Photopolymerizable adhesive composition for encapsulating electronic or optoelectronic devices

Abstract

The present invention relates to a photopolymerizable adhesive composition comprising, in weight of the total weight of the photopolymerizable adhesive composition, 20 to 35% by weight of at least one block copolymer, preferably a (meth)acrylic block copolymer; 45 to 75% by weight of a mixture P of (meth)acrylate monomers, wherein the mixture P comprises at least one methacrylate monomer, wherein the homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C; and at least 5% by weight of a monoacrylate monomer, wherein the homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C; 2 to 15% by weight of at least one alkoxysilane (meth)acrylate monomer; and 0.1 to 5% by weight of 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 and perovskite 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 being considered, such as display applications (e.g., OLED and QLED), photovoltaic applications (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 solar cells (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 organic semiconductors, perovskite semiconductors, 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 of gases from the atmosphere (especially water vapor and oxygen), 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 sealing of flexible electronic or optoelectronic devices is achieved by a cover that is impermeable to gases, particularly water vapor and oxygen. This cover must have at least the same degree of flexibility as the device, or, if the sealing is intentionally used to limit the bending radius of the device to prevent damage to the device, it must have controlled flexibility.

[0011] Therefore, there is a pressing need to provide adhesive compositions that enable the manufacture of electronic or optoelectronic modules having satisfactory properties, particularly adhesion, optical properties, thermal properties, electrical properties, gas barrier properties, elasticity, and satisfactory resistance properties. There is also a need to provide adhesive compositions suitable for encapsulating flexible electronic or optoelectronic devices. Furthermore, there is a need to provide adhesive compositions that enable the manufacture of electronic or optoelectronic modules in which photodegradation over time (e.g., yellowing) is suppressed. There is also a need to provide adhesive compositions that enable the manufacture of electronic or optoelectronic modules in which lateral gas and water penetration over time is suppressed. There is also a need to provide adhesive compositions that enable the manufacture of electronic or optoelectronic modules with optimal efficiency and performance and satisfactory durability. Finally, there is interest in providing adhesive compositions that polymerize rapidly and have a high monomer-to-polymer conversion rate. [Overview of the Initiative]

[0012] This application mainly relates to a photopolymerizable adhesive composition, wherein the photopolymerizable adhesive composition is, in relation to the total weight of the photopolymerizable adhesive composition, 20-35% by weight of at least one block copolymer, preferably a (meth)acrylic block copolymer, A mixture P comprising 45-75% by weight of (meth)acrylate monomers, wherein the glass transition temperature (Tg) of the homopolymer obtained after polymerization is at least 85°C, wherein the mixture P comprises at least one methacrylate monomer having a glass transition temperature (Tg) of at least 85°C, and at least 5% by weight of monoacrylate monomer having a glass transition temperature (Tg) of at least 85°C, 2-15% by weight of at least one alkoxysilane (meth)acrylate monomer, The solution comprises 0.1 to 5% by weight of at least one photoinitiator.

[0013] Preferably, 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.

[0014] In one embodiment, the mixture P comprises at least one methacrylate monomer, preferably methyl methacrylate, 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, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C; and at least 5% by weight of the total weight of the mixture P, a monoacrylate monomer, preferably isobornyl acrylate, which is selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, phenyl methacrylate, isopropyl methacrylate, isobornyl methacrylate, and mixtures thereof, wherein the homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C; and a monoacrylate monomer, preferably isobornyl acrylate, which has a glass transition temperature (Tg) of at least 85°C.

[0015] In one embodiment, the mixture P further comprises at least one diacrylate monomer having a glass transition temperature (Tg) of at least 85°C of the homopolymer obtained after polymerization. Preferably, the diacrylate monomer is selected from dipropylene glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, and tricyclodecanedimethanol diacrylate. Preferably, the diacrylate monomer having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization is tricyclodecanedimethanol diacrylate (TCDDMDA).

[0016] Preferably, the mixture P is - The mixture P is given 20 to 95% by weight, more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight, and preferably 40 to 60% by weight of at least one methacrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C, - At least 5% by weight, preferably at least 10% by weight, more preferably 5 to 80% by weight, more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight, preferably 40 to 60% by weight, of a monoacrylate monomer whose glass transition temperature (Tg) of the homopolymer obtained after polymerization is at least 85°C, and 1 to 20% by weight, more preferably 1 to 10% by weight, preferably 1 to 5% by weight, of at least one diacrylate monomer whose glass transition temperature of the homopolymer obtained after polymerization is at least 85°C.

[0017] In one embodiment, the alkoxysilane (meth)acrylate monomer is selected from the group consisting of trialkoxysilane (meth)acrylate monomers.

[0018] Preferably, the composition according to the present invention is preferably, based on the total weight of the composition, - 25 to 35% by weight, preferably 28 to 32% by weight, of at least one block copolymer, and - 45 to 65% by weight of a mixture P of (meth)acrylate monomers whose glass transition temperature of the homopolymer obtained after polymerization is at least 85°C, comprising 40 to 60% by weight of a methacrylate monomer whose glass transition temperature of the homopolymer obtained after polymerization is at least 85°C, preferably methyl methacrylate, and 40 to 60% by weight of a monoacrylate monomer whose glass transition temperature of the homopolymer obtained after polymerization is at least 85°C, preferably isobornyl acrylate or dicyclopentadienyl acrylate, and 0 to 10% by weight, preferably 0 to 5% by weight, of a diacrylate monomer whose glass transition temperature of the homopolymer obtained after polymerization is at least 85°C, preferably TCDDMDA, and - 3 to 10% by weight, preferably 4 to 6% by weight, of at least one alkoxysilane (meth)acrylate monomer, preferably trimethoxysilane methacrylate, and - 0.5 to 4% by weight, preferably 1 to 3% by weight, of at least one photoinitiator. -1 to 16% by weight, preferably 3 to 15% by weight of methacrylic acid, and is included.

[0019] Preferably, the composition according to the present invention is preferably, based on the total weight of the composition, -28 to 32% by weight of at least one block copolymer, and -45 to 65% by weight of a mixture P of (meth)acrylate monomers having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization, the mixture P containing 40 to 60% by weight of methyl methacrylate, 40 to 60% by weight of preferably isobornyl acrylate, and 0 to 5% by weight of TCDDMDA, and -4 to 6% by weight of trimethoxysilane methacrylate, and -1 to 3% by weight of at least one photoinitiator, and -3 to 15% by weight of methacrylic acid, and is included.

[0020] In one embodiment, the composition is a single-component composition.

[0021] Preferably, the composition according to the present invention has a glass transition temperature after polymerization of at least 85°C, preferably at least 90°C, more preferably at least 100°C.

[0022] The present invention also relates to an adhesive product comprising the photopolymerizable adhesive composition according to the present invention and an opaque container containing the same.

[0023] The present invention also relates to an adhesive, the adhesive comprising a step of applying the photopolymerizable adhesive composition according to the present invention 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, and optionally, a step of shaping the polymerized adhesive, and is obtained by a method comprising the above steps.

[0024] The present application also relates to an electronic or optoelectronic module, the electronic or optoelectronic module comprising 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. Preferably, in the electronic or optoelectronic module, the flexible electronic or optoelectronic device is selected from organic light-emitting diodes, organic photocells, organic transistors, organic sensors, or a combination thereof.

[0025] Preferably, in the electronic or optoelectronic module, the flexible electronic or optoelectronic device is a perovskite type device.

[0026] 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 process of preparing the first 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.

[0027] 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.

[0028] The inventors have found that a combination of a methacrylate monomer having a glass transition temperature (Tg) of at least 85°C for the homopolymer obtained after polymerization, a monoacrylate monomer having a glass transition temperature (Tg) of at least 85°C for the homopolymer obtained after polymerization, and optionally a diacrylate monomer having a glass transition temperature (Tg) of at least 85°C for the homopolymer obtained after polymerization, can advantageously improve the polymerization reaction rate and conversion rate of the photopolymerizable adhesive composition of the present invention compared to a composition containing only a methacrylate monomer having a glass transition temperature (Tg) of at least 85°C for the homopolymer obtained after polymerization. This can advantageously improve industrial productivity in the manufacture of electronic or optoelectronic modules. The inventors have also found that this combination can advantageously limit the shrinkage rate associated with the polymerization of the photopolymerizable composition. [Brief explanation of the drawing]

[0029] [Figure 1] The changes in the active surface area over time for the reference composition (CExC) and compositions 1 and 2 (Ex1 and Ex2, respectively) according to the present invention are shown. [Figure 2] The VA of the reference composition (CExC) and compositions 1 and 2 (Ex1 and Ex2, respectively) according to the present invention are shown. [Figure 3] The reference composition (CExC) and the DA12 of compositions 1 and 2 (Ex1 and Ex2, respectively) according to the present invention are shown. [Figure 4] The average thickness of the active surface of the reference composition (CExC) and compositions 1 and 2 (Ex1 and Ex2, respectively) according to the present invention changes over time. [Figure 5] The VE of the reference composition (CExC) and compositions 1 and 2 (Ex1 and Ex2, respectively) according to the present invention are shown. [Figure 6] The DE380 values ​​for the reference composition (CExC) and compositions 1 and 2 (Ex1 and Ex2, respectively) according to the present invention are shown. [Modes for carrying out the invention]

[0030] The present invention will be described in more detail and in a non-limiting manner in the following description.

[0031] Unless otherwise specified, all percentages are based on weight.

[0032] In this specification, the quantities given for a given species can be applied to that species according to all of its definitions (as referred to herein), including more restrictive definitions.

[0033] 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.

[0034] 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 with a very small radius of curvature.

[0035] The term "adhesive" refers to a matrix / structure formed around an electronic or optoelectronic device by a photopolymerizable adhesive composition. In this specification, the terms "adhesive" and "encapsulant" are used interchangeably.

[0036] 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.

[0037] 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."

[0038] 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.

[0039] 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.

[0040] 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).

[0041] 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.

[0042] The term "polymer" refers to copolymer or homopolymer.

[0043] The term "homopolymer" refers to a polymer that contains multiple identical monomer units.

[0044] The term "copolymer" refers to a polymer formed by grouping together at least two different types of monomer units (the comonomers shown).

[0045] 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.

[0046] 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.

[0047] 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.

[0048] The term "polymerization" refers to a chemical method in which molecules can bond together to form a three-dimensional network.

[0049] 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 method of molecular interconnection known as polymerization.

[0050] 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.

[0051] The term "ambient temperature" refers to a temperature of approximately 20°C.

[0052] 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.

[0053] In this invention, "mixture P" of (meth)acrylate monomers, in which the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C, should be understood to mean a mixture P of (meth)acrylate monomers characterized in that, for each of the (meth)acrylate monomers, the homopolymer obtained after polymerization of each monomer has a glass transition temperature of at least 85°C.

[0054] Photopolymerizable adhesive composition In a first aspect, the present invention relates to a photopolymerizable adhesive composition.

[0055] Block copolymer The composition comprises at least one block copolymer, preferably at least one (meth)acrylic block copolymer.

[0056] The composition may contain at least one block copolymer in an amount of 20-35% by weight, preferably 25-35% by weight, and more preferably 28-32% by weight, based on the total weight of the composition.

[0057] 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).

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] Other monomers that make up the M block, other than methyl methacrylate, may be other (meth)acrylic monomers or non-(meth)acrylic monomers.

[0063] 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).

[0064] 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.

[0065] 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.

[0066] 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.

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

[0068] 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.

[0069] In the case of triblock copolymer MBM, the two M blocks are composed of the same monomers (or comonomers) as the M blocks of the diblock copolymer BM described above. These two M blocks may be identical or different. For example, these two blocks M may be composed of the same monomers, but their molar masses may differ.

[0070] Block B is composed of the same monomers (or comonomers) as Block B of the diblock copolymer BM described above.

[0071] 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.

[0072] 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.

[0073] Preferably, the triblock copolymer MBM is a polymethyl methacrylate-poly(styrene-co-butylacrylate)-polymethyl methacrylate block copolymer.

[0074] 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.

[0075] 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.

[0076] Block copolymers are marketed by Arkema under the name Nanostrength® (registered trademark).

[0077] Monoacrylate monomer The composition comprises a mixture P of (meth)acrylate monomers in an amount of 45 to 75% by weight relative to the total weight of the composition, wherein the resulting homopolymer has a glass transition temperature (Tg) of at least 85°C, and the mixture P comprises at least one methacrylate monomer having a glass transition temperature (Tg) of at least 85°C, and at least 5% by weight of monoacrylate monomer having a glass transition temperature (Tg) of at least 85°C.

[0078] The composition of the present invention preferably contains 45 to 75% by weight, preferably 45 to 70% by weight, and more preferably 45 to 65% by weight of mixture P, based on the total weight of the composition.

[0079] Preferably, mixture P is - Mixture P is mixed with at least one methacrylate monomer in an amount of 20-95% by weight, more preferably 20-80% by weight, even more preferably 30-70% by weight, and preferably 40-60% by weight, wherein the 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 mixture P 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 "Measuring viscosity of adhesives".

[0080] The methacrylate monomer having a glass transition temperature 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, isopropyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, and mixtures thereof. Preferably, the methacrylate monomer having a glass transition temperature of at least 85°C in the homopolymer obtained after polymerization is methyl methacrylate.

[0081] The monoacrylate monomer having a glass transition temperature (Tg) of the homopolymer obtained after polymerization at least 85°C can be selected from the group consisting of isobornyl acrylate, dihydrodicyclopentadienyl acrylate, and mixtures thereof. Preferably, the acrylate monomer having a glass transition temperature (Tg) of the homopolymer obtained after polymerization at least 85°C is isobornyl acrylate.

[0082] Mixture P 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).

[0083] Alkoxysilane (meth)acrylate monomer The composition comprises at least one alkoxysilane (meth)acrylate monomer.

[0084] The composition may contain at least one alkoxysilane (meth)acrylate monomer in an amount of 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.

[0085] 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.

[0086] 3-(trimethoxysilyl)propyl methacrylate is commercially available from Momentive® under the name Silquest® A174.

[0087] 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 urethane monomers and / or oligomers by ultraviolet (UV) or visible light irradiation to obtain the adhesive, can be used.

[0088] 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, and preferably 1 to 3% by weight, based on the total weight of the composition. 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.

[0089] Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide is marketed by IGM Resins under the name Omnirad® 819 (formerly Irgacure® 819 by Ciba® Specialty Chemicals). A mixture containing benzophenone, α-hydroxyketone, and triethylbenzoyl-diphenylphosphine oxide is marketed by Lehvoss under the name Esacure® KTO 46.

[0090] 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.

[0091] The composition may contain, in an amount of 0 to 5% by weight, at least one (meth)acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature of less than 0°C. If present, the composition may contain, in an amount of 0.1 to 5% by weight, at least one (meth)acrylate monomer whose homopolymer obtained after polymerization has a glass transition temperature of less than 0°C.

[0092] 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.

[0093] Preferably, 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.

[0094] Methacrylic acid The composition may contain methacrylic acid monomers.

[0095] Please understand that the methacrylic acid monomer is not the methacrylate of mixture P.

[0096] 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 15% by weight of methacrylic acid based on the total weight of the composition.

[0097] Preferably, the composition contains 5 to 12% by weight of methacrylic acid based on the total weight of the composition.

[0098] Urethane (meth)acrylate oligomer The composition may contain at least one urethane (meth)acrylate oligomer.

[0099] 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.

[0100] Preferably, the composition is substantially free of urethane (meth)acrylate oligomers.

[0101] 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.

[0102] The composition may further contain at least one monofunctional reactive diluent.

[0103] 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.

[0104] 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 from Sartomer under the name CN966H90®.

[0105] viscosity The photopolymerizable adhesive composition is preferably a liquid composition.

[0106] The viscosity of the composition may be 100 to 20,000 mPa·s, preferably 100 to 10,000 mPa·s, 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".

[0107] 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.

[0108] Preferably, the composition is - At least one block copolymer, preferably at least one (meth)acrylic block copolymer, preferably a (meth)acrylic block copolymer having a triblock MBM structure, - A mixture P of at least one (meth)acrylate monomer having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization, the mixture P comprising: at least one methacrylate monomer 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, having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization, preferably methyl methacrylate; and at least 5% by weight of isobornyl acrylate, dihydrodicyclopentadienyl acrylate relative to the total weight of the mixture P. A mixture P comprising: a monoacrylate monomer, preferably isobornyl acrylate, selected from diacrylate and mixtures thereof, having a glass transition temperature (Tg) of at least 85°C for the homopolymer obtained after polymerization; and a diacrylate monomer, preferably tricyclodecanedimethanol diacrylate, selected from dipropylene glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, and tricyclodecanedimethanol diacrylate, having a glass transition temperature (Tg) of at least 85°C for the homopolymer obtained after polymerization; and a mixture P comprising: - A monomer selected from the group consisting of at least one alkoxysilane (meth)acrylate monomer, preferably trialkoxysilane (meth)acrylate monomer, 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, - A photoinitiator selected from the group consisting of at least one photoinitiator, preferably 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 and mixtures thereof, -Optionally, at least one (meth)acrylate monomer having a glass transition temperature of less than 0°C of the homopolymer obtained after polymerization, 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 acrylate, and mixtures thereof, preferably a monomer that is butyl acrylate. -Optionally, methacrylic acid monomer and -Optionally, an oligomer selected from at least one urethane (meth)acrylate oligomer, preferably an oligomer selected from aliphatic urethane diacrylate oligomers, preferably an oligomer that is an aliphatic urethane diacrylate, -Optionally, the solution comprises (or is composed of) at least one monofunctional reactive diluent, preferably 2-(2-ethoxy-ethoxy)ethyl acrylate.

[0109] Preferably, the composition is, with respect to the total weight of the composition, -20 to 35% by weight, preferably 25 to 35% by weight, more preferably 28 to 32% by weight of at least one block copolymer, A mixture P comprising -45 to 75% by weight, preferably 45 to 70% by weight, more preferably 45 to 65% by weight, of (meth)acrylate monomers, wherein the glass transition temperature of the homopolymer obtained after polymerization is at least 85°C, the mixture P comprising: at least one methacrylate monomer, wherein the glass transition temperature of the homopolymer obtained after polymerization is at least 85°C; at least 5% by weight, preferably at least 10% by weight, preferably 5 to 80% by weight, more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight, of monoacrylate monomers, wherein the glass transition temperature of the homopolymer obtained after polymerization is at least 85°C; and optionally, a diacrylate monomer, wherein the glass transition temperature of the homopolymer obtained after polymerization is at least 85°C. -2 to 15% by weight, preferably 3 to 10% by weight, more 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% by weight, at least one photoinitiator, -0 to 5% by weight of at least one (meth)acrylate monomer, the homopolymer obtained after polymerization has a glass transition temperature of less than 0°C, - 0 to 20% by weight, preferably 1 to 16% by weight, more preferably 3 to 15% by weight of methacrylic acid, A compound comprising (or composed of) at least one monofunctional reactive diluent in an amount of -0 to 0.7% by weight.

[0110] Preferably, the composition is, with respect to the total weight of the composition, -20 to 35% by weight, preferably 25 to 30% by weight, at least one block copolymer, A mixture P comprising -45 to 75% by weight, preferably 45 to 70% by weight, more preferably 45 to 65% by weight of (meth)acrylate monomers, wherein the resulting homopolymer has a glass transition temperature of at least 85°C, the mixture P comprising: at least one methacrylate monomer having a glass transition temperature of at least 85°C; at least 5% by weight, preferably at least 10% by weight, more preferably 5 to 80% by weight, more preferably 20 to 80% by weight, and even more preferably 30 to 70% by weight of monoacrylate monomers having a glass transition temperature of at least 85°C; and optionally 0 to 40% by weight, preferably 1 to 20% by weight of diacrylate monomers having a glass transition temperature of at least 85°C. -2 to 15% by weight, preferably 3 to 10% by weight, more 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% by weight, at least one photoinitiator, -0 to 5% by weight of at least one (meth)acrylate monomer, the homopolymer obtained after polymerization has a glass transition temperature of less than 0°C, - 0 to 20% by weight, preferably 1 to 16% by weight, more preferably 3 to 15% by weight of methacrylic acid, A compound comprising (or composed of) at least one monofunctional reactive diluent in an amount of -0 to 0.7% by weight.

[0111] Preferably, the composition is, with respect to the total weight of the composition, -25 to 35% by weight, preferably 28 to 32% by weight, at least one block copolymer, A mixture P comprising -45 to 65% by weight of (meth)acrylate monomers, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C, wherein the mixture P comprises: 40 to 60% by weight of methacrylate monomers, preferably methyl methacrylate, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C; 40 to 60% by weight of monoacrylate monomers, preferably isobornyl acrylate or dihydrodicyclopentadienyl acrylate, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C; and 0 to 10% by weight, preferably 0 to 5% by weight of diacrylate monomers, preferably TCDDMDA, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C. -3 to 10% by weight, preferably 4 to 6% by weight, of at least one alkoxysilane (meth)acrylate monomer, preferably trimethoxysilane methacrylate, -0.5 to 4% by weight, preferably 1 to 3% by weight, at least one photoinitiator, A solution comprising (or composed of) -1 to 16% by weight, preferably 3 to 15% by weight, of methacrylic acid.

[0112] Preferably, the composition is, with respect to the total weight of the composition, -28~32% by weight of at least one block copolymer, A mixture P of (meth)acrylate monomers in an amount of -45 to 65% by weight, wherein the glass transition temperature of the homopolymer obtained after polymerization is at least 85°C, comprising 40 to 60% by weight of methyl methacrylate, 40 to 60% by weight of preferably isobornyl acrylate, and 0 to 5% by weight of TCDDMDA. -4 to 6% by weight of trimethoxysilane methacrylate, preferably 3-(trimethoxysilyl)propyl methacrylate, -1 to 3% by weight of at least one photoinitiator, - Contains (or is composed of) 3 to 15% by weight of methacrylic acid.

[0113] 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.

[0114] 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 should not be exposed to light.

[0115] 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.

[0116] 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.

[0117] The container can be selected from, for example, a group consisting of bottles or tubes.

[0118] glue In a third aspect, the present invention relates to adhesives, and more particularly to adhesives obtained from the above-described photopolymerizable adhesive compositions. 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.

[0119] 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, obtained by a method including the step of molding a polymerized adhesive.

[0120] The adhesive can take the form of a film.

[0121] 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.

[0122] 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 sealed 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.

[0123] The adhesive can have a thickness of 10 to 200 μm, preferably 10 to 100 μm, and preferably 10 to 30 μm.

[0124] The adhesive has several advantages, particularly that it can be used at temperatures of at least 70°C, preferably at least 85°C, when, for example, the electronic or optoelectronic device is a photocell, or when the device needs to meet temperature test criteria (e.g., automotive applications).

[0125] 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).

[0126] 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.

[0127] 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.

[0128] 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.

[0129] The adhesive preferably exhibits satisfactory strength, particularly against aging under ultraviolet light, abrasion, and / or impact.

[0130] 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 of 5 g / m² per 1 mm thickness. 2 .d -1 Less than 2 g.m 2 .d -1 It should be less than [amount].

[0131] 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.

[0132] 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.

[0133] 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.

[0134] The electronic or optoelectronic device itself may include a semiconductor layer deposited on a support substrate.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] The module can have a total thickness of 50 to 500 μm, preferably 50 to 300 μm, and more preferably 50 to 150 μm.

[0139] 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.

[0140] 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.

[0141] The covers may be the same or different.

[0142] The cover may be single-layered or multi-layered.

[0143] The cover may be flexible or rigid, and is preferably flexible.

[0144] 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.

[0145] Depending on the electronic or optoelectronic devices used, and the desired features and characteristics of the module, the cover may have specific properties.

[0146] The cover may be a polymer cover.

[0147] The cover could be an inorganic cover.

[0148] 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.

[0149] The polymer cover may include at least one polymer layer (or PET layer) and a fluorinated polymer layer obtained from polyethylene terephthalate (PET).

[0150] 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.

[0151] The cover may include at least one glass layer.

[0152] The cover may include at least one polymer layer (or PMMA layer) obtained from poly(methyl methacrylate) (PMMA). The glass layer or PMMA layer is particularly suitable for use as a top or front cover.

[0153] Flexible covers, particularly suitable for encapsulating flexible electronic or optoelectronic devices, especially organic or perovskite batteries, are commercially available from 3M® under the name 3M Ultra-Barrier Solar Film. This cover is a multilayer laminated cover comprising a PET film, a 20-300 nm silica, alumina, or silicon nitride type inorganic barrier layer, a so-called PSA film (pressure-sensitive adhesive), and a fluorinated polymer film or layer called a "weather-resistant layer" positioned to protect the overall environment from external conditions.

[0154] 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 the step of photopolymerizing a layer of a photopolymerizable adhesive composition.

[0155] 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.

[0156] In one particular embodiment, the rigid module is obtained by vacuum lamination technology ("sheet-to-sheet").

[0157] 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.

[0158] 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.

[0159] Examples The following examples illustrate the present invention, but are not intended to limit it.

[0160] List of materials and equipment Block copolymer: Triblock copolymer MBM-[polymethyl methacrylate-poly(styrene-co-butyl acrylate)-polymethyl methacrylate block copolymer] (abbreviation: MBM) supplied by Arkema.

[0161] A methacrylate monomer (abbreviated as MAM) whose homopolymer obtained after polymerization has a glass transition temperature of at least 85°C: methyl methacrylate A monoacrylate monomer whose glass transition temperature of the resulting homopolymer is at least 85 °C: isobornyl acrylate (abbreviation: IBOA) An acrylate monomer whose glass transition temperature of the resulting homopolymer is at least 85 °C: tricyclodecane dimethanol diacrylate (abbreviation: TCDDMDA) supplied by Arkema An alkoxysilane (meth)acrylate monomer: 3-(trimethoxysilyl)propyl methacrylate (product Silquest® A174 from Momentive®) (abbreviation: A174) A photoinitiator: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (abbreviation: BAPO) available from Sigma-Aldrich Methacrylic acid (abbreviation: AMA) A light source: UV LED system Delolux® 03S

[0162] Test target module The test target module is generally called a test piece.

[0163] PK layer: a layer with a surface area of 4×4 cm (16 cm 2 ) of the formula Cs 0.05 FA 0.95 Pb(l 0.8 8Br 0.12 )3 perovskite layer Glass layer: a layer with a surface area of 5×5 cm (25 cm 2 ) ITO layer: indium tin oxide layer The ITO glass layer itself forms a support substrate.

[0164] The PK layer is deposited by spin coating technology. The upper ITO layer is deposited by physical vapor deposition.

[0165] The perovskite layer is deposited on the support substrate and has an overhang of 5 mm between the edge of the substrate and the perovskite layer.

[0166] The modules are individually sealed between two 1.2 mm thick glass covers with the test photopolymerizable composition.

[0167] Test method Viscosity measurement The viscosity of the composition was 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".

[0168] Polymerization reaction rate and conversion rate The polymerization reaction rate and final conversion rate of the photopolymerizable composition were determined by real-time Fourier transform infrared spectroscopy (RT-FTIR). The characterized composition was deposited as a 300 μm thick film between two polypropylene films. The sample was set in an RT-FTIR spectrophotometer at a wavelength of 395 nm and an output of 630 mW / cm². 2 By irradiating the composition with light from a light-emitting diode (LED) lamp, continuous measurement of the infrared absorption spectrum of the composition is possible. Measuring the absorbance at a frequency of 6170 nm, corresponding to one of the characteristic infrared absorption peaks of the double bond of the (meth)acrylate functional group, allows monitoring of the monomer conversion rate (expressed as a percentage of the number of moles of reacted double bonds relative to the number of initial double bonds) over time. After several tens of seconds, this conversion rate reaches a plateau, representing the maximum conversion rate of the composition under these irradiation conditions. The conversion rate (percent) at time t (denoted as conversion rate (t)) was calculated by the following relation: conversion rate (t) = (A0 - At) / (A0) x 100, where A0 and At represent the absorbance at time t=0 and a given time t, respectively.

[0169] The efficiency of the polymerization reaction rate was evaluated by calculating the propagation constant (kp) and the maximum polymerization rate (Rp) from this conversion rate curve as a function of irradiation time. In Table 2, kp[P·] corresponds to the slope of the curve plotted as a function of time of ln([M0] / [Mt]), and [M0] and [Mt] are the concentrations of the (meth)acrylate function at time t=0 and a given time t, respectively. In this equation, kp corresponds to the propagation rate constant, and [P·] corresponds to the steady-state concentration of the propagating radical. The term Rp / [M0]x100 corresponds to the maximum slope of the conversion rate versus time curve, which is for the maximum polymerization reaction rate. The system is more efficient with respect to the polymerization reaction rate when the values ​​of kp, [P·], and Rp are high.

[0170] Thermal properties and gas barrier properties The thermal 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.

[0171] The gas barrier properties were determined by optical testing to measure the degradation rate of the perovskite layer of the test specimen. The degradation of the tested module was evaluated using the following method: The above-mentioned test specimen was 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 (cm) was measured. 2The algorithm parameters for the perovskite test ( / h) were determined. The paper "Perovskite Test: A high throughput method to screen ambient encapsulation conditions" by E. Booker et al., Energy Technology (2020) 8(12), and the paper "A machine vision tool for facilitating the optimization of large area perovskite photovoltaics" by N. Taherimakhsousi et al., npj Computational Materials (2021) 190 were referenced, with the latter paper providing a more detailed description of the algorithm used. To evaluate the aging of the perovskite layer, photographic images of the specimens were taken periodically, for example, every 48 hours. In all these tests, the initial thickness of the perovskite (PK) was 400 nm, and the initial area was approximately 14 cm² in all tests. 2 Based on this premise, the area of ​​the "active" surface, which is the area of ​​the PK layer with a thickness greater than the empirical threshold (180 nm), was measured. By monitoring this area, 12-3 cm² was determined. 2 The VA parameter (layer degradation rate cm) was established by linear regression between the two parameters. 2 / h) and the "active" surface is 12cm 2 This makes it possible to determine the DA12 parameter (Figure 3), which is the time it takes to reach a certain point.

[0172] By monitoring the average thickness of the "active" surface, it becomes possible to determine the VE parameter (thickness degradation rate) obtained by linear regression established at 340-230 nm, and the DE380 parameter, which corresponds to the time it takes for the average thickness, starting from 400 nm, to reach 380 nm.

[0173] 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).

[0174] [Table 1]

[0175] 3 g of the photoinitiator BAPO was added to 100 g of the composition described in Table 1.

[0176] Compositions CExA, CExB, and CExC are comparative compositions. Compositions Ex1 and Ex2 according to the present invention have a viscosity level suitable for the method of implementation, i.e., a viscosity of 200 to 10,000 cP. Compositions CExA and CExB have too high a viscosity to be handled.

[0177] result Reaction rate and conversion rate Table 2 below summarizes the reaction rates and conversion data obtained for the compositions (Ex1 and Ex2) and comparative composition (CExC) according to the present invention, with each composition being tested twice.

[0178] [Table 2]

[0179] As can be seen from Table 2, formulations Ex1 and Ex2 have significantly higher kp, [P·], and Rp values ​​compared to the reference (CExC), indicating remarkably high polymerization efficiency. Furthermore, the maximum conversion rate is higher for Ex1 and Ex2 compared to CExC.

[0180] vapor barrier The degradation rate of multilayer modules obtained using compositions Ex1 and Ex2 according to the present invention, and comparative composition CExC, was tested.

[0181] The tested module was 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.

[0182] 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 Assuming the above, the area of ​​the "active" surface is the area of ​​the PK layer having a thickness greater than the empirical threshold (180 nm) (Figure 1).

[0183] By monitoring this area, 12-3cm 2 The established linear regression allows us to determine the VA parameters (Figure 2). The VA parameters are observed to be similar across the three formulations.

[0184] Monitoring of the same area revealed that the "active" surface was 12 cm². 2 It becomes possible to define the DA12 parameter (Figure 3), which is the time it takes to reach a certain point. DA12 is observed to be similar in the formulation.

[0185] By monitoring the average thickness of the "active" surface (Figure 4), the following can be obtained: The VE parameters (Figure 5) obtained by linear regression established at 340-230 nm are observed to be superior in the composition according to the present invention.

[0186] The DE380 parameter (Figure 6) corresponds to the time it takes for the average thickness, starting from 400 nm, to reach 380 nm. The DE380 values ​​are observed to be very similar across the three formulations.

[0187] contraction rate The linear shrinkage rates during polymerization of the three example formulations were measured. This measurement was performed using photorheology with a Thermofischer Haake Mars 40 plate / plate device, resulting in a shrinkage rate of 286 MW / cm². 2The measurement was performed by monitoring the thickness of the sample (denoted as h) in a rheometer gap irradiated with a mercury UV lamp in real time at a shear rate of 0.01%. The temperature was stabilized at 25°C for 120 seconds before the start of the measurement. Next, the shrinkage rate was calculated as a percentage of the shrinkage amount of term h. The results are shown in Table 3 below.

[0188] [Table 3]

[0189] Therefore, the composition of the present invention makes it possible to significantly reduce the shrinkage rate.

Claims

1. A photopolymerizable adhesive composition, wherein, with respect to the total weight of the photopolymerizable adhesive composition, 20 to 35% by weight of at least one block copolymer, preferably a (meth)acrylic block copolymer, A mixture P comprising 45 to 75% by weight of (meth)acrylate monomers, wherein the glass transition temperature (Tg) of the homopolymer obtained after polymerization is at least 85°C, wherein the mixture P comprises at least one methacrylate monomer having a glass transition temperature (Tg) of at least 85°C, and at least 5% by weight of monoacrylate monomer having a glass transition temperature (Tg) of at least 85°C. 2 to 15% by weight of at least one alkoxysilane (meth)acrylate monomer, A photopolymerizable adhesive composition comprising 0.1 to 5% by weight of at least one photoinitiator.

2. 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 claim 1, 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.

3. The photopolymerizable adhesive composition according to any one of the preceding claims, wherein the mixture P comprises at least one methacrylate monomer, preferably methyl methacrylate, 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, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C; and at least 5% by weight of the total weight of the mixture P, a monoacrylate monomer, preferably isobornyl acrylate, wherein the homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C, selected from isobornyl acrylate, dihydrodicyclopentadienyl acrylate, and mixtures thereof.

4. The photopolymerizable adhesive composition according to any one of the preceding claims, wherein the mixture P further comprises at least one diacrylate monomer having a glass transition temperature (Tg) of at least 85°C of the homopolymer obtained after polymerization, preferably the diacrylate monomer is selected from dipropylene glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, and tricyclodecanedimethanol diacrylate, and preferably the diacrylate monomer having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization is tricyclodecanedimethanol diacrylate (TCDDMDA).

5. The aforementioned mixture P is - With respect to the weight of the mixture P, at least one methacrylate monomer is present in an amount of 20 to 95% by weight, more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight, and preferably 40 to 60% by weight, wherein the homopolymer obtained after polymerization has a glass transition temperature (Tg) of at least 85°C. - A monoacrylate monomer having a glass transition temperature (Tg) of at least 85°C for the homopolymer obtained after polymerization, in an amount of at least 5% by weight, preferably at least 10% by weight, more preferably 5 to 80% by weight, more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight, and more preferably 40 to 60% by weight. A photopolymerizable adhesive composition according to any one of the preceding claims, comprising: - 1 to 20% by weight, more preferably 1 to 10% by weight, and preferably 1 to 5% by weight, of at least one diacrylate monomer having a glass transition temperature of at least 85°C of the homopolymer obtained after polymerization.

6. 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.

7. With respect to the total weight of the above composition, preferably, - 25 to 35% by weight, preferably 28 to 32% by weight of at least one block copolymer, A mixture P comprising -45 to 65% by weight of (meth)acrylate monomers, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C, wherein the mixture P comprises: 40 to 60% by weight of methacrylate monomers, preferably methyl methacrylate, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C; 40 to 60% by weight of monoacrylate monomers, preferably isobornyl acrylate or dihydrodicyclopentadienyl acrylate, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C; and 0 to 10% by weight, preferably 0 to 5% by weight of diacrylate monomers, preferably TCDDMDA, wherein the homopolymer obtained after polymerization has a glass transition temperature of at least 85°C. -3 to 10% by weight, preferably 4 to 6% by weight, of at least one alkoxysilane (meth)acrylate monomer, preferably trimethoxysilane methacrylate, - 0.5 to 4% by weight, preferably 1 to 3% by weight, at least one photoinitiator, A composition according to any one of the preceding claims, comprising -1 to 16% by weight, preferably 3 to 15% by weight, of methacrylic acid.

8. With respect to the total weight of the above composition, preferably, -28 to 32% by weight of at least one block copolymer, A mixture P of (meth)acrylate monomers in an amount of -45 to 65% by weight, wherein the glass transition temperature of the homopolymer obtained after polymerization is at least 85°C, comprising 40 to 60% by weight of methyl methacrylate, 40 to 60% by weight of preferably isobornyl acrylate, and 0 to 5% by weight of TCDDMDA. -4 to 6% by weight of trimethoxysilane methacrylate, -1 to 3% by weight of at least one photoinitiator, A composition according to any one of the preceding claims, comprising -3 to 15% by weight of methacrylic acid.

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

10. 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.

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

12. A step of applying a photopolymerizable adhesive composition according to any one of claims 1 to 10 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.

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

14. The flexible electronic or optoelectronic device is selected from organic light-emitting diodes, organic photocells, organic transistors, organic sensors, or combinations thereof, as described in claim 13.

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

16. A method for obtaining the module described in any one of claims 13 to 15, 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 10, 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.

17. Use of a photopolymerizable adhesive composition according to any one of claims 1 to 10, or the adhesive according to claim 11 or 12, for encapsulating a flexible electronic or optoelectronic device.

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