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WO2025094586A1 - Composition d'encapsulation de dispositif électronique pour impression jet d'encre, procédé de formation de film d'encapsulation de dispositif électronique et film d'encapsulation de dispositif électronique - Google Patents

Composition d'encapsulation de dispositif électronique pour impression jet d'encre, procédé de formation de film d'encapsulation de dispositif électronique et film d'encapsulation de dispositif électronique Download PDF

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Publication number
WO2025094586A1
WO2025094586A1 PCT/JP2024/035477 JP2024035477W WO2025094586A1 WO 2025094586 A1 WO2025094586 A1 WO 2025094586A1 JP 2024035477 W JP2024035477 W JP 2024035477W WO 2025094586 A1 WO2025094586 A1 WO 2025094586A1
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WO
WIPO (PCT)
Prior art keywords
electronic device
sealing
meth
acrylate
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/035477
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English (en)
Japanese (ja)
Inventor
宏元 井
慎一郎 森川
幸宏 牧島
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of WO2025094586A1 publication Critical patent/WO2025094586A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass

Definitions

  • the present invention relates to an inkjet electronic device sealing composition, a method for forming an electronic device sealing film, and an electronic device sealing film.
  • the present invention relates to an electronic device sealing composition that can produce an electronic device sealing film with good adhesion, flexibility, and heat resistance.
  • organic electroluminescence devices have the advantage of being able to be made thin and lightweight, and active research is being conducted into flexible organic electroluminescence devices.
  • organic electroluminescence devices are also referred to as “organic EL devices” or “organic EL elements.”
  • Patent Document 1 discloses a technique for an ultraviolet-curable resin for sealing an organic EL element, which can be molded by an inkjet method and the cured product can be easily made to have a low dielectric constant.
  • the present inventors examined the cured product using a film-like support substrate, peeling of the cured product was observed more significantly as the flexibility became more severe, and it was found that there was a problem with the adhesion of the cured product.
  • Patent Document 2 discloses a technology for a self-repairing resin composition having excellent curability with active energy rays.
  • a resin composition having excellent self-repairing properties, adhesion, and flexibility is provided.
  • the present inventors checked the resin composition, they found that the repeated bending performance assumed for foldable and rollable was insufficient, and that there was a problem in adapting it to flexible organic EL devices.
  • the self-repair function utilizes ladder (zipper) type crosslinking that utilizes the reversibility of intermolecular hydrogen bonds, the heat resistance was insufficient.
  • the present invention has been made in consideration of the above problems and circumstances.
  • the problem to be solved by the present invention is to provide a composition for electronic device sealing that can produce an electronic device sealing film with good adhesion, flexibility, and heat resistance. It is also to provide an electronic device sealing film that uses the electronic device sealing composition, and a method for forming an electronic device sealing film.
  • the present inventors have investigated the causes of the above problems and have found that an electronic device sealing film having good adhesion, flexibility and heat resistance can be obtained by controlling the loss factor peak value and storage modulus of the dynamic viscoelasticity of the sealing composition after curing. That is, the above-mentioned problems of the present invention are solved by the following means.
  • a composition for electronic device encapsulation for inkjet printing comprising a photopolymerizable monomer and a photopolymerization initiator,
  • the photopolymerizable monomer contains a (meth)acrylate
  • the loss factor (tan ⁇ ) peak value is within the range of 0.3 to 1.0
  • An ink-jet composition for electronic device sealing having a storage modulus (G') in the range of 1.0 to 3.0 GPa.
  • the (meth)acrylate contains a monofunctional (meth)acrylate, 2.
  • composition for electronic device sealing for inkjet printing described in paragraph 1, wherein the (meth)acrylate has a phenyl group.
  • An electronic device sealing film for sealing an electronic device comprising: a first encapsulation layer comprising silicon nitride, silicon oxide, or silicon oxynitride; 5.
  • An electronic device sealing film comprising: a second sealing layer formed using the composition for sealing an electronic device according to any one of items 1 to 4.
  • the electronic device sealing film according to claim 8 having a third sealing layer containing silicon nitride, silicon oxide or silicon oxynitride on the second sealing layer.
  • the present invention it is possible to provide a composition for electronic device encapsulation that can provide an electronic device encapsulating film having good adhesion, flexibility, and heat resistance. Also, according to the above-mentioned means of the present invention, it is possible to provide an electronic device encapsulating film using the electronic device encapsulating composition, and a method for forming an electronic device encapsulating film.
  • suitable adhesion and heat resistance can be obtained by setting the loss factor peak value within the range of 0.3 to 1.0. This is presumably because, by setting the loss factor peak value within the range, a balance is achieved between the components that store the energy generated by external force and strain inside the object and the components that diffuse it to the outside, and the stress and heat load can be alleviated as dissipated (thermal) energy.
  • the storage modulus (G') within the range of 1.0 to 3.0 GPa, the density of entanglement of molecular chains of the polymer increases, so that the modulus of elasticity increases and flexibility becomes good.
  • the loss factor peak value and storage modulus can be controlled within a preferred range by appropriately adjusting the film thickness and curing rate of the sealing film.
  • the (meth)acrylate preferably contains a monofunctional (meth)acrylate. Since monofunctional (meth)acrylates have one reactive group, the molecular weight variation of the polymer when polymerized is narrow. When the molecular weight variation is narrow, the thermal mobility of the polymer chain becomes uniform. In general, it is known that the thermal mobility of the polymer chain corresponds to the peak value and waveform of the loss factor (tan ⁇ ) of dynamic viscoelasticity. Therefore, in order to set the loss factor peak value within the specific range, it is preferable to use a monofunctional (meth)acrylate in the present invention.
  • the electronic device encapsulation composition of the present invention is an electronic device encapsulation composition for inkjet use, which contains a photopolymerizable monomer and a photopolymerization initiator, and contains a (meth)acrylate as the photopolymerizable monomer.
  • the loss factor (tan ⁇ ) peak value is in the range of 0.3 to 1.0
  • the storage modulus (G') is in the range of 1.0 to 3.0 GPa.
  • the (meth)acrylate preferably contains a monofunctional (meth)acrylate, and the content ratio of the monofunctional (meth)acrylate to the total amount of the photopolymerizable monomer is preferably 41% by mass or more.
  • the content ratio as described above, the density of entanglement of the molecular chains of the polymer when the monofunctional (meth)acrylate is polymerized is increased, and the narrow variation in molecular weight makes the thermal mobility of the polymer chains uniform, resulting in good adhesion, heat resistance, and flexibility.
  • the (meth)acrylate preferably has a phenyl group, which improves the heat resistance of the molecule and provides excellent adhesion, flexibility, and heat resistance.
  • the curing rate of the electronic device sealing film formed is preferably 80% or more in terms of adhesion.
  • Adhesion For example, when a CVD film is used as the base of a sealing film, it is considered that when the sealing film is peeled off from the CVD film, it peels off due to interfacial peeling and cohesive peeling. Interfacial peeling is related to the mechanical properties and stress of the film. It is considered that adhesion is improved by the film being appropriately polymerized and crosslinked, as these mechanical properties are high and the film stress is in an appropriate range. In addition, by making the film sufficiently hardened, the strength of the film itself is also increased, and cohesive peeling can be suppressed.
  • the sealing film by setting the curing rate of the sealing film to 80% or more, the mechanical properties of the film are improved, the stress of the film is within an appropriate range, and the film has good adhesion. In addition, since the film is sufficiently cured, coagulation peeling is suppressed.
  • the method for forming an electronic device sealing film of the present invention is a method for forming a sealing film using the electronic device sealing composition of the present invention described above, and includes the steps of forming a first sealing layer on an electronic device by a vapor phase method, and forming a second sealing layer by applying the electronic device sealing composition onto the first sealing layer. This makes it possible to obtain an electronic device sealing film having good adhesion, flexibility and heat resistance.
  • a step of forming a third sealing layer on the second sealing layer by a vapor phase method it is preferable to include a step of forming a third sealing layer on the second sealing layer by a vapor phase method, as this provides excellent sealing performance.
  • the step of forming the second sealing layer preferably uses an inkjet method, which allows for highly accurate layer formation.
  • the electronic device sealing film of the present invention is an electronic device sealing film for sealing an electronic device, and has a first sealing layer containing silicon nitride, silicon oxide or silicon oxynitride, and a second sealing layer using the electronic device sealing composition. This makes it possible to obtain an electronic device sealing film having good adhesion, flexibility and heat resistance.
  • a third sealing layer containing silicon nitride, silicon oxide or silicon oxynitride on the second sealing layer it is preferable to have a third sealing layer containing silicon nitride, silicon oxide or silicon oxynitride on the second sealing layer, as this provides excellent sealing performance.
  • the electronic device encapsulating composition of the present invention is an electronic device encapsulating composition for inkjet use, which contains a photopolymerizable monomer and a photopolymerization initiator, and contains a (meth)acrylate as the photopolymerizable monomer.
  • the loss factor (tan ⁇ ) peak value is in the range of 0.3 to 1.0
  • the storage modulus (G') is in the range of 1.0 to 3.0 GPa.
  • composition for sealing electronic devices may also be simply referred to as the “sealing composition”.
  • (meth)acrylate means at least one of acrylate and methacrylate.
  • the term “electronic device” refers to an element that generates, amplifies, converts, or controls an electric signal by utilizing the kinetic energy, potential energy, etc. of electrons. Examples of such elements include active elements such as light-emitting diode elements, organic electroluminescence elements, photoelectric conversion elements, and transistors.
  • the sealing composition of the present invention is used to form a sealing film for sealing the above-mentioned electronic device.
  • the loss factor (tan ⁇ ) peak value is in the range of 0.3 to 1.0, and the loss factor peak value is preferably in the range of 0.6 to 0.8.
  • the storage modulus (G') is in the range of 1.0 to 3.0 GPa, and preferably in the range of 2.4 to 2.7 GPa.
  • the "loss factor (loss tangent)" is a physical property expressed as the ratio (G"/G') of the loss modulus G" to the storage modulus G'.
  • the storage modulus G' (unit: GPa) represents elasticity and is an index of the force stored when deformed by an external force. That is, the storage modulus G' is an elastic response component of the elastic modulus in the relationship between the strain and the stress generated when deforming, and the energy for the deformation work is stored.
  • the "loss modulus G'' (unit: GPa) represents viscosity and is an index of the force S that is lost as heat when deformed by an external force.
  • the loss factor tan ⁇ is an index that represents the balance between viscosity and elasticity. In other words, tan ⁇ is a measure of the ratio of energy loss and storage to the work of deformation.
  • monofunctional (meth)acrylate refers to a monomer that has one (meth)acryloyl group in one molecule.
  • polyfunctional (meth)acrylate refers to a monomer that has two or more (meth)acryloyl groups in one molecule.
  • the monofunctional (meth)acrylate preferably has an aryl group including a phenyl group, a vinyl group, an alkyl group, a hydroxyl group, an aldehyde group, a carbonyl group, a carboxy group, a nitro group, an amino group, a sulfo group, a halogeno group, an ether bond, an ester bond, or the like.
  • the content ratio of the monofunctional (meth)acrylate to the total amount of the photopolymerizable monomers is preferably within a range of 41 to 80% by mass, and more preferably within a range of 45 to 70% by mass.
  • the dynamic viscoelasticity is preferably measured by a method and under measurement conditions that are generally used in the past. For example, the following method is preferably used for the measurement.
  • the dynamic viscoelasticity measuring device used was RSA3 manufactured by TA Instruments Co., Ltd. A tensile tool was used to attach the sample.
  • a coating film of the sealing composition having a thickness of 10 to 20 ⁇ m was prepared on a glass substrate having dimensions of 50 mm ⁇ 50 mm under a nitrogen environment.
  • This coating film was irradiated with ultraviolet light having a wavelength of 395 nm (IST MZ 240 mm 395 nm UVLED ) under a nitrogen environment so that the accumulated light amount was 1.0 to 1.8 J/cm2 under a condition of 300 mW/ cm2 , thereby curing the coating film.
  • the obtained cured film (sealing film) was peeled off from the glass substrate.
  • the sample was cut to a length of 40 mm and a width of 5 mm.
  • the conditions for measuring the dynamic viscoelasticity were a gap length of 20 mm, a strain of 0.05%, a frequency of 10 Hz, a temperature range of 0 to 180° C., and a temperature rise rate of 5° C./min.
  • the loss factor (tan ⁇ ) peak value can be adjusted to a value within the range of 0.3 to 1.0 by adjusting the type of monofunctional (meth)acrylate contained in the sealing composition, and by adjusting the content ratio of the monofunctional (meth)acrylate to the total amount of the photopolymerizable monomer.
  • the type of monofunctional (meth)acrylate contained in the sealing composition and the content ratio of the monofunctional (meth)acrylate to the total amount of the photopolymerizable monomer can be adjusted, etc.
  • adjustment of the film thickness and curing rate of the sealing film is also possible.
  • the film thickness is preferably within a range of 3 to 10 ⁇ m.
  • the sealing composition of the present invention preferably has a curing rate of 80% or more when cured by irradiation with 1.5 to 1.8 J/cm2 of ultraviolet light having a wavelength of 395 nm in a nitrogen gas atmosphere.
  • the curing rate is more preferably 90% or more, with the upper limit being 100%.
  • Examples of means for achieving a cure rate of 80% or more include the use of a (meth)acrylate that is prone to radical reaction, and the use of a photopolymerization initiator or sensitizer that effectively absorbs 395 nm light to improve reaction efficiency.
  • Examples of (meth)acrylates that easily undergo radical reactions include amine-containing (meth)acrylates and (meth)acrylates having an ethylene oxide group.
  • Examples of (meth)acrylates that easily undergo radical reactions include (meth)acrylates having a hydroxyl group and (meth)acrylates having two or more (meth)acrylate functional groups. Since acrylates are more reactive than methacrylates, compositions with a low methacrylate ratio can be used.
  • the composition of the sealing composition of the present invention will be described below.
  • the sealing composition of the present invention contains a photopolymerizable monomer and a photopolymerization initiator.
  • photopolymerizable monomer refers to a photopolymerizable monomer (also referred to as a "photocurable monomer”) that can undergo a polymerization (curing) reaction by absorbing light itself or a photopolymerization initiator to generate active ions or radicals.
  • the photopolymerizable monomer may be a non-silicon monomer that does not contain silicon (Si), and may be, for example, a monomer consisting of only an element selected from C, H, O, N, or S, but is not limited thereto.
  • the photopolymerizable monomer may be synthesized by a conventional synthesis method and used, or a commercially available product may be purchased and used.
  • the photopolymerizable monomer according to the present invention contains a (meth)acrylate.
  • the (meth)acrylate preferably contains a monofunctional (meth)acrylate, and may further contain a polyfunctional (meth)acrylate.
  • the (meth)acrylate preferably has an aromatic hydrocarbon group, and more preferably has a phenyl group.
  • the monofunctional (meth)acrylate includes a straight-chain structure and a branched structure in which two or more carbon atoms are linked in a row, when focusing on the longest continuous carbon atom linkage in the molecule.
  • the chain structure may include an atom selected from O, N, and S.
  • the chain structure may include an ether bond, a sulfide bond, or the like.
  • the monofunctional (meth)acrylate according to the present invention preferably has an alkylene skeleton or an alkylene oxide skeleton.
  • the monofunctional (meth)acrylate preferably has an alkylene skeleton or an ethylene oxide skeleton from the viewpoints of inkjet ejection property and bending resistance.
  • alkylene oxide skeleton refers to a structure (skeleton) of a divalent linking group (also called an "alkyleneoxy group”) in which an oxygen atom (-O-) is bonded to one end of an alkylene group.
  • a divalent linking group also called an "alkyleneoxy group”
  • ethylene oxide skeleton which is an example of the "alkylene oxide skeleton”
  • the ethylene oxide skeleton may have a structure of a monovalent ethylene oxide group (also called an “epoxy ring group”), or may have a structure (skeleton) of a divalent linking group (also called an "ethyleneoxy group”) formed by ring-opening of the epoxy ring group.
  • monofunctional (meth)acrylate examples include mono(meth)acrylates having a substituted or unsubstituted C2 to C20 alkylene group, an ethylene oxide group, etc.
  • Examples of monofunctional (meth)acrylates include, but are not limited to, unsaturated carboxylic acid esters including (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decanyl (meth)acrylate, undecanyl (meth)acrylate, and dodecyl (meth)acrylate; unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; saturated or unsaturated carboxylic acid vinyl esters such as vinyl acetate; cyanide vinyl compounds such as (meth)acrylonitrile; unsaturated amide compounds
  • epoxy (meth)acrylates can also be mentioned.
  • the monofunctional (meth)acrylate according to the present invention may contain, as part of a linear or branched structure, at least one cyclic group selected from a phenyl group or a phenylene group, a heterocyclic group, and a cycloalkyl group.
  • the heterocyclic group may be either an aromatic heterocyclic group or a non-aromatic heterocyclic group (e.g., one having a heteroatom in the cycloalkyl skeleton).
  • the (meth)acrylates having a cycloalkyl group include mono(meth)acrylates having a substituted or unsubstituted C3 to C20 cycloalkyl group, and refer to monomers having a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, dicyclodecane structure, tricyclodecane ring, adamantane ring, or isobornyl ring in the skeleton.
  • the cycloalkyl group contains a dicyclodecane group or a tricyclodecane group.
  • the monofunctional (meth)acrylate include alicyclic (meth)acrylates such as isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate, as well as 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, and 1-adamantyl (meth)acrylate.
  • alicyclic (meth)acrylates such as isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate, as well as 2-methyl-2-a
  • the (meth)acrylates having a heterocyclic group refer to monomers having a heterocyclic ring (heterocycle) in the skeleton.
  • heterocyclic (heterocyclic) skeleton examples include a dioxane structure, a trioxane structure, and an isocyanurate structure.
  • the (meth)acrylate having a heterocyclic group may include, but is not limited to, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl acrylate caprolactone-modified tetrahydrofurfuryl (meth)acrylate, morpholine (meth)acrylate, ⁇ -caprolactone-modified tris(acryloxyethyl)isocyanurate (M-327), pentamethylpiperidinyl methacrylate (FA-711), tetramethylpiperidinyl methacrylate (FA-712HM), cyclic trimethylolpropane formal acrylate (SR531), or a mixture thereof.
  • (meth)acrylates having one phenyl group or one phenylene group may include, but are not limited to, benzyl (meth)acrylate, ethoxy-modified cresol (meth)acrylate, propoxy-modified cresol (meth)acrylate, neopentyl glycol benzoate (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-acryloyloxyethyl-phthalic acid, neopentyl glycol-acrylic acid-benzoic acid ester, nonylphenol ethylene oxide (meth)acrylate, nonylphenol propylene oxide acrylate, or mixtures thereof.
  • the heterocyclic (heterocyclic) skeleton contains a dioxane glycol group, and one phenyl group contains a phenoxyethyl group, a phenoxydiethylene glycol group, or a nonylphenolethylene oxide group. This stabilizes the compound due to the planar molecular structure, and provides excellent heat resistance, sealing performance, and adhesion.
  • monofunctional (meth)acrylates include orthophenylphenoxyethyl acrylate (compound a-1 below), nonylphenol EO-modified acrylate (compound a-2 below), phenoxydiethylene glycol acrylate (compound a-3 below), stearyl acrylate (compound a-4 below), isobornyl acrylate (compound a-5 below), and 4-phenylbenzyl acrylate (compound a-6 below).
  • the monofunctional (meth)acrylate according to the present invention preferably has an aromatic hydrocarbon group, and particularly preferably has a phenyl group.
  • monofunctional (meth)acrylates having a phenyl group include orthophenylphenoxyethyl acrylate (compound a-1), nonylphenol EO-modified acrylate (compound a-2), phenoxydiethylene glycol acrylate (compound a-3), and 4-phenylbenzyl acrylate (compound a-6).
  • the content ratio of the monofunctional (meth)acrylate of the present invention to the total amount of photopolymerizable monomers is preferably 41% by mass or more.
  • the content ratio is more preferably in the range of 50 to 75% by mass.
  • the polyfunctional (meth)acrylate according to the present invention includes a straight-chain structure and a branched structure in which two or more carbon atoms are linked in a row, when focusing on the longest continuous carbon atom linkage in the molecule.
  • the chain structure may include an atom selected from O, N, and S.
  • the chain structure may include an ether bond, a sulfide bond, or the like.
  • the polyfunctional (meth)acrylate according to the present invention may have an alkylene skeleton or an alkylene oxide skeleton, like the monofunctional (meth)acrylate.
  • the polyfunctional (meth)acrylate according to the present invention may contain, as a part of a linear or branched structure, at least one cyclic group selected from one phenyl group or phenylene group, a heterocyclic group, and a cycloalkyl group, in the same manner as the monofunctional (meth)acrylate.
  • polyfunctional (meth)acrylates include di(meth)acrylates, tri(meth)acrylates, and tetra(meth)acrylates having a substituted or unsubstituted C2 to C20 alkylene group, an ethylene oxide group, etc.
  • ethylene glycol di(meth)acrylate having a structure represented by the following general formula (1) it is preferable to select from ethylene glycol di(meth)acrylate having a structure represented by the following general formula (1) or di(meth)acrylates having 6 to 10 carbon atoms in the alkylene skeleton.
  • triethylene glycol di(meth)acrylate is particularly preferred.
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, polytetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol dimethacrylate, octanediol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, undecanediol di(meth)acrylate,
  • polyfunctional (meth)acrylates of the present invention examples include triethylene glycol diacrylate (compound a-7 below), triethylene glycol dimethacrylate (compound a-8 below), decyl diacrylate (compound a-9 below), tricyclodecane dimethanol diacrylate (compound a-10 below), etc.
  • the polyfunctional (meth)acrylate of the present invention preferably has a content ratio of 25 to 59 mass% relative to the total amount of photopolymerizable monomers, in order to obtain an appropriate loss coefficient (tan ⁇ ) and storage modulus (G').
  • the content ratio is more preferably within the range of 25 to 40 mass%.
  • the photopolymerization initiator is not particularly limited as long as it is a normal photopolymerization initiator capable of carrying out a photocuring reaction.
  • the photopolymerization initiator may include, for example, a triazine-based, acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, phosphorus-based, oxime-based, or a mixture thereof.
  • Triazine initiators include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine.
  • 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl(piperonyl)-6-triazine, 2,4-(trichloromethyl(4'-methoxystyryl)-6-triazine, or a mixture thereof.
  • the acetophenone initiator may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and mixtures thereof.
  • the benzophenone initiator may be benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, or acrylated benzophenone.
  • the benzophenone initiator may also be 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, or 3,3'-dimethyl-2-methoxybenzophenone.
  • the benzophenone initiator may also be a mixture of the above.
  • the thioxanthone initiator may be thioxanthone, 2-methylthioxanthone, or isopropylthioxanthone.
  • the thioxanthone initiator may also be 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, or 2-chlorothioxanthone.
  • the thioxanthone initiator may also be a mixture of the above.
  • the benzoin initiator may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzil dimethyl ketal, or a mixture thereof.
  • the phosphorus-based initiator may be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide, or a mixture thereof.
  • the oxime may be 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione.
  • the oxime may also be 1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone.
  • the oxime may also be a mixture of the above.
  • a preferred commercially available photopolymerization initiator is IRGACURE (registered trademark) 819: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF Corporation).
  • the photopolymerization initiator is preferably contained in the encapsulating composition of the present invention in a range of about 0.1 to 20 parts by mass per 100 parts by mass of the total of the photopolymerizable monomer and the photopolymerization initiator.
  • the photopolymerization initiator is preferably contained within a range of 0.5 to 10 parts by weight, more specifically, within a range of 1 to 5 parts by weight.
  • the photopolymerization initiator is preferably contained in the sealing composition of the present invention in an amount of 0.1 to 10 mass % based on the solid content, more preferably in the range of 0.1 to 5 mass %. By setting the amount within the above range, photopolymerization can be sufficiently performed, and a decrease in transmittance due to remaining unreacted initiator can be prevented.
  • a photoacid generator or photopolymerization initiator such as a carbazole type, a diketone type, a sulfonium type, an iodonium type, a diazo type, or a biimidazole type may be used.
  • the encapsulating composition of the present invention may further contain other components including an antioxidant, a heat stabilizer, a photosensitizer, a dispersant, a thermal crosslinking agent, a surfactant, and a polymerization inhibitor, within the range in which the effects of the present invention can be obtained. Only one of these components may be contained in the encapsulating composition of the present invention, or two or more kinds of these components may be contained.
  • the antioxidant can improve the thermal stability of the sealing layer.
  • the antioxidant may include at least one selected from the group consisting of phenols, quinones, amines, and phosphites, but is not limited thereto.
  • the antioxidant may include tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, tris(2,4-di-tert-butylphenyl)phosphite, etc.
  • the antioxidant is preferably contained in the sealing composition in a range of 0.01 to 3 parts by mass per 100 parts by mass of the photopolymerizable monomer and the photopolymerization initiator combined. It is more preferable that the antioxidant is contained in the sealing composition in a range of 0.01 to 1 part by mass. By containing the antioxidant in the above range, excellent thermal stability can be exhibited.
  • the heat stabilizer is contained in the sealing composition and serves to suppress a change in viscosity of the sealing composition at room temperature, and any ordinary heat stabilizer can be used without any restrictions.
  • the heat stabilizer may be a sterically hindered phenolic heat stabilizer.
  • heat stabilizer examples include poly(di-cyclopentadiene-co-p-cresol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methano-bi(4-methyl-6-tert-butyl-phenol), 6,6'-di-tert-butyl-2,2'-thiodi-p-cresol, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl), 4,4'-thiobis(6-tert-butyl-m-cresol), 3,3'-bis ...2'-dimethylbenzyl-4-hydroxyphenyl)propionate, 2,2'-dimethylbenzyl-4-hydroxyphenyl)propyl
  • the heat stabilizer is preferably contained in the sealing composition in an amount of 2000 ppm or less based on the solid content relative to the total amount of the photocurable monomer and the photopolymerization initiator.
  • the heat stabilizer is preferably contained within a range of 0.01 to 2000 ppm, more preferably within a range of 100 to 1000 ppm.
  • the photosensitizer has the function of transferring the absorbed light energy to the photopolymerization initiator. Therefore, it is a compound that can give the photopolymerization initiator used the original photopolymerization initiator function even if it does not absorb light corresponding to the light from the light source.
  • Photosensitizers include, for example, anthracene derivatives such as 9,10-dibutoxyanthracene; benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-di Benzophenone derivatives such as methyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide and (4-benzoylbenzyl)trimethylammonium chloride; thioxan
  • the polymerization inhibitor it is preferable to contain any one of an N-oxyl-based polymerization inhibitor, a phenol-based polymerization inhibitor containing an o-t-butyl group, and a polymerization inhibitor having two or more aromatic rings.
  • an N-oxyl-based polymerization inhibitor it is preferable to use an N-oxyl-based polymerization inhibitor.
  • An example of a commercially available N-oxyl polymerization inhibitor is IRGASTAB (registered trademark) UV10 (manufactured by BASF).
  • the sealing composition of the present invention is preferably cured by irradiation with ultraviolet light in the range of 10 to 500 mW/ cm2 for 1 to 100 seconds, but is not limited thereto.
  • the ultraviolet light it is preferable to use an LED with a wavelength of 395 nm in order to prevent deterioration of electronic devices.
  • the viscosity of the sealing composition of the present invention is preferably within a range of 3 to 30 mPa ⁇ s. By having the viscosity within this range, the ejection properties from an inkjet head can be further improved.
  • the surface tension of the sealing composition of the present invention is preferably 15 mN/m or more and less than 45 mN/m, from the viewpoint of further improving the ejection property from an inkjet head.
  • the viscosity of the sealing composition of the present invention can be determined by measuring the temperature change of the dynamic viscoelasticity of the sealing composition using, for example, various rheometers.
  • these viscosities are values obtained by the following method.
  • the sealing composition of the present invention is set in a stress-controlled rheometer Physica MCR300 (cone plate diameter: 75 mm, cone angle: 1.0°) manufactured by Anton Paar.
  • the sealing composition is heated to 100° C. and cooled to 20° C. under conditions of a temperature drop rate of 0.1° C./s, a strain of 5%, and an angular frequency of 10 radian/s to obtain a temperature change curve of the dynamic viscoelasticity.
  • the sealing composition of the present invention may contain pigment particles.
  • the average particle size of the pigment particles is preferably in the range of 0.08 to 0.5 ⁇ m, and the maximum particle size is preferably in the range of 0.3 to 10 ⁇ m.
  • the average particle size of pigment particles in this invention refers to the value determined by dynamic light scattering using a Datasizer Nano ZSP manufactured by Malvern. Note that the sealing composition containing the colorant is highly concentrated, and light does not pass through this measuring device, so the sealing composition is diluted 200 times before measurement.
  • the measurement temperature is room temperature (25°C).
  • the sealing composition of the present invention preferably has a density ⁇ , a surface tension ⁇ of the sealing composition, a viscosity ⁇ of the sealing composition, and an Ohnesorge number (Oh) expressed by the following formula 1, calculated by the nozzle diameter D0, within the range of 0.1 to 1. This provides excellent inkjet ejection properties and droplet stabilization during ink flight.
  • the sealing composition of the present invention It is preferable to prepare the sealing composition of the present invention and provide a cured polymer having a Tg (glass transition point) of 80°C or higher in the film after polymerization.
  • the Tg of the film after polymerization is preferably 80°C or higher from the viewpoint of ensuring stability in the electronic device formation process, operating temperature, and reliability testing.
  • the method for forming an electronic device sealing film of the present invention is a method for forming a sealing film using the electronic device sealing composition of the present invention described above, and includes the steps of forming a first sealing layer on an electronic device by a vapor phase method, and forming a second sealing layer by applying the electronic device sealing composition onto the first sealing layer. Further, it is preferable to include a step of forming a third sealing layer on the second sealing layer by a vapor phase method, since the sealing performance of the electronic device can be further improved.
  • the first encapsulation layer forming step forms a first encapsulation layer on the electronic device by a vapor phase method.
  • the gas phase method include sputtering, deposition, thermal CVD, and catalytic chemical vapor deposition (Cat-CVD).
  • the gas phase method include capacitively coupled plasma CVD (CCP-CVD), photo-assisted CVD, plasma enhanced CVD (PECVD), epitaxial growth, and chemical vapor deposition such as atomic layer deposition (ALD). Among these, the ALD and CVD methods are preferred.
  • the sputtering methods include reactive sputtering methods such as magnetron cathode sputtering, planar magnetron sputtering, bipolar AC planar magnetron sputtering, and bipolar AC rotating magnetron sputtering.
  • the deposition methods include, for example, resistance heating deposition, electron beam deposition, ion beam deposition, plasma assisted deposition, and the like.
  • the first encapsulation layer contains silicon nitride (SiNx), silicon oxynitride (SiNOx) or silicon oxide (SiOx).
  • a specific example of a method for forming the first sealing layer includes reducing the pressure inside a chamber, and supplying heated source gases, such as silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ), into the chamber to form the first sealing layer.
  • the thickness of the first sealing layer is, for example, preferably in the range of 10 to 1000 nm, and more preferably in the range of 100 to 500 nm.
  • the sealing composition of the present invention is applied onto the first sealing layer to form the second sealing layer.
  • the method includes a step of applying the sealing composition onto the first sealing layer (application step), and curing the resulting coating film by irradiating it with ultraviolet light under a nitrogen gas atmosphere.
  • the method may include a step of modifying the coating film by irradiating it with vacuum ultraviolet light.
  • any suitable method can be used as the coating method of the sealing composition.
  • the coating method include spin coating, roll coating, flow coating, inkjet, spray coating, printing, dip coating, casting, bar coating, and gravure printing.
  • the inkjet method is preferred because it allows fine patterning required for sealing electronic devices such as organic EL elements to be performed on demand.
  • Inkjet printing methods can be broadly divided into two types: drop-on-demand printing and continuous printing, and either can be used.
  • the drop-on-demand method includes an electro-mechanical conversion method, an electro-thermal conversion method, an electrostatic attraction method, and a discharge method.
  • electromechanical conversion types include single cavity type, double cavity type, bender type, piston type, shear mode type, and shared wall type.
  • electro-thermal conversion type include a thermal inkjet type and a bubble jet (registered trademark) type.
  • electrostatic attraction method include an electric field control type and a slit jet type.
  • the discharge method may be, for example, a spark jet type. From the viewpoint of cost and productivity of the inkjet head, it is preferable to use a head of an electro-mechanical conversion type or an electro-thermal conversion type.
  • a method of dropping droplets (for example, a coating liquid) by an inkjet method is sometimes called an "inkjet method".
  • the sealing composition is preferably applied in a nitrogen gas atmosphere.
  • the resulting coating film is irradiated with ultraviolet light in a nitrogen gas atmosphere.
  • the illuminance of the ultraviolet light on the surface of the coating film is preferably within a range of 10 to 500 mW/ cm2 for 1 to 100 seconds to cure the coating film, but is not limited thereto.
  • the ultraviolet light it is preferable to use an LED with a wavelength of 395 nm in order to prevent deterioration of electronic devices.
  • a modification treatment may be performed in the second sealing layer forming step.
  • the modification treatment step after the coating step, the resulting coating film is irradiated with vacuum ultraviolet light in a nitrogen gas atmosphere to carry out a modification treatment.
  • the modification treatment refers to a reaction of converting polysilazane into silicon oxide or silicon oxynitride.
  • the modification treatment is also carried out in a nitrogen gas atmosphere or under reduced pressure, such as in a glove box.
  • a known method based on a conversion reaction of polysilazane can be selected.
  • a conversion reaction using plasma, ozone, or ultraviolet light which allows a conversion reaction at low temperatures, is preferred.
  • plasma or ozone a conventionally known method can be used.
  • the second sealing layer is preferably in the range of 0.5 to 10 ⁇ m, and more preferably in the range of 3 to 10 ⁇ m.
  • the second sealing layer may be a layer in which the entire layer is modified, but the thickness of the modified layer that has been modified is preferably in the range of 1 to 50 nm, and more preferably in the range of 1 to 30 nm.
  • the illuminance of the vacuum ultraviolet rays on the coating film surface is preferably within a range of 30 to 200 mW/cm 2.
  • the illuminance of the vacuum ultraviolet rays is more preferably within a range of 50 to 160 mW/cm 2 .
  • the modification efficiency can be sufficiently improved.
  • the illuminance of the vacuum ultraviolet ray is 200 mW/cm2 or less , the occurrence rate of damage to the coating film can be significantly suppressed, and damage to the substrate can also be reduced.
  • the amount of irradiation energy of the vacuum ultraviolet rays on the coating film surface is preferably within a range of 1 to 10 J/cm 2.
  • the amount of irradiation energy is more preferably within a range of 3 to 7 J/cm 2 .
  • a rare gas excimer lamp is preferably used as a light source for the vacuum ultraviolet rays. Since the efficiency of the vacuum ultraviolet light irradiation process is easily reduced due to absorption by oxygen, it is preferable to perform the irradiation with vacuum ultraviolet light in a state where the oxygen concentration is as low as possible. That is, it is preferable that the oxygen concentration during the irradiation with vacuum ultraviolet light is in the range of 10 to 10,000 ppm. The oxygen concentration is more preferably in the range of 50 to 5,000 ppm, and even more preferably in the range of 80 to 4,500 ppm. The oxygen concentration is most preferably in the range of 100 to 1,000 ppm.
  • the modification treatment can also be carried out in combination with a heat treatment.
  • the heating conditions are preferably a temperature in the range of 50 to 300° C., more preferably a temperature in the range of 60 to 150° C., and a time of preferably 1 second to 60 minutes, more preferably 10 seconds to 10 minutes.
  • Examples of the heat treatment include a method in which the substrate is brought into contact with a heating element such as a heat block and the coating film is heated by thermal conduction, and a method in which the atmosphere is heated by an external heater such as a resistance wire.
  • Examples of the heat treatment include a method using light in the infrared region such as an IR heater, but these are not particularly limited.
  • a method that can maintain the smoothness of the coating film containing the silicon compound may be appropriately selected.
  • a third sealing layer is formed on the second sealing layer by a vapor phase method.
  • the gas phase method includes sputtering, deposition, thermal CVD, and catalytic chemical vapor deposition (Cat-CVD) as in the gas phase method used in the first sealing layer formation step.
  • the gas phase method includes chemical vapor deposition methods such as capacitively coupled plasma CVD (CCP-CVD), photo-assisted CVD, plasma CVD (PE-CVD), epitaxial growth, and atomic layer deposition (ALD). Among them, the ALD method and CVD method are preferable.
  • the sputtering methods include reactive sputtering methods such as magnetron cathode sputtering, planar magnetron sputtering, bipolar AC planar magnetron sputtering, and bipolar AC rotating magnetron sputtering.
  • the deposition methods include, for example, resistance heating deposition, electron beam deposition, ion beam deposition, plasma assisted deposition, and the like.
  • the third encapsulation layer contains silicon nitride (SiNx), silicon oxynitride (SiNOx) or silicon oxide (SiOx).
  • a specific example of a method for forming the third sealing layer includes reducing the pressure inside a chamber, and supplying heated source gases, such as silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ), into the chamber to form the third sealing layer.
  • the thickness of the third sealing layer is, for example, preferably in the range of 10 to 1000 nm, and more preferably in the range of 100 to 500 nm.
  • a conductive film for a touch sensor may be further formed.
  • the conductive film can be composed of a metal compound film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide).
  • the conductive film can also be composed of a graphene film or a metal nanowire film (e.g., a film containing silver nanowires or copper nanowires) that has excellent flexibility.
  • the conductive film can also be composed of a metal nanoparticle film (e.g., a film containing silver nanoparticles or copper nanoparticles).
  • the conductive film can also be composed of a laminated film of multiple metals such as an Al film/Ti film/Al film.
  • the electronic device sealing film of the present invention is an electronic device sealing film that seals an electronic device, and has a first sealing layer containing silicon nitride, silicon oxide or silicon oxynitride, and a second sealing layer using the electronic device sealing composition of the present invention described above.
  • the electronic device sealing film of the present invention is formed by the method for forming an electronic device sealing film, that is, a second sealing layer is formed using the electronic device sealing composition of the present invention.
  • the electronic device sealing film of the present invention preferably further comprises a third sealing layer containing silicon nitride, silicon oxide or silicon oxynitride on the second sealing layer.
  • the first sealing layer is a layer formed on the electronic device by the above-mentioned vapor phase method, and specifically contains silicon nitride, silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
  • the second sealing layer is provided adjacent to the first sealing layer and is formed by applying the sealing composition onto the first sealing layer. Therefore, the second sealing layer contains a polymer made of the photopolymerizable monomer.
  • the photopolymerizable monomer preferably contains a monofunctional (meth)acrylate and further a polyfunctional (meth)acrylate.
  • various analytical methods known in the art such as chromatography, infrared spectroscopy, ultraviolet-visible spectroscopy, nuclear magnetic resonance analysis, X-ray diffraction, mass spectrometry, and X-ray photoelectron spectroscopy, can be used.
  • the content of the polymer in the second sealing layer is preferably within a range of 85 to 100% by mass, and more preferably within a range of 90 to 95% by mass.
  • the third sealing layer is a layer formed adjacent to the second sealing layer by the vapor phase method described above. Specifically, like the first sealing layer, it contains silicon nitride, silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
  • examples of electronic devices to be sealed include organic EL elements, LED elements, and liquid crystal display elements (LCDs).
  • the electronic devices include thin film transistors, touch panels, electronic paper, solar cells (PV), and the like. From the viewpoint of more efficiently obtaining the effects of the present invention, the electronic device is preferably an organic EL element, a solar cell, or an LED element, and more preferably an organic EL element.
  • the organic EL element employed as the electronic device according to the present invention may be of a bottom emission type, that is, one in which light is extracted from the transparent substrate side.
  • the bottom emission type is configured by laminating a transparent electrode serving as a cathode, a light emitting functional layer, and a counter electrode serving as an anode in this order on a transparent substrate.
  • the organic EL element according to the present invention may be of a top emission type, that is, an organic EL element in which light is extracted from the transparent electrode side serving as the cathode opposite to the substrate.
  • the top emission type has a structure in which a counter electrode serving as an anode is provided on the substrate side, and a light emitting functional layer and a transparent electrode serving as a cathode are laminated on the surface of the counter electrode in this order.
  • Representative examples of the structure of an organic EL element are shown below.
  • anode/hole injection transport layer/light emitting layer/electron injection transport layer/cathode ii) anode/hole injection transport layer/light emitting layer/hole blocking layer/electron injection transport layer/cathode
  • anode/hole injection transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron injection transport layer/cathode iv) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
  • anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode v) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
  • the organic EL element may have a non-light-emitting intermediate layer, which may be a charge generating layer or may have a multi-photon unit structure.
  • a non-light-emitting intermediate layer which may be a charge generating layer or may have a multi-photon unit structure.
  • organic EL elements applicable to the present invention, see, for example, JP-A-2013-157634, JP-A-2013-168552, JP-A-2013-177361, JP-A-2013-187211, JP-A-2013-191644, JP-A-2013-191804, JP-A-2013-225678, JP-A-2013-235994, JP-A-2013-243234, Examples of the configurations described in JP-A-2013-243236, JP-A-2013-242366, JP-A-2013-243371, JP-A-2013-245179, JP-A-2014-003249, JP-A-2014-003299, JP-A-2014
  • the substrate usable in the organic EL element is preferably glass or a resin film, and when flexibility is required, a resin film is preferable.
  • the substrate is also called a supporting substrate, a base, a substrate, a support, or the like.
  • the substrate may be transparent or opaque. In the case of a so-called bottom emission type in which light is extracted from the substrate side, the substrate is preferably transparent.
  • Preferred resins include substrates containing thermoplastic resins such as polyester resins, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent fluororesins, polyimides, fluorinated polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, cellulose acylate resins, polyurethane resins, polyether ether ketone resins, polycarbonate resins, alicyclic polyolefin resins, polyarylate resins, polyethersulfone resins, polysulfone resins, cycloolefin copolymers, fluorene ring-modified polycarbonate resins, alicyclic modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the substrate is preferably made of a heat-resistant material, specifically, a substrate having a linear expansion coefficient of 15 ppm/K to 100 ppm/K and a glass transition temperature (Tg) of 100° C. to 300° C. is used.
  • the substrate satisfies the necessary conditions for electronic component applications and laminated films for displays. That is, when the sealing film of the present invention is used for these applications, the substrate may be exposed to processes at 150° C. or higher. If the linear expansion coefficient of the substrate exceeds 100 ppm/K, the substrate dimensions are not stable when the substrate is subjected to processes at the above-mentioned temperatures, and the barrier performance is deteriorated due to thermal expansion and contraction, or the substrate is likely to be unable to withstand thermal processes. If the linear expansion coefficient is less than 15 ppm/K, the film may crack like glass, and the flexibility may be deteriorated.
  • the Tg and linear expansion coefficient of the substrate can be adjusted by additives or the like. More preferred examples of the thermoplastic resin that can be used as the substrate include polyethylene terephthalate (PET: 70° C.), polyethylene naphthalate (PEN: 120° C.), polycarbonate (PC: 140° C.), alicyclic polyolefin (e.g., Zeonor (registered trademark) 1600, manufactured by Zeon Corporation: 160° C.), polyarylate (PAr: 210° C.), polyethersulfone (PES: 220° C.), polysulfone (PSF: 190° C.), cycloolefin copolymer (COC: JP-A-2002-236625), and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • alicyclic polyolefin e.g., Zeonor (registered trademark) 1600, manufactured by Zeon Corporation: 160° C.
  • polyimide e.g., Neoprim (registered trademark), manufactured by Mitsubishi Gas Chemical Company, Inc.: 260°C
  • fluorene ring-modified polycarbonate BCF-PC: compound described in JP-A-2000-227603: 225°C
  • alicyclic modified polycarbonate IP-PC: compound described in JP-A-2000-227603: 205°C
  • acryloyl compound compound described in JP-A-2002-80616: 300°C or higher
  • the substrate is preferably transparent, i.e., the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.
  • the light transmittance can be calculated by the method described in JIS K7105:1981, that is, by measuring the total light transmittance and the amount of scattered light using an integrating sphere type light transmittance measuring device and subtracting the diffuse transmittance from the total light transmittance.
  • the above-mentioned substrates may be unstretched films or stretched films.
  • the substrate can be produced by a conventional method.
  • the methods for producing the substrate can be appropriately selected from those described in paragraphs “0051” to “0055” of WO 2013/002026.
  • the surface of the substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, etc., or may be a combination of the above treatments as necessary.
  • the substrate may also be subjected to an easy-adhesion treatment.
  • the substrate may be a single layer or a laminated structure of two or more layers. When the substrate is a laminated structure of two or more layers, the substrates may be the same or different in type.
  • the thickness of the substrate according to the present invention is preferably from 10 to 200 ⁇ m, and more preferably from 20 to 150 ⁇ m.
  • the film substrate has a gas barrier layer.
  • the gas barrier layer for the film substrate may be formed by forming a coating of an inorganic material, an organic material, or a hybrid coating of both on the surface of the film substrate.
  • the gas barrier layer is preferably a barrier film having a water vapor permeability (25 ⁇ 0.5° C., relative humidity (90 ⁇ 2)% RH) of 0.01 g/m 2 ⁇ 24 h or less.
  • the water vapor permeability is a value measured by a method in accordance with JIS K 7129-1992.
  • the gas barrier layer is preferably a high gas barrier film having an oxygen permeability of 1 ⁇ 10 ⁇ 3 mL/m 2 ⁇ 24 h ⁇ atm or less and a water vapor permeability of 1 ⁇ 10 ⁇ 3 g/m 2 ⁇ 24 h or less.
  • the oxygen permeability is a value measured by a method in accordance with JIS K 7126-1987.
  • the material for forming the gas barrier layer may be any material that has a function of suppressing the intrusion of substances that cause deterioration of the element, such as moisture and oxygen, etc.
  • Examples of such materials that can be used include silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, and silicon oxycarbide.
  • the gas barrier layer is not particularly limited, but in the case of an inorganic gas barrier layer such as silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, or silicon oxycarbide, it is preferable to form a layer from an inorganic material by a sputtering method (e.g., magnetron cathode sputtering, planar magnetron sputtering, bipolar AC planar magnetron sputtering, bipolar AC rotating magnetron sputtering, or the like), a deposition method (e.g., resistance heating deposition, electron beam deposition, ion beam deposition, plasma assisted deposition, or the like), a thermal CVD method, a catalytic chemical vapor deposition method (Cat-CVD), a capacitively coupled plasma CVD method (CCP-CVD), a photo-CVD method, a plasma CVD method (PE-CVD), an epitaxial growth method, an atomic layer deposition
  • the inorganic gas barrier layer can be formed by applying a coating liquid containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) onto a support, and then modifying the coating by irradiation with vacuum ultraviolet light or the like.
  • the inorganic gas barrier layer can also be formed by a film metallization technique such as metal plating on a resin substrate or bonding a metal foil to a resin substrate.
  • the inorganic gas barrier layer may also include an organic layer containing an organic polymer, i.e., the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.
  • the organic layer can be formed by first applying, for example, an organic monomer or an organic oligomer to a resin substrate to form a layer, followed by polymerization and, if necessary, crosslinking, using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device.
  • the organic layer can also be formed by, for example, depositing a flash-evaporated and radiation-crosslinkable organic monomer or oligomer, and then forming a polymer from the organic monomer or oligomer. Coating efficiency can be improved by cooling the resin substrate.
  • Examples of the method for applying the organic monomer or organic oligomer include roll coating (e.g., gravure roll coating), spray coating (e.g., electrostatic spray coating), etc.
  • Examples of the laminate of an inorganic layer and an organic layer include the laminates described in WO 2012/003198 and WO 2011/013341.
  • the thicknesses of the layers may be the same or different.
  • the thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 300 nm.
  • the thickness of the organic layer is preferably in the range of 100 nm to 100 ⁇ m, more preferably in the range of 1 to 50 ⁇ m.
  • BAPO bisacylphosphine oxide
  • IRGACURE registered trademark 819: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF) 5 parts by mass
  • UV10 [1,10-dioxodecane-1,10-diylbis(oxy)bis(2,2,6,6-tetramethyl-4,1-piperidinediyl)bisoxy]radical (manufactured by BASF) 0.1 part by mass
  • ⁇ Diacrylate> a-7 Triethylene glycol diacrylate (SR272, manufactured by Arkema) a-8: Triethylene glycol dimethacrylate (SR205, manufactured by Arkema) a-9: Decyl diacrylate (ADODN, manufactured by Shin-Nakamura Chemical Co., Ltd.) a-10: Tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • the coating film was irradiated with ultraviolet light having a wavelength of 395 nm (IST MZ 240 mm 395 nm UVLED) under a nitrogen environment so that the accumulated light amount was 1.5 J/ cm2 under a condition of 300 mW/cm2, and the coating film was cured.
  • the obtained cured film (sealing film) was peeled off from the glass substrate.
  • the sealing films 7-1 and 7-2 were irradiated with the integrated light amount of 1.0 J/cm 2 and 1.8 J/cm 2 , respectively.
  • the sample was cut to have a length of 40 mm and a width of 5 mm.
  • the conditions for measuring the dynamic viscoelasticity were a gap length of 20 mm, a strain of 0.05%, a frequency of 10 Hz, a temperature range of 0 to 180° C., and a temperature rise rate of 5° C./min.
  • a coating film of the sealing composition having a thickness of 10 ⁇ m or 20 ⁇ m was formed on a glass substrate having a size of 50 mm ⁇ 50 mm, as shown in Table II below.
  • This coating film was irradiated with ultraviolet light having a wavelength of 395 nm (MZ 240 mm 395 nm UVLED manufactured by IST Corporation) under a nitrogen gas atmosphere so that the accumulated light amount was 1.5 J/ cm2 under the condition of 300 mW/ cm2 , and the coating film was cured to obtain a sealing film.
  • the sealing films 7-1 and 7-2 were irradiated with the integrated light amount of 1.0 J/cm 2 and 1.8 J/cm 2 , respectively.
  • the obtained cured film (sealing film) and the composition before curing were subjected to FTIR (Nexus 870 infrared spectrometer) measurement.
  • the cure rate was calculated from the intensity of the peak (810 cm ⁇ 1 ) of the C ⁇ C bond derived from the (meth)acryloyl group in the obtained spectrum according to the following formula.
  • sealing films 7-1 and 7-2 irradiation was performed so that the cumulative light amount was 1.0 J/cm 2 and 1.8 J/cm 2 , respectively.
  • the ultraviolet light used was MZ (240 mm, 395 nm: UVLED) manufactured by IST Corporation.
  • the silicon nitride film was formed by reducing the pressure in the chamber and supplying silane (SiH 4 ), ammonia (NH 3 ), and hydrogen (H 2 ) as raw material gases into the chamber after heating them.
  • the thickness of the sealing film was adjusted to the values shown in Table II below by adjusting the number of inkjet coatings and the resolution.
  • the evaluation was performed by a peel test using a tape (600 manufactured by 3M Co.) after making a cut in the sealing film with a cutter.
  • A, B and C were evaluated as pass.
  • D The adhesion strength between the sealing film and the silicon nitride film is 0.1N or more and less than 1N.
  • Preparation of Organic EL Element 1 (1) Preparation of substrate A 15 ⁇ m polyimide film was prepared as a film substrate. Furthermore, a gas barrier layer for the film substrate ( SiO2 film: 250 nm/SiNx film: 50 nm/SiO2 film: 500 nm ( upper layer/middle layer/lower layer)) was formed on this polyimide film by plasma CVD.
  • Al film was formed as a first electrode (metal layer) on one surface of the substrate under the following conditions.
  • the thickness of the formed first electrode was 150 nm.
  • the thickness of the first electrode was measured using a contact surface profiler (DECTAK).
  • the Al film was formed by using a vacuum deposition apparatus, reducing the pressure to a degree of vacuum of 1 ⁇ 10 ⁇ 4 Pa, and then using a tungsten crucible for resistance heating.
  • compound BD-1 and compound H-1 shown below were co-deposited at a deposition rate of 0.1 nm/sec so that the concentration of compound BD-1 was 7% by mass, to form a light-emitting layer (fluorescent light-emitting layer) having a thickness of 15 nm and emitting blue light.
  • compound GD-1, compound RD-1, and compound H-2 were co-deposited at a deposition rate of 0.1 nm/sec so that the concentrations of compound GD-1 and RD-1 were 20% by mass and 0.5% by mass, respectively, to form a yellow-emitting layer (phosphorescent-emitting layer) having a thickness of 15 nm.
  • silicon nitride SiNx, Vickers hardness HV900 having a thickness of 500 nm was formed by plasma CVD as a first sealing layer for covering the light-emitting portion of the organic EL element produced above.
  • the sealing composition 1 prepared above was left to stand in a thermostatic chamber at 60° C. for one week, and then filled into a cartridge-integrated head of an inkjet device under a nitrogen gas atmosphere. Then, the sealing composition 1 after aging was applied to the organic EL element formed up to the first sealing layer under a nitrogen gas atmosphere using an inkjet method. Thereafter, the formed coating film was irradiated with ultraviolet light having a wavelength of 395 nm (IST MZ 240 mm 395 nm UVLED) under a nitrogen gas atmosphere so that the accumulated light amount was 1.5 J/cm 2 under a condition of 300 mW/cm 2 , and the coating film was cured to form a second sealing layer. The thickness of the second sealing layer was adjusted to the values shown in Table II below by adjusting the number of times the inkjet was applied and the resolution.
  • a silicon nitride (SiNx, Vickers hardness HV900) having a thickness of 500 nm was formed as a third sealing layer on the second sealing layer by a plasma CVD method, thereby obtaining an organic EL element 1 for evaluation in which the first to third sealing layers were formed.
  • Organic EL elements 2 to 16 for evaluation were prepared in the same manner as in the preparation of the organic EL element 1, except that the sealing composition 1 used in forming the second sealing layer was changed as shown in the table below.
  • Organic EL elements 7-1 and 7-2 were prepared in the same manner, except that the sealing composition 1 and film thickness were changed as shown in Table II below, and the integrated light amount was changed to 1.0 J/cm 2 and 1.8 J/cm 2 , respectively.
  • the sealing composition of the present invention is found to have superior adhesion, flex resistance, and heat resistance compared to the sealing composition of the comparative example.
  • the present invention can be used in an inkjet electronic device sealing composition, an electronic device sealing film forming method, and an electronic device sealing film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Une composition d'encapsulation de dispositif électronique selon la présente invention est destinée à une impression jet d'encre et contient un monomère photopolymérisable et un initiateur de photopolymérisation, la composition contenant un (méth)acrylate en tant que monomère photopolymérisable, et, en ce qui concerne la viscoélasticité dynamique après durcissement de la composition d'encapsulation de dispositif électronique, la valeur de pic du facteur de dissipation diéléctrique (tanδ) est située dans la plage de 0,3 à 1,0 et le module de conservation (G') est situé dans la plage de 1,0 à 3,0 GPa.
PCT/JP2024/035477 2023-10-31 2024-10-03 Composition d'encapsulation de dispositif électronique pour impression jet d'encre, procédé de formation de film d'encapsulation de dispositif électronique et film d'encapsulation de dispositif électronique Pending WO2025094586A1 (fr)

Applications Claiming Priority (2)

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JP2023-186518 2023-10-31
JP2023186518 2023-10-31

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018051732A1 (fr) * 2016-09-15 2018-03-22 Jnc株式会社 Complexe d'encre et élément électroluminescent organique l'utilisant
WO2022039019A1 (fr) * 2020-08-19 2022-02-24 コニカミノルタ株式会社 Composition pour le scellement de dispositif électronique, procédé de formation de film d'étanchéité de dispositif électronique, et film d'étanchéité de dispositif électronique
WO2023032372A1 (fr) * 2021-08-30 2023-03-09 コニカミノルタ株式会社 Composition de protection pour dispositif électronique, procédé de formation de film de protection pour dispositif électronique et film de protection pour dispositif électronique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018051732A1 (fr) * 2016-09-15 2018-03-22 Jnc株式会社 Complexe d'encre et élément électroluminescent organique l'utilisant
WO2022039019A1 (fr) * 2020-08-19 2022-02-24 コニカミノルタ株式会社 Composition pour le scellement de dispositif électronique, procédé de formation de film d'étanchéité de dispositif électronique, et film d'étanchéité de dispositif électronique
WO2023032372A1 (fr) * 2021-08-30 2023-03-09 コニカミノルタ株式会社 Composition de protection pour dispositif électronique, procédé de formation de film de protection pour dispositif électronique et film de protection pour dispositif électronique

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