsubstituted carboxyalkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted silane groups, or a mixture thereof, preferably N+ Organically modified clay containing quaternary ammonium ions of type R1R2R3R4, -A mixture of the zeolite and the organically modified clay.

[0014] In one embodiment, the block copolymer is selected from the group consisting of block copolymers comprising at least one M block and at least one B block. The M block refers to a polymer block containing at least 50% by weight of methyl methacrylate. The aforementioned Block B represents an elastomer polymer block that is incompatible with Block M and has a glass transition temperature (Tg) of less than 20°C.

[0015] In one embodiment, the alkoxysilane (meth)acrylate monomer is selected from the group consisting of trialkoxysilane (meth)acrylate monomers.

[0016] In one embodiment, the photopolymerizable adhesive composition of the present invention further comprises at least one (meth)acrylate monomer, a methacrylic acid monomer, at least one urethane (meth)acrylate oligomer, at least one monofunctional reactive diluent, and a mixture thereof, the glass transition temperature of the homopolymer obtained after polymerization being less than 0°C. Preferably, the (meth)acrylate monomer, if present, is 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 acrylate, and mixtures thereof.

[0017] In one embodiment, the composition is a single-component composition.

[0018] Preferably, the photopolymerizable adhesive composition according to the present invention has a glass transition temperature of at least 85°C, more preferably at least 90°C, and more preferably at least 100°C after polymerization.

[0019] This application also relates to an adhesive product comprising a photopolymerizable adhesive composition according to the present invention and an opaque container for containing the same.

[0020] This application also relates to an adhesive, and the adhesive is A step of applying the photopolymerizable adhesive composition according to the present invention to at least one cover and / or electronic or optoelectronic device, A step of photopolymerizing the applied photopolymerizable adhesive composition to obtain a polymerized adhesive, The method is obtained by optionally including a step of molding the polymerized adhesive.

[0021] This application also relates to an electronic or optoelectronic module, wherein the electronic or optoelectronic module is First cover, A first adhesive according to the present invention, or a first adhesive obtained from a photopolymerizable adhesive composition according to the present invention, Flexible electronic or optoelectronic devices, A second adhesive according to the present invention, or a second adhesive obtained from a photopolymerizable adhesive composition according to the present invention, The assembly includes a series of layers, including the second cover, in order.

[0022] Preferably, the electronic or optoelectronic module according to the present invention is characterized in that the flexible electronic or optoelectronic device is selected from organic light-emitting diodes, organic photocells, organic transistors, organic sensors, or a combination thereof.

[0023] Preferably, in the electronic or optoelectronic module according to the present invention, the flexible electronic or optoelectronic device is a perovskite type device.

[0024] This application also relates to a method for obtaining a module according to the present invention, the method being: A process of preparing an electronic or optoelectronic device, A step of preparing a photopolymerizable adhesive composition according to the present invention, The first step is to prepare the cover, The process of preparing the second cover, A step of applying a layer of the photopolymerizable adhesive composition to the surface of the device and / or to the inner surfaces of the first and second covers, respectively. A step of laminating the device and the photopolymerizable adhesive composition between the inner surfaces of the first and second covers, The process includes a step of photopolymerizing a layer of the photopolymerizable adhesive composition.

[0025] This application also relates to the use of a photopolymerizable adhesive composition or adhesive according to the present invention for encapsulating flexible electronic or optoelectronic devices. [Brief explanation of the drawing]

[0026] [Figure 1] This shows the change over time in the average surface area of ​​the active surfaces of compositions Cref, C1, and C2. [Figure 2] This shows the change over time in the average thickness of the active surface of compositions Cref, C1, and C2. [Figure 3] The VA of compositions Cref, C1, and C2 is shown. [Figure 4] The VE of compositions Cref, C1, and C2 is shown. [Figure 5] The DA12 of compositions Cref, C1, and C2 is shown. [Figure 6] DE380 of compositions Cref, C1, and C2 is shown. [Figure 7] This shows the change over time in the average surface area of ​​the active surfaces of compositions Cref, C2, C3, and C4. [Figure 8] This shows the change over time in the average thickness of the active surface of compositions Cref, C2, C3, and C4. [Figure 9] The VA of compositions Cref, C2, C3, and C4 is shown. [Figure 10]The VE of compositions Cref, C2, C3, and C4 is shown. [Figure 11] The DA12 of compositions Cref, C2, C3, and C4 is shown. [Figure 12] DE380 of compositions Cref, C2, C3, and C4 is shown. [Figure 13] This shows the change over time in the average surface area of ​​the active surfaces of compositions C5, C3, C6, and C7. [Figure 14] This shows the change over time in the average thickness of the active surface of compositions C5, C3, C6, and C7. [Modes for carrying out the invention]

[0027] The present invention will be described in more detail and in a non-limiting manner in the following description.

[0028] Unless otherwise specified, all percentages are based on weight. In this specification, the quantities shown for a given species may be applied to that species according to all of its definitions (as referred to herein), including more restrictive definitions.

[0029] The present invention will be described in more detail and in a non-limiting manner in the following description.

[0030] The term "flexibility" or "suppleness" refers to the ability of a material to be easily bent, folded, or folded, particularly due to its inherent properties and / or thinness.

[0031] The term "flexible electronic or optoelectronic device" (and modules derived therefrom) refers to a device (module) that maintains its electronic conductivity or semiconductor properties without the risk of buckling or delamination of electronic components, even when bent at a very small bending radius.

[0032] The term "adhesive" refers to a matrix / structure formed around an electronic or optoelectronic device by a photopolymerized adhesive composition. In this specification, the terms "adhesive" and "encapsulant" are used interchangeably.

[0033] The term "module" refers to an assembly of electronic or optoelectronic devices that is sealed with a polymer adhesive composition and inserted between two covers.

[0034] The term "cover" refers to an element that is layered with a sealed electronic or optoelectronic device in between. In this specification, this element is interchangeably referred to as a "support," "plate," or "sheet." The term "photopolymerizable composition" or "photocurable composition" refers to a composition in which polymerization is initiated (induced) by exposure to electromagnetic radiation, particularly ultraviolet (UV) light.

[0035] The term "photopolymerizable adhesive composition" advantageously refers to a composition that exhibits adhesive properties when exposed to electromagnetic radiation, particularly ultraviolet (UV) radiation, which initiates (induces) its polymerization.

[0036] The term "monomer" refers to a polymerizable molecule. When the term "monomer" is used to describe a component of a polymer, it refers to a unit (or residue) derived from a monomer (or monomer unit) (by polymerization with at least one other monomer).

[0037] The term "polymerization" refers to the process of converting a single type of monomer or a mixture of different types of monomers into a polymer.

[0038] The term "polymer" refers to copolymer or homopolymer.

[0039] The term "homopolymer" refers to a polymer formed by grouping multiple identical monomer units.

[0040] The term "copolymer" refers to a polymer formed by grouping together at least two different types of monomer units (the comonomers shown).

[0041] The term "oligomer" refers to a small polymer compound obtained by polymerizing 2 to 30 monomers (containing 2 to 30 monomer units), i.e., a compound with a degree of polymerization of 2 to 30.

[0042] The term "block copolymer" refers to a polymer in which each of different polymer species contains one or more consecutive sequences, where these polymer sequences are chemically distinct from one another and linked together by covalent bonds. These polymer sequences are also called polymer blocks.

[0043] The term "(meth)acrylic" (or "(meth)acrylate") refers to any type of compound, polymer, monomer, or oligomer, acrylic and / or methacrylic (or acrylate and / or methacrylate). For example, (meth)acrylic acid means acrylic acid or methacrylic acid, and isobornyl (meth)acrylate means isobornyl acrylate or isobornyl methacrylate, etc.

[0044] The term "polymerization" refers to a chemical method in which molecules can bond together to form a three-dimensional network.

[0045] The term "initiator" refers to a chemical species that reacts with a monomer to form an intermediate compound that can combine with many other monomers to form a polymer, or a chemical species that reacts with a polymer to initiate a process of molecular interconnection called polymerization.

[0046] The term "Tg" refers to the glass transition temperature of a polymer material. The glass transition temperature can be measured by differential scanning calorimetry (DSC), for example, using the tangential method at an intermediate height between two inflection points located between 40 and 140°C during the third heating cycle. In the context of this invention, a particular monomer is described by the Tg of the homopolymer obtained after polymerization of the monomer. In this case, the Tg is measured as follows: A homopolymer is formed by polymerizing the monomer to the maximum conversion rate, and the Tg of the obtained homopolymer is measured by DSC as described above.

[0047] The term "ambient temperature" refers to a temperature of approximately 20°C.

[0048] The term "substantially contained" means that the composition contains less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, and most preferably about 0% by weight of the compound, based on the total weight of the composition.

[0049] Photopolymerizable adhesive composition In a first aspect, the present invention relates to a photopolymerizable adhesive composition.

[0050] Block copolymer The composition comprises at least one block copolymer, preferably at least one (meth)acrylic block copolymer.

[0051] The composition may contain at least one block copolymer in an amount of 10-60% by weight, preferably 10-50% by weight, preferably 20-40% by weight, preferably 20-35% by weight, and more preferably 25-35% by weight, based on the total weight of the composition.

[0052] The term "(meth)acrylic block copolymer" means a (meth)acrylic block copolymer containing at least 10% by weight or less (e.g., 0.1 to 10% by weight), preferably 5% by weight or less (e.g., 0.1 to 5% by weight), of the total weight of the copolymer, of at least one non-(meth)acrylic monomer. The non-(meth)acrylic monomer can be selected from the group consisting of butadiene, isoprene, styrene, vinylnaphthalene, cyclosiloxane monomer, vinylpyridine, and their derivatives (e.g., α-methylstyrene or tert-butylstyrene).

[0053] The block copolymer can be selected from block copolymers comprising at least one M block and at least one B block, particularly block copolymers having a diblock BM structure (or diblock copolymer BM) or a triblock MBM structure (or triblock copolymer MBM), where each block is bonded to the other block by covalent bonds, or bonded by intermediate molecules that are bonded to one block by covalent bonds and to the other block by other covalent bonds. The block copolymer is preferably a triblock copolymer MBM.

[0054] Block M represents a polymer block containing at least 50% by weight of methyl methacrylate. Block M can represent a homopolymer block of polymethyl methacrylate (PMMA-100% by weight of methyl methacrylate), or a copolymer block containing at least 50% by weight of methyl methacrylate and 50% by weight or less of another monomer other than methyl methacrylate, relative to the total weight of Block M.

[0055] Block B is an elastomer polymer block that is incompatible with Block M and has a glass transition temperature (Tg) lower than the ambient temperature, preferably lower than 0°C, and more preferably lower than -20°C.

[0056] With respect to diblock copolymer BM, the M block may consist of monomers of methyl methacrylate. Alternatively, the M block may contain, based on the total weight of the M block, at least 50% by weight (e.g., 50-99.9% by weight), preferably at least 75% by weight (e.g., 75-99.9% by weight) of methyl methacrylate and 50% by weight or less (e.g., 0.1-25% by weight), preferably 25% by weight or less (e.g., 0.1-25% by weight) of at least one other monomer different from methyl methacrylate.

[0057] Other monomers that make up the M block, other than methyl methacrylate, may be other (meth)acrylic monomers or non-(meth)acrylic monomers.

[0058] Non-(meth)acrylic monomers can be selected from the group consisting of butadiene, isoprene, styrene, vinylnaphthalene, cyclosiloxane monomer, vinylpyridine, and their derivatives (e.g., α-methylstyrene or tert-butylstyrene).

[0059] Other (meth)acrylic monomers can be selected from the group consisting of methyl acrylate, ethyl (meth)acrylate, (meth)acrylic acid, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, amides derived from (meth)acrylic acid (e.g., N,N-dimethylacrylamide), 2-methoxyethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, polyethylene glycol (PEG) (meth)acrylate having a molar mass of polyethylene glycol (PEG) groups of 400 to 10,000 g / mol, and mixtures thereof.

[0060] Elastomer block B may consist of alkyl (meth)acrylate monomers. Alternatively, block B may contain at least 95% by weight (e.g., 95-99.9% by weight) of alkyl (meth)acrylate and 5% by weight or less (e.g., 0.1-5% by weight) of other monomers different from alkyl (meth)acrylate, based on the total weight of block B.

[0061] The alkyl (meth)acrylate can be selected from the group consisting of ethyl acrylate (Tg = -24°C of the homopolymer obtained after polymerization), butyl acrylate (Tg = -54°C of the homopolymer obtained after polymerization), 2-ethylhexyl acrylate (Tg = -85°C of the homopolymer obtained after polymerization), hydroxyethyl acrylate (Tg = -15°C of the homopolymer obtained after polymerization), 2-ethylhexyl methacrylate (Tg = -10°C of the homopolymer obtained after polymerization), and mixtures thereof, and preferably the alkyl (meth)acrylate is butyl acrylate.

[0062] Other monomers distinct from alkyl (meth)acrylates can be selected from the group consisting of butadiene, isoprene, styrene, vinylnaphthalene, cyclosiloxane monomers, vinylpyridine, and their derivatives (e.g., α-methylstyrene or tert-butylstyrene).

[0063] Diblock copolymer BM can have a number-average molar mass of 10,000 g / mol to 500,000 g / mol, preferably 20,000 to 200,000 g / mol.

[0064] The diblock copolymer BM may have a mass fraction of M block of 5 to 95% by weight, preferably 15 to 85% by weight (relative to the total weight of the copolymer), and a mass fraction of B block of 5 to 95% by weight, preferably 15 to 85% by weight.

[0065] In the case of triblock copolymer MBM, the two blocks M are composed of the same monomers (or comonomers) as the M blocks of the diblock copolymer BM described above. These two blocks M may be identical or different. For example, these two M blocks may have different molar masses but are composed of the same monomers.

[0066] Block B is composed of the same monomers (or comonomers) as Block B of the diblock copolymer BM described above.

[0067] The triblock copolymer MBM can have a number-average molar mass of 10,000 g / mol to 500,000 g / mol, preferably 20,000 to 200,000 g / mol.

[0068] The triblock copolymer MBM may have a mass fraction of M block of 10-80% by weight, preferably 15-70% by weight, more preferably 40-60% by weight (relative to the total weight of the copolymer), and a mass fraction of B block of 20-90% by weight, preferably 30-85% by weight, more preferably 40-60% by weight.

[0069] Preferably, the triblock copolymer MBM is a polymethyl methacrylate-poly(styrene-co-butylacrylate)-polymethyl methacrylate block copolymer.

[0070] Block copolymers can be produced by controlled radical polymerization (CRP), for example, according to the methods described in PCT applications WO96 / 24620A and WO00 / 71501A1, or by anionic polymerization.

[0071] At least one of blocks M and B can be functionalized with one or more functional groups selected from the group consisting of acids, amines, amides, epoxys, thiols, quaternary ammonium groups, chlorinating groups, and fluorinating groups.

[0072] Block copolymers are marketed under the trademark name Nanostrength® by Arkema.

[0073] Filler The composition of the present invention contains a filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay in an amount of 1 to 15% by weight, preferably 1 to 12% by weight, more preferably 1 to 10% by weight, and more preferably 1.5 to 10% by weight, based on the total weight of the composition.

[0074] Organic modified clay The clay can be selected from phyllosilicate, inosilicate, nesosilicate, solosilicate, cyclosilicate, tectosilicate, and mixtures thereof. These clays typically have a sheet structure, with K between the sheets. + and Na + Alternatively, it may contain alkaline cations such as alkaline earth cations in their original state (non-organic modified).

[0075] Preferably, the clay is selected from phyllosilicates.

[0076] Examples of phyllosilicates include montmorillonite, vermiculite, and kaolinite.

[0077] Preferably, the clay is montmorillonite.

[0078] In the context of the present invention, "organically modified clay" or "organically-friendly modified clay" is typically obtained by exchanging alkali ions or alkaline earth ions present in a gallery separating clay sheets with organic cations such as quaternary ammonium, sulfonium, or phosphonium cations. These modified clays typically have a sheet structure and contain organic cations between the sheets, such as alkylammonium ions and / or alkylphosphonium ions and / or alkylsulfonium ions, obtained by ion exchange reactions with naturally occurring alkali or alkaline earth cations.

[0079] The organically modified clay can be an organically modified phyllosilicate, an organically modified inosilicate, an organically modified nesosilicate, an organically modified sorosilicate, an organically modified cyclosilicate, an organically modified tectosilicate, or a mixture thereof.

[0080] Preferably, the organically modified clay is selected from organically modified phyllosilicates, more preferably organically modified montmorillonite.

[0081] The organically modified clay preferably has an N + clay having a quaternary ammonium ion of the R1R2R3R4 type, S + a clay having a sulfonium ion of the R1R2R3 type, P + a clay having a phosphonium ion of the R1R2R3R4 type, wherein R1 to R4 are the same or different and are hydrogen, a substituted or unsubstituted C1-C25 alkyl group, examples of the substituted alkyl group include dimethyldialkyl (C14-C18) amine, octadecylamine, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted carboxyalkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted silane group such as an aminopropyltriethoxysilane group, an octasilane group, etc., or a clay selected from a mixture of such clays.

[0082] Preferably, the organically modified clay is an N + montmorillonite having a quaternary ammonium ion of the R1R2R3R4 type, wherein R1 to R4 are the same or different and are hydrogen, a substituted or unsubstituted C1-C twenty-five alkyl group, examples of the substituted alkyl group include dimethyldialkyl (C14-C18) amine, octadecylamine, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted carboxyalkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted silane group such as an aminopropyltriethoxysilane group, an octasilane group, etc., or a montmorillonite selected from a mixture of such clays.

[0083] Preferably, the organically modified clay is N + Montmorillonite having a quaternary ammonium ion of type R1R2R3R4, wherein R1 to R4 are the same or different and represent hydrogen, a substituted or unsubstituted benzyl group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted C1 to C25 alkyl group, examples of which include dimethyldialkyl(C14 to C18)amine, octadecylamine, a substituted or unsubstituted carboxyalkyl group, an aminopropyltriethoxysilane group, an octasilane group, or other substituted or unsubstituted silane groups.

[0084] Examples of organically modified clays include those marketed by Southern Clay Products under the trademark name Cloisite® (e.g., Cloisite® C10A, Cloisite® C15, Cloisite® C14-C18A), or those marketed by Nanocore under the trademark name Nanomer®, such as Nanoclay Nanomer® l.44P or Nanoclay Nanomer® l.31PS.

[0085] Zeolite The zeolite adsorbent, or more simply the zeolite, that can be used in the context of the present invention may be any type known to those skilled in the art.

[0086] Zeolites are typically aluminosilicate-based, crystalline, and porous compounds having a three-dimensional crystalline structure formed by an assembly of SiO4 and AlO4 tetrahedra bonded together by sharing one or more oxygen atoms. Thus, these compounds form a crystalline network containing nanometer-sized pores. These structures generally contain cations to electrically neutralize the system, and these cations are most often sodium, potassium, or calcium, but may also include barium, rare earth elements, or even mixtures of any proportion of two or more of these cations.

[0087] Zeolites can be selected from type A, type CHA (chabazite), faujasite-type zeolites (X, MSX, and LSX (abbreviation for "low silica X"), Y), type HEU (clinoptilolite), and mixtures thereof.

[0088] The structure and properties of zeolite A are well known and are extensively described in the literature, particularly in Donald W. Breck's "Zeolite Molecular Sieves," John Wiley and Sons edition (1974), pages 83 onwards, as well as in the patents by Milton (US2882243) and Barrer (FR1257034).

[0089] The change in properties resulting from the exchange of all or part of the cations may involve changes in pore size or specific interactions with the adsorbed molecules, thereby altering the adsorption properties and resulting in changes in selectivity.

[0090] Therefore, in zeolite A (often referred to as "zeolite 4A"), which has a 4 Å pore opening in the synthesized sodium form, it is possible to impart desired properties by performing various cation exchanges. In many cases, these are lithium (Li + ), potassium (K + ), cesium (Cs + ), magnesium (Mg 2+ ), calcium (Ca 2+ ), strontium (Sr 2+ ), barium (Ba 2+ ), Cerium (Ce 3+ Alkali or alkaline earth cations such as ) or, for example, lanthanum (La2+ / La3+), silver (Ag+), copper (Cu 2+ ), nickel (Ni 2+ ), zinc (Zn 2+ ), iron (Fe 2+ Fe 3+ ), chromium (Cr 2+ ~Cr6+ ) are rare earth elements or other cations such as metal cations. Therefore, depending on the type of cation exchange performed, zeolite A may be, for example, -It can be converted to the calcium form by exchange with a calcium salt in an aqueous solution, yielding a zeolite with pores having an effective opening of 5 Å (therefore, it is often referred to as "zeolite 5A"). -By exchange with potassium salts in aqueous solution, it can be converted to the potassium form, yielding a zeolite with pores having an effective opening of 3 Å (for which it is often called "zeolite 3A"). - For example, different forms can be converted by mixing aqueous solutions of lithium, calcium, or potassium salts.

[0091] The term Zeolite 3A, as used herein, refers to a zeolite in which 20-70% of the exchangeable cation moieties (reported in equivalents) are potassium ions (K + This refers to Type A zeolite, which is composed of 30-80% by equivalent weight of alkalis, alkaline earth elements, rare earth elements, or metal ions as defined above.

[0092] The term zeolite 4A, as used herein, refers to a zeolite in which substantially all replaceable cation sites are sodium cation Na + This refers to type A zeolite, which is dominated by the (sodium form after synthesis).

[0093] The term Zeolite 5A, as used herein, refers to a zeolite with 40-100% replaceable cation moieties (reported in equivalents) on an equivalent basis, where Ca2 + The composition is dominated by ions, with 0-5% on an equivalent basis being alkalis, alkaline earth elements, rare earth elements, or metal ions as defined above, such as sodium Na. + This refers to type A zeolite occupied by [specific cations], but the presence of other cations as described above is not outside the scope of the present invention.

[0094] Forjasite constitutes a group of mineral species characterized by crystallographic topographic structures, as specifically described in Donald W. Breck's "Zeolite Molecular Sieves," John Wiley and Sons edition (1974), starting on page 92.

[0095] Preferably, the zeolite is type A zeolite, more preferably type 3A or 4A.

[0096] More preferably, the zeolite is a type 3A zeolite.

[0097] The zeolite of the present invention may be in the form of a powder or aggregates. The term aggregate means the molding of zeolite powder with minerals and / or organic binders. The molding of these aggregates can be carried out according to any method known to those skilled in the art, such as extrusion molding, compression molding, or agglomeration molding. For example, the aggregates may be in the form of pellets, beads ranging from a few nanometers to a few millimeters, filaments or extruded products, bars, rods, or molded parts of various sizes and shapes that may be collectively referred to as "cores" according to related terminology.

[0098] This molding can be performed by mixing a paste-like mixture of zeolite with a binder and, optionally, one or more additives to facilitate the handling of the paste, for example, by altering its rheology and / or adhesive strength. The binder is almost always inert and is intended to ensure the aggregation of the zeolite crystals.

[0099] Among mineral binders, alumina, montmorillonite, attapulgite, sepiolite, zeolitizable clays such as kaolin, kaolinite, nacrite, dichlorite, halloysite, metakaolin, such as atagel-type colloidal clay, or selected from other minerals or natural zeolites (clinoptilolite, mordenite, or chabazite), diatomaceous earth, talc, and other mineral binders known to those skilled in the art can be used, either alone or in mixtures of two or more thereof.

[0100] Among organic binders that can be used alone or in combination with the mineral binders described above, the inventors mean any polymer matrix known to those skilled in the art specializing in polymers. This includes, but is not limited to, thermoplastic and / or thermosetting homopolymers and / or copolymers, such as polyurethanes, fluorinated polymers such as PVDF, and epoxy resins. These polymers may be in any form, such as foam, foamed, or semi-foamed.

[0101] In addition to mineral and / or organic binders, one or more commonly used additives known to those skilled in the art, such as silica, colloidal silica, cellulose, corn starch, or any other type of pologen, may be added to the zeolite.

[0102] Zeolites in aggregate form generally have a size distribution with an average diameter of 0.3 mm to 1.6 mm.

[0103] The granule size distribution is measured, for example, by laser particle size measurement in liquid mode using a Mastersizer2000 device.

[0104] The atomic ratio Si / Al of zeolite is generally 1.0 to 2.0, preferably 1.0 to 1.8, and more preferably 1.0 to 1.4.

[0105] The atomic ratio Si / Al of zeolite can be measured by solid-state NMR of silicon-29 if it is in powder form, or by X-ray fluorescence analysis (e.g., wavelength-dispersive X-ray fluorescence spectrometer (WDXRF)) as described in the NF EN ISO 12677:2011 standard if it is in aggregate form.

[0106] The zeolite may contain crystals with an average particle size (D50) measured by scanning electron microscopy (SEM) of less than 20 microns, preferably 0.1 to 19 microns, more preferably 0.5 to 10 microns, and even more preferably 1 to 5 microns.

[0107] Non-limiting examples of zeolites that can be used in the context of the present invention include Siliporite® H3Ri, Siliporite® NK10, Siliporite® NK30, Siliporite® SA 1720, Siliporite® NK20, and Siliporite® G5, manufactured by Arkema. Examples include products marketed under the name XP, products marketed by ZEOCHEM under the trademark names Purmol® 3ST(3A), Purmol® 4ST(A), Zeochem® Z4-01, and Zeochem® 4A-8BL, products marketed by GRACE under the names Sylosiv® and Cryosiv®, and products marketed by UOP under the trademark names Molsiv® 3A, Molsiv® 4A, Molsiv® 5A, XH-7®, XH-9®, and XH-11®. In particularly advantageous embodiments, the filler is a mixture of zeolite and organically modified clay. The inventors have shown that this combination allows for an increase in the amount of filler in the composition of the present invention without adversely affecting its viscosity and light transmittance. Preferably, this mixture contains 30-70% by weight, preferably 40-60% by weight, of zeolite and 70-30% by weight, preferably 60-40% by weight, of organically modified clay, based on the total weight of the zeolite and organically modified clay mixture.

[0108] (meth)acrylate monomer The composition comprises at least one (meth)acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C.

[0109] The composition contains, in an amount of 30-80% by weight, preferably 40-75% by weight, preferably 45-75% by weight, preferably 45-60% by weight, and more preferably 45-55% by weight, of the total weight of the composition, at least one (meth)acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C.

[0110] The (meth)acrylate monomer having a glass transition temperature (Tg) of at least 85°C in the homopolymer obtained after polymerization can be selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, phenyl methacrylate, isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, dihydrodicyclopentadienyl acrylate, and mixtures thereof. Preferably, the (meth)acrylate monomer having a glass transition temperature of at least 85°C is methyl methacrylate.

[0111] The composition according to the present invention may include a mixture of (meth)acrylate monomers, the glass transition temperature (Tg) of the homopolymer obtained after polymerization being at least 85°C, the mixture may include at least one methacrylate monomer, the glass transition temperature (Tg) of the homopolymer obtained after polymerization being at least 85°C, and at least 5% by weight of a monoacrylate monomer, the glass transition temperature (Tg) of the homopolymer obtained after polymerization being at least 85°C. The mixture may further include at least one diacrylate monomer. Preferably, the mixture is - The mixture contains 20-95% by weight, more preferably 20-80% by weight, even more preferably 30-70% by weight, and preferably 40-60% by weight, at least one methacrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C, -The mixture contains at least 5% by weight, preferably at least 10% by weight, more preferably 5-80% by weight, more preferably 20-80% by weight, even more preferably 30-70% by weight, and more preferably 40-60% by weight of a monoacrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C. Preferably, the amount of monoacrylate monomer in the mixture is such that the viscosity of the resulting photopolymerizable adhesive composition according to the present invention is 100-20,000 mPa.s, preferably 100-10,000 mPa.s, more preferably 500-5,000 mPa.s, and more preferably 1,000-2,500 mPa.s. The viscosity can be measured using a Brookfield DVIII Ultra viscometer (spindle: SC4-27, rotation: 20 rpm, temperature: 25°C) in accordance with the NF EN 12092 standard "Adhesives - Measurement of Viscosity".

[0112] The methacrylate monomer in the above mixture, whose homopolymer obtained after polymerization has a glass transition temperature of at least 85°C, can be selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, phenyl methacrylate, isopropyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, and mixtures thereof. Preferably, the methacrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature of at least 85°C is methyl methacrylate.

[0113] The monoacrylate monomer in the above mixture, whose homopolymer obtained after polymerization has a glass transition temperature of at least 85°C, can be selected from the group consisting of isobornyl acrylate, dihydrodicyclopentadienyl acrylate, and mixtures thereof. Preferably, the acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C is isobornyl acrylate.

[0114] The mixture may further contain 0 to 40% by weight, preferably 0 to 20% by weight, or 1 to 20% by weight, more preferably 0 to 10% by weight, or 1 to 10% by weight, preferably 0 to 5% by weight, or 1 to 5% by weight, of at least one diacrylate monomer having a glass transition temperature of at least 85°C for the homopolymer obtained after polymerization, particularly dipropylene glycol diacrylate (CAS No. 57472-68-1), neopentyl glycol hydroxypivalate diacrylate (CAS No. 2136366-99-7), or tricyclodecanedimethanol diacrylate (CAS No. 52594-17-2), and preferably, the diacrylate monomer having a glass transition temperature of at least 85°C for the homopolymer obtained after polymerization is tricyclodecanedimethanol diacrylate (TCDDMDA).

[0115] Alkoxysilane (meth)acrylate monomer The composition comprises at least one alkoxysilane (meth)acrylate monomer.

[0116] The composition may contain at least one alkoxysilane (meth)acrylate monomer in an amount of 1 to 20% by weight, preferably 2 to 15% by weight, preferably 3 to 10% by weight, and more preferably 4 to 6% by weight, based on the total weight of the composition.

[0117] Alkoxysilane (meth)acrylate monomers, including alkylalkoxysilane (meth)acrylate monomers, can be selected from trialkoxysilane (meth)acrylate monomers, preferably trimethoxysilane (meth)acrylate monomers, and preferably the alkoxysilane (meth)acrylate monomer is selected from 3-(trimethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, trimethoxysilyl acrylate, trimethoxysilyl methacrylate, and mixtures thereof, and preferably the alkoxysilane (meth)acrylate monomer is 3-(trimethoxysilyl)propyl methacrylate.

[0118] 3-(trimethoxysilyl)propyl methacrylate is marketed under the trademark name Silquest® A174 by Momentive®.

[0119] Photoinitiator The composition comprises 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 (meth)acrylate monomers and / or urethane oligomers by ultraviolet (UV) or visible light irradiation to obtain the adhesive, can be used.

[0120] The composition may contain at least one photoinitiator in an amount of 0.1 to 5% by weight, preferably 0.5 to 4% by weight, preferably 1 to 3.5% by weight, and preferably 1 to 3% by weight, based on the total weight of the composition.

[0121] The photoinitiator can be selected from the group consisting of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, triethylbenzoyl-diphenylphosphine oxide, thioxanthene-9-one, 4,4-bis(diethylamino)benzophenone, 9,10-phenanthrenequinone, benzoyltrimethylgermane, dibenzoyldiethylgermane, bis-(4-methoxybenzoyl)diethylgermanium, and mixtures thereof, preferably phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. For example, the mixture may include benzophenone, α-hydroxyketone, and triethylbenzoyl-diphenylphosphine oxide. Another mixture may include, for example, benzoyltrimethylgermane, dibenzoyldiethylgermane, and bis-(4-methoxybenzoyl)diethylgermanium.

[0122] Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide is marketed under the trademark name Omnirad® 819 (formerly Irgacure® 819) by IGM Resins (formerly Irgacure® 819 by Ciba® Specialty Chemicals). A mixture containing benzophenone, α-hydroxyketone, and triethylbenzoyl-diphenylphosphine oxide is marketed under the trademark name Esacure® KTO 46 by Lehvoss.

[0123] Other (meth)acrylate monomers The composition may contain at least one (meth)acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of less than 0°C. In this embodiment, the composition contains a mixture of a (meth)acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature of at least 85°C and a (meth)acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature of less than 0°C.

[0124] The composition may contain 0 to 5% by weight of at least one (meth)acrylate monomer, based on the total weight of the composition, wherein the resulting homopolymer has a glass transition temperature of less than 0°C. If present, the composition may contain 0.1 to 5% by weight, preferably 1 to 5% by weight, preferably 2 to 4% by weight of at least one (meth)acrylate monomer, based on the total weight of the composition, wherein the resulting homopolymer has a glass transition temperature of less than 0°C.

[0125] The (meth)acrylate monomers whose homopolymer obtained after polymerization has a glass transition temperature of less than 0°C can be 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 acrylate, and mixtures thereof, and butyl acrylate is preferred.

[0126] Alternatively, the composition may substantially not contain (meth)acrylate monomers whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of less than 0°C.

[0127] Methacrylic acid The composition may contain methacrylic acid monomers.

[0128] The composition may contain 0 to 20% by weight of methacrylic acid based on the total weight of the composition. If present, the composition contains 1 to 16% by weight, preferably 3 to 12% by weight, 3 to 10% by weight, and preferably 3.5 to 7% by weight of methacrylic acid based on the total weight of the composition.

[0129] Urethane (meth)acrylate oligomer The composition may contain at least one urethane (meth)acrylate oligomer.

[0130] The composition may contain at least one urethane (meth)acrylate oligomer in an amount of 0 to 7% by weight, relative to the total weight of the composition. If present, the composition contains at least one urethane (meth)acrylate oligomer in an amount of 0.1 to 7% by weight, preferably 3 to 6% by weight, relative to the total weight of the composition.

[0131] The urethane (meth)acrylate oligomer can be selected from aliphatic urethane diacrylate oligomers, and preferably the urethane (meth)acrylate oligomer is an aliphatic urethane diacrylate.

[0132] The composition may further contain at least one monofunctional reactive diluent.

[0133] The composition may contain at least one monofunctional reactive diluent in an amount of 0 to 0.7% by weight relative to the total weight of the composition. If present, the composition contains at least one monofunctional reactive diluent in an amount of 0.1 to 0.7% by weight, preferably 0.3 to 0.7% by weight, relative to the total weight of the composition.

[0134] The monofunctional reactive diluent may be 2-(2-ethoxy-ethoxy)ethyl acrylate. A mixture of urethane (meth)acrylate oligomer and monofunctional reactive diluent consists of approximately 90% by weight of aliphatic urethane diacrylate and approximately 10% by weight of 2-(2-ethoxy-ethoxy)ethyl acrylate, based on the total weight of the mixture, and is commercially available under the trademark name CN966H90® by Sartomer.

[0135] viscosity The photopolymerizable adhesive composition is preferably a liquid composition.

[0136] The composition may have a viscosity of 100 to 20,000 mPa.s, preferably 100 to 10,000 mPa.s, more preferably 500 to 5,000 mPa.s, and more preferably 1,000 to 2,500 mPa.s. The viscosity can be measured using a Brookfield DVIII Ultra viscometer (spindle: SC4-27, rotation: 20 rpm, temperature: 25°C) in accordance with the NF EN 12092 standard "Measuring viscosity of adhesives".

[0137] After polymerization, the composition preferably has a glass transition temperature (Tg) of at least 85°C, preferably at least 90°C, and preferably at least 100°C.

[0138] In a particular embodiment, the composition is, relative to the total weight of the composition, -10 to 60% by weight, preferably 10 to 50% by weight, preferably 20 to 40% by weight, preferably 20 to 35% by weight, and more preferably 25 to 35% by weight of at least one block copolymer, -30 to 80% by weight, preferably 40 to 75% by weight, preferably 45 to 75% by weight, preferably 45 to 60% by weight, more preferably 45 to 55% by weight, at least one (meth)acrylate monomer having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization, -1 to 15% by weight, preferably 1 to 10% by weight, of a filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay, -1 to 20% by weight, preferably 2 to 15% by weight, preferably 3 to 10% by weight, preferably 4 to 6% by weight, at least one alkoxysilane (meth)acrylate monomer, -0.1 to 5% by weight, preferably 0.5 to 4% by weight, preferably 1 to 3.5% by weight, preferably 1 to 3% by weight, at least one photoinitiator, -0 to 5% by weight, preferably 0.1 to 5%, of at least one (meth)acrylate monomer having a glass transition temperature of less than 0°C of the homopolymer obtained after polymerization, - 0 to 20% by weight, preferably 1 to 16% by weight, preferably 3 to 12% by weight of methacrylic acid, -0 to 7% by weight, preferably 0.1 to 7% by weight, more preferably 3 to 6% by weight, at least one urethane (meth)acrylate oligomer, It may also contain (or be composed of) at least one monofunctional reactive diluent in an amount of -0 to 0.7% by weight, preferably 0.1 to 0.7% by weight, preferably 0.3 to 0.7% by weight.

[0139] In a particular embodiment, the composition is, relative to the total weight of the composition, -20 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 35% by weight of at least one block copolymer, -45 to 75% by weight, preferably 45 to 60% by weight, more preferably 45 to 55% by weight, at least one (meth)acrylate monomer having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization, -1 to 15% by weight, preferably 1 to 12% by weight, preferably 1 to 10% by weight, more preferably 1.5 to 10% by weight, a filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay, -3 to 10% by weight, preferably 4 to 6% by weight, of at least one alkoxysilane (meth)acrylate monomer, -1 to 3.5% by weight, preferably 1 to 3% by weight, at least one photoinitiator, It may also contain (or be composed of) -1 to 16% by weight, preferably 3 to 12% by weight, of methacrylic acid.

[0140] In a particular embodiment, the composition is, relative to the total weight of the composition, -20 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 35% by weight of at least one (meth)acrylic block copolymer, preferably a (meth)acrylic block copolymer having a triblock MBM structure, -45 to 75% by weight, preferably 45 to 60% by weight, more preferably 45 to 55% by weight, of at least one (meth)acrylate monomer having a glass transition temperature of at least 85°C after polymerization, preferably a monomer selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, phenyl methacrylate, isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, dihydrodicyclopentadienyl acrylate, and mixtures thereof, preferably methyl methacrylate or monoacrylate mono A monomer which is a mixture of a methyl methacrylate monomer and a diacrylate monomer selected from dipropylene glycol diacrylate (CAS No. 57472-68-1), neopentyl glycol hydroxypivalate diacrylate (CAS No. 2136366-99-7), tricyclodecane dimethanol diacrylate, preferably tricyclodecane dimethanol diacrylate (TCDDMDA), preferably a mixture of a methyl methacrylate monomer and a monoacrylate monomer selected from isobornyl acrylate, dihydrodicyclopentadienyl acrylate, preferably isobornyl acrylate, - Preferably 3 to 10% by weight, preferably 4 to 6% by weight, of at least one alkoxysilane (meth)acrylate monomer selected from the group consisting of trialkoxysilane (meth)acrylate monomers, preferably a monomer that is a trimethoxysilane (meth)acrylate monomer, preferably a monomer selected from 3-(trimethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate, trimethoxysilyl acrylate, trimethoxysilyl methacrylate, and mixtures thereof, preferably a monomer that is 3-(trimethoxysilyl)propyl methacrylate, -1 to 15% by weight, preferably 1 to 12% by weight, preferably 1 to 10% by weight, preferably 1.5 to 10% by weight, a filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay, wherein the zeolite is type A zeolite, preferably type 3A or 4A zeolite, and the clay is -N + Organically modified clay containing quaternary ammonium ions of type R1R2R3R4, S + Organically modified clay containing R1R2R3 type sulfonium ions, P + Organically modified clay having R1R2R3R4 type phosphonium ions, wherein R1 to R4 are the same or different, and the R1 to R4 represent hydrogen, substituted or unsubstituted C1 to C25 alkyl groups (examples of substituted alkyl groups include dimethyldialkyl(C14-C18)amine and octadecylamine), substituted or unsubstituted phenyl groups, substituted or unsubstituted benzyl groups, substituted or unsubstituted carboxyalkyl groups, substituted or unsubstituted acyl groups, aminopropyltriethoxysilane groups, octasilane groups, and other substituted or unsubstituted silane groups, or a mixture of such clays, preferably N + The filler is an organically modified clay containing quaternary ammonium ions of type R1R2R3R4. -1 to 3.5% by weight, preferably 1 to 3% by weight, of at least one photoinitiator selected from the group consisting of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, triethylbenzoyl-diphenylphosphine oxide, thioxanthene-9-one, 4,4-bis(diethylamino)benzophenone, 9,10-phenanthrenequinone, benzoyltrimethylgermane, dibenzoyldiethylgermane, bis-(4-methoxybenzoyl)diethylgermanium, and mixtures thereof, preferably a photoinitiator which is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, It may also contain (or be composed of) -1 to 16% by weight, preferably 3 to 12% by weight, of methacrylic acid.

[0141] Single-component composition Preferably, the composition is a single-component composition, i.e., a ready-to-use composition. Conversely, preferably, the composition is a multi-component composition, i.e., not a kit containing at least two separately packaged components, and these components are not intended to be immediately mixed together immediately before application of the thus obtained composition.

[0142] Single-component compositions do not need to be prepared in the form of at least two separate components that are mixed immediately before use to avoid premature polymerization. In fact, single-component compositions contain at least one photoinitiator, which allows polymerization to begin as soon as the composition is exposed to light radiation, particularly ultraviolet (UV) radiation. To avoid any premature or early polymerization, the composition must be kept away from light.

[0143] Adhesive products In a second aspect, the present invention includes an adhesive product. The adhesive product includes the photopolymerizable adhesive composition described above and an opaque container containing it. The term “opaque container” means a container whose walls do not allow light that may activate the photoinitiator, particularly visible light and ultraviolet light (less than 600 nm), to pass through.

[0144] Opaque containers may be used to contain the composition and maintain its properties, particularly its adhesive properties. Using opaque containers prevents the composition from being exposed to light (especially ultraviolet light) before use, i.e., during storage and transport, thereby avoiding premature or early polymerization.

[0145] The container can be selected from, for example, a group consisting of bottles or tubes.

[0146] glue In a third aspect, the present invention relates to adhesives, and more particularly to adhesives obtained from the photopolymerized adhesive compositions described above. The terms “adhesive” or “photopolymerizable adhesive composition” mean an adhesive layer obtained by applying a photopolymerizable adhesive composition, photopolymerizing it, and optionally molding the adhesive thus obtained.

[0147] The adhesive is, - A step of applying the above-described photopolymerizable adhesive composition to at least one cover and / or electronic or optoelectronic device, - A step of photopolymerizing the applied photopolymerizable adhesive composition to obtain a polymerized adhesive, -Optionally, the method includes the step of molding the polymerized adhesive.

[0148] The adhesive can take the form of a film.

[0149] The composition can be applied by conventional coating techniques, such as slot die coating, deep coating, inkjet printing, screen printing, spin coating, spray coating, or doctor blade applicator.

[0150] Photopolymerization of the composition can be carried out by using a UV lamp that emits ultraviolet (UV) radiation and visible light within a range that can activate the photoinitiator without absorption by the sealing cover. A suitable UV lamp may be, for example, the UV LED system Delolux® 03S. Photopolymerization can be carried out for 1 to 10 minutes.

[0151] The adhesive can have a thickness of 10 to 200 μm, preferably 10 to 100 μm, and preferably 10 to 30 μm.

[0152] The adhesive has several advantages, particularly that it can be used at temperatures of at least 70°C, preferably at least 85°C, for example, when the electronic or optoelectronic device is a photocell, or when the device needs to meet temperature test criteria (e.g., automotive or photovoltaic applications).

[0153] Advantageously, the adhesive formulations according to the present invention enable the use of sealed objects up to at least 70°C, or even up to at least 85°C, for example, when the electronic or optoelectronic device is a photocell, or when the device needs to meet temperature test criteria (e.g., automotive applications).

[0154] The adhesive preferably exhibits satisfactory adhesive properties, particularly in the case of flexible modules, to enable satisfactory adhesion between the electronic or optoelectronic device and the cover.

[0155] The adhesive preferably exhibits satisfactory optical properties, particularly satisfactory transparency, especially when the electronic or optoelectronic device is a photocell, in order to enable the transmission of light waves to the device and / or limit the diffraction of light waves. The adhesive can have a transparency of 90% with a transmittance of 400-800 nm. Transparency can be measured by UV-Vis transmission spectroscopy.

[0156] The adhesive preferably exhibits satisfactory electrical properties, particularly satisfactory electrical insulation properties, especially to avoid short circuits within the module. Electrical insulation properties can be measured according to the ASTM D149 standard.

[0157] The adhesive preferably exhibits satisfactory strength, particularly against aging under ultraviolet light, abrasion, and / or impact. The adhesive preferably exhibits satisfactory barrier properties, particularly water and oxygen (air) barrier properties. Barrier properties are measured according to ASTM F1249 standard at a temperature of 38°C and a relative humidity of 85%, with a water vapor transmission rate (WVTR) of 5 g / m² per 1 mm thickness. 2 .d- 1 Less than 2g.m- 2 .d- 1 It should be less than [amount].

[0158] The adhesive preferably exhibits satisfactory elastic properties. Elastic properties, particularly flexibility, can be measured by a three-point or four-point bending test using a bending tester equipped with a cylindrical mandrel, or by tensile strength measurement.

[0159] Electronic or optoelectronic module In a fourth aspect, the present invention relates to a module, preferably a flexible module, which corresponds to a sealed electronic or optoelectronic device.

[0160] A module can be obtained by assembling a series of layers. The series of layers are: -First cover, - The first adhesive described above, or the first adhesive obtained from the photopolymerizable adhesive composition described above, - Electronic or optoelectronic devices, - The second adhesive described above, or the second adhesive obtained from the photopolymerizable adhesive composition described above, and -This may include the second cover, in order.

[0161] The electronic or optoelectronic device itself may include a semiconductor layer deposited on a support substrate.

[0162] This series of layers may further include additional layers, particularly layers inserted between the cover and the adhesive, such as additional layers to improve adhesion between the inner surface of the cover and the layer of the adhesive composition, and surface treatments for the cover.

[0163] In the module thus obtained, the electronic or optoelectronic devices are preferably wrapped in two overlapping adhesive layers around them to form a tight seal. Sealing the electronic or optoelectronic devices with adhesive and then sealing them with two covers makes it possible to insulate the devices from the environment.

[0164] The modules thus obtained exhibit satisfactory properties and enable the restriction, and even prevention, of both orthogonal and lateral penetration while maintaining the flexibility of the electronic or optoelectronic device.

[0165] The module can have a total thickness of 50 to 500 μm, preferably 50 to 300 μm, and more preferably 50 to 150 μm.

[0166] The electronic or optoelectronic device can be selected from rigid devices, flexible devices, or a combination thereof, preferably the device is a flexible device, and preferably the device is selected from organic light-emitting diodes, organic or perovskite photocells, organic or perovskite transistors or sensors, or a combination thereof.

[0167] In one particular embodiment, the photocell is a perovskite device. So-called halide perovskite materials may contain metals (e.g., lead or tin), organic and inorganic cations (e.g., cesium, formamidinium, and / or ammonium), and halide anions (e.g., boron or iodine) within their crystalline structure. Perovskite devices are particularly suitable for photovoltaic applications. However, perovskite devices can develop stability problems over time due to their sensitivity to the atmosphere, especially water vapor.

[0168] The covers may be the same or different.

[0169] The cover may be single-layered or multi-layered.

[0170] The cover may be flexible or rigid, and is preferably flexible.

[0171] The module may have an orientation that includes, for example, a lower or rear cover (commonly referred to as a "back sheet") and an upper or front cover (commonly referred to as a "front sheet"). The upper or front cover is preferably transparent, and the lower or rear cover is preferably opaque.

[0172] Depending on the electronic or optoelectronic devices used, and the desired features and characteristics of the module, the cover may have specific properties.

[0173] The cover may be a polymer cover.

[0174] The cover could be an inorganic cover.

[0175] The polymer cover may include at least one fluorinated polymer layer obtained from at least one fluorinated polymer, such as poly(vinyl fluoride) (PVF), poly(vinylidene fluoride) (PVDF), and mixtures thereof. The polymer cover may also include at least one polymer layer (or PET layer) and a fluorinated polymer layer obtained from polyethylene terephthalate (PET).

[0176] Fluorinated polymer layers, PET layers, and combinations thereof, as well as single-layer or multi-layer covers obtained therefrom, are particularly suitable for use as bottom or rear covers.

[0177] The cover may include at least one glass layer.

[0178] The cover may include at least one polymer layer (or PMMA layer) obtained from polymethyl methacrylate (PMMA).

[0179] The glass layer or PMMA layer is particularly suitable for use as an upper or front cover.

[0180] Flexible covers, particularly suitable for encapsulating flexible electronic or optoelectronic devices, especially organic or perovskite batteries, are commercially available under the trademark name 3M Ultra-Barrier Solar Film from 3M®. These covers are multilayer laminated covers comprising a PET film, an inorganic barrier layer of silica, alumina, or silicon nitride with a thickness of 20-300 nm, a so-called PSA (pressure-sensitive adhesive) film, and a fluorinated polymer film or layer called a "weather-resistant layer" positioned on the outside to protect the entire structure from the external environment.

[0181] Method for obtaining an electronic or optoelectronic module In a fifth aspect, the present invention relates to a method for obtaining the above-described module, wherein the method is: - A process of preparing an electronic or optoelectronic device, - The process of preparing the above-mentioned photopolymerizable adhesive composition, - The process of preparing the first cover, - The process of preparing the second cover, - A step of applying a layer of photopolymerizable adhesive composition to the surface of the device and / or to the inner surfaces of the first and second covers, - A step of laminating the device and a layer of the photopolymerizable adhesive composition between the inner surfaces of the first and second covers, The process includes a step of photopolymerizing a layer of the photopolymerizable adhesive composition.

[0182] The method may further include a step of irradiating the first cover and / or the second cover with ultraviolet-ozone before the coating step and / or lamination step.

[0183] In one particular embodiment, the rigid module is obtained by vacuum lamination technique ("sheet-to-sheet") under heating.

[0184] In one particular embodiment, the flexible module is obtained by a “roll-to-roll” technique, such as that described, for example, in the paper “Research Update: Large-area deposition, coating, printing, and processing techniques for the upscaling of perovskite solar cell technology” by S. Razza et al., APL Materials (2016) 4(9). This technique is particularly suitable for flexible electronic or optoelectronic devices, preferably organic light-emitting diodes, organic or perovskite photocells, organic or perovskite transistors and sensors, or devices selected from combinations thereof, preferably perovskite devices.

[0185] Uses and applications In a sixth aspect, the present invention relates to the use of the above-described photopolymerizable adhesive composition and the adhesive obtained therefrom for encapsulating electronic or optoelectronic devices, particularly flexible electronic or optoelectronic devices, such as organic photovoltaic devices, particularly perovskite-type devices.

[0186] Examples The following examples illustrate the present invention, but are not intended to limit it.

[0187] List of materials and equipment Block copolymer: Triblock copolymer MBM [polymethyl methacrylate-poly(styrene-co-butyl acrylate)-polymethyl methacrylate] (abbreviation: MBM) (Meth)acrylate monomer: Methyl methacrylate (abbreviation: MAM) whose homopolymer obtained after polymerization has a glass transition temperature of at least 85°C. Alkoxysilane (meth)acrylate monomer: 3-(trimethoxysilane)propyl methacrylate (Silquest® A174 product of Momentive®) (Abbreviation: A174) Photoinitiator: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Omnirad® 819 product from IGM Resins) (abbreviation: I819), also available from Sigma-Aldrich. Methacrylic acid (abbreviation: AMA) Zeolite: 3A zeolite, Siliporite® NK30APSC grade, commercially available from Arkema. Clay: C10A, commercially available from Southern Clay Products; Modified clay: C14-C18 (montmorillonite MMT modified with 35-45 wt% dimethyldialkyl (C14-C18)amine). These are from the Nanoclay range supplied by Sigma Aldrich, and octasilane clay (montmorillonite modified with 15-35 wt% octadecylamine and 0.5-5 wt% aminopropyltriethoxysilane). These are from the Nanoclay range supplied by Sigma Aldrich. Light source: UV LED Delolux(registered trademark) 03S system

[0188] Modules under test The module under test is generally called a test specimen.

[0189] PK layer: Surface area of ​​4 x 4 cm (16 cm) 2 ) Formula Cs 0.05 FA 0.95 Pb(I 0.88 Br 0.12 )3 perovskite layers Glass layer: Surface area 5 x 5 cm (25 cm) 2 ) layer ITO layer: Indium tin oxide layer The ITO glass layer itself forms the support substrate.

[0190] The PK layer is deposited by spin coating technology. The upper ITO layer is deposited by physical vapor deposition.

[0191] The perovskite layer is deposited on a supporting substrate, with a 5 mm overhang between the edge of the substrate and the perovskite layer.

[0192] The modules are individually sealed between two 1.2 mm thick glass covers with the test photopolymerizable composition.

[0193] Test method Thermal properties and gas barrier The thermal properties and gas barrier properties of the tested modules were analyzed by differential scanning calorimetry (DSC). Three cooling and heating cycles were measured at a rate of 10°C per minute in the range of -80 to 200°C. The glass transition temperature was measured in the third heating cycle using the tangent method at an intermediate height calculated between 40 and 140°C. The gas barrier properties were determined by optical testing to measure the degradation rate of the perovskite layer of the specimen. The degradation rate (cm) related to the degradation of the perovskite layer was measured. 2 The degradation rate (cm² / h) was determined. The degradation of the tested modules was evaluated using the following method: The above-mentioned test specimens were placed in an artificial climate chamber at a temperature of 85°C and a relative humidity of 85%, according to the climate test conditions for photovoltaic modules reported in the standard method IEC 61615, and the degradation rate (cm² / h) was determined. 2 The algorithm parameters for / h) were determined. Refer to the paper by E. Booker et al., entitled "Perovskite Test: A high throughput method to screen ambient encapsulation conditions," Energy Technology (2020) 8(12). To evaluate the aging of the perovskite layer, photographic images of the specimen were taken periodically, for example, every 48 hours. The residual surface (thickness) of the perovskite layer was measured to 12 cm. 2 ~2cm 2 The degradation rate of these layers (cm) is obtained from the linear regression of the points between them. 2 The calculation ( / h) was performed. Areas with a thickness of 180 nm or less were considered degraded areas (areas shown in black by the algorithm analysis), and areas with a thickness exceeding 180 nm were considered healthy areas (areas shown in gray by the algorithm analysis).

[0194] Photopolymerizable adhesive composition The following photopolymerizable adhesive compositions were prepared (see Table 1; the values ​​in Table 1 represent percentages, expressed as weight percentages of the total weight of the photopolymerizable adhesive composition).

[0195] [Table 1]

[0196] result vapor barrier The degradation rate of multilayer modules obtained using compositions C1 to C7 and comparative composition CRef according to the present invention was tested. The tested modules were photographed periodically. Images were taken at 0 hours, 159 hours, 280 hours, 351 hours, 447 hours, 521 hours, 624 hours, 737 hours, 852 hours, 948 hours, and 1091 hours.

[0197] From these images, several parameters were extracted, which are as follows: The initial thickness of the perovskite (PK) was 400 nm in all tests, and the initial area was approximately 14 cm² in all tests. 2 The area of ​​the "active" surface is the area of ​​the PK layer having a thickness greater than the empirical threshold (180 nm), assuming that this condition is met. By monitoring this area (Figures 1, 7, and 13), we can determine the following: 12-3cm 2 The established linear regression allows for the determination of the VA parameters (Figures 3 and 9). It is observed that the VA parameters improve in the presence of zeolite and / or modified clay compared to the reference composition. The combination of zeolite and modified clay significantly improves the VA. Monitoring of the same area revealed that the "active" surface was 12 cm². 2 It becomes possible to define the DA12 parameter (Figures 5 and 11), which is the time it takes to reach a certain state. DA12 is observed to be higher in the compositions according to the present invention (having zeolite and / or clay) compared to the reference composition. The combination of zeolite and clay further improves DA12. By monitoring the average thickness of the "active" surface (Figures 2, 8, and 14), the following can be obtained: VE parameters obtained by linear regression established at 340-230 nm (Figures 4 and 10). VE is observed to be superior in the composition according to the present invention (having zeolite and / or clay) compared to the reference composition. These results also indicate that the combination of zeolite and modified clay significantly improves VA. DE380 parameters corresponding to the time it takes for the average thickness, starting at 400 nm, to reach 380 nm (Figures 6 and 12). DE380 is observed to be higher in the composition according to the present invention (including zeolite) compared to the reference composition. The combination of zeolite and clay further improves DE380.

[0198] The changes in the area of ​​the "active" surface, which is the area of ​​the perovskite (PK) layer, are also shown in Figure 13 for compositions C3, C5, C6, and C7. The changes in the average thickness of the active surface are also shown in Figure 14 for compositions C3, C5, C6, and C7.

[0199] It has also been observed that the addition of fillers to the photopolymerizable composition of the present invention does not affect UV transmission.

Claims

1. A photopolymerizable adhesive composition, wherein, with respect to the total weight of the photopolymerizable adhesive composition, At least one block copolymer, preferably a (meth)acrylic block copolymer, At least one (meth)acrylate monomer having a glass transition temperature (Tg) of at least 85°C of the homopolymer obtained after polymerization, At least one alkoxysilane (meth)acrylate monomer, A filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay in an amount of 1 to 15% by weight, A photopolymerizable adhesive composition comprising at least one photoinitiator.

2. With respect to the total weight of the aforementioned photopolymerizable adhesive composition, 10 to 60% by weight, preferably 10 to 50% by weight, preferably 20 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 35% by weight of at least one block copolymer, preferably a (meth)acrylic block copolymer, 30 to 80% by weight, preferably 40 to 75% by weight, preferably 45 to 75% by weight, preferably 45 to 60% by weight, more preferably 45 to 55% by weight, at least one (meth)acrylate monomer having a glass transition temperature (Tg) of at least 85°C of the homopolymer obtained after polymerization, 1 to 20% by weight, preferably 2 to 15% by weight, preferably 3 to 10% by weight, preferably 4 to 6% by weight, at least one alkoxysilane (meth)acrylate monomer, A filler selected from zeolite, organically modified clay, or a mixture of zeolite and organically modified clay in an amount of 1 to 15% by weight, preferably 1 to 12% by weight, preferably 1 to 10% by weight, preferably 1.5 to 10% by weight, A photopolymerizable adhesive composition according to claim 1, comprising 0.1 to 5% by weight, preferably 0.5 to 4% by weight, preferably 1 to 3.5% by weight, and preferably 1 to 3% by weight of at least one photoinitiator.

3. The aforementioned filler is - Type A zeolite, preferably 3A or 4A, -N ＋ R １ R ２ R ３ R ４ An organically modified clay having a quaternary ammonium ion of the R type, S ＋ R １ R ２ R ３ An organically modified clay having a sulfonium ion of the R type, P ＋ R １ R ２ R ３ R ４ An organically modified clay having a phosphonium ion of the R type, wherein R １ to R ４ are the same or different and are selected from hydrogen, a substituted or unsubstituted C1-C25 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted carboxyalkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted silane group, or an organically modified clay selected from a mixture of these clays, preferably an organically modified clay having a quaternary ammonium ion of the N ＋ R １ R ２ R ３ R ４ type quaternary ammonium ion - The photopolymerizable adhesive composition according to claim 1 or 2, which is a mixture of the zeolite and the organically modified clay.

4. The block copolymer is selected from the group consisting of block copolymers comprising at least one M block and at least one B block. The M block represents a polymer block containing at least 50% by weight of methyl methacrylate. The photopolymerizable adhesive composition according to any one of the preceding claims, wherein block B is an elastomer polymer block that is incompatible with block M and has a glass transition temperature (Tg) of less than 20°C.

5. The alkoxysilane (meth)acrylate monomer is selected from the group consisting of trialkoxysilane (meth)acrylate monomers, as described in any one of the preceding claims, for the photopolymerizable adhesive composition.

6. A photopolymerizable adhesive composition according to any one of the preceding claims, further comprising at least one (meth)acrylate monomer, a methacrylic acid monomer, at least one urethane (meth)acrylate oligomer, at least one monofunctional reactive diluent, and a mixture thereof, wherein the homopolymer obtained after polymerization has a glass transition temperature of less than 0°C.

7. The photopolymerizable adhesive composition according to claim 7, wherein the (meth)acrylate monomer, if present, is 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 acrylate, and mixtures thereof.

8. A photopolymerizable adhesive composition according to any one of the preceding claims, wherein the composition is a single-component composition.

9. The photopolymerizable adhesive composition according to any one of the preceding claims, wherein the glass transition temperature after polymerization is at least 85°C, preferably at least 90°C, and more preferably at least 100°C.

10. An adhesive product comprising a photopolymerizable adhesive composition according to any one of the preceding claims, and an opaque container for containing the same.

11. A step of applying a photopolymerizable adhesive composition according to any one of claims 1 to 9 to at least one cover and / or an electronic or optoelectronic device, A step of photopolymerizing the applied photopolymerizable adhesive composition to obtain a polymerized adhesive, An adhesive obtained by a method comprising, optionally, a step of molding the polymerized adhesive.

12. First cover, A first adhesive according to claim 10, or a first adhesive obtained from a photopolymerizable adhesive composition according to any one of claims 1 to 9, Flexible electronic or optoelectronic devices, The second adhesive according to claim 11, or the second adhesive obtained from the photopolymerizable adhesive composition according to any one of claims 1 to 9, and An electronic or optoelectronic module comprising an assembly of a series of layers, including a second cover, in order.

13. The electronic or optoelectronic module according to claim 12, wherein the flexible electronic or optoelectronic device is selected from organic light-emitting diodes, organic photocells, organic transistors, organic sensors, or combinations thereof.

14. The electronic or optoelectronic module according to claim 12 or 13, wherein the flexible electronic or optoelectronic device is a perovskite type device.

15. A method for obtaining the module described in any one of claims 12 to 14, A process of preparing an electronic or optoelectronic device, A step of preparing a photopolymerizable adhesive composition according to any one of claims 1 to 9, The first step is to prepare the cover, The process of preparing the second cover, A step of applying a layer of the photopolymerizable adhesive composition to the surface of the device and / or to the inner surfaces of the first and second covers, respectively. A step of laminating the device and the photopolymerizable adhesive composition between the inner surfaces of the first and second covers, A method comprising the step of photopolymerizing a layer of the photopolymerizable adhesive composition.

16. Use of a photopolymerizable adhesive composition according to any one of claims 1 to 9, or the adhesive according to claim 10 or 11, for encapsulating flexible electronic or optoelectronic devices.

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