Classifications

• • 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
  • H10K50/842—Containers
  • H10K50/8423—Metallic sealing arrangements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/057—Metal alcoholates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
  • H05B33/04—Sealing arrangements, e.g. against humidity
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
• • 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
  • H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers

Definitions

• the present invention relates to a composition for electronic device sealing, a method for forming an electronic device sealing film, and an electronic device sealing film.
• the present invention relates to a composition for encapsulating an electronic device, which has excellent encapsulation performance and, as a result, excellent luminous efficiency.
• organic electroluminescence devices (hereinafter also referred to as “organic EL devices” or “organic EL elements”) are manufactured using organic EL elements in order to prevent the organic materials and electrodes used from deteriorating due to moisture. It has been proposed to cover the surface of the with a sealing layer.
• the technique described in Patent Document 1 includes a monomer having no aromatic hydrocarbon group and a monomer having an aromatic hydrocarbon group, and has an aromatic hydrocarbon group.
• a display device is disclosed.
• the diffusion coefficient of the organic protective film is sufficiently low, so moisture permeation is a problem under severe conditions of high temperature and high humidity such as 85° C., 85% RH, and 100 hours or more.
• the sealing performance was poor, which affected the decrease in luminous efficiency.
• the stress difference between the organic protective film and the adjacent layer, lack of adhesive strength, and bending resistance during bending have also been regarded as problems.
• a curable resin composition for encapsulating electronic devices which is improved in flexibility, encapsulation performance and resin viscosity by adding (meth)acrylic oligomer, low-molecular-weight (meth)acrylate and moisture absorbent.
• (meth)acrylic oligomer low-molecular-weight (meth)acrylate and moisture absorbent.
• Patent Document 2 See Patent Document 2, for example.
• the technique disclosed in Patent Document 2 has a problem that nozzle clogging occurs during ink jet ejection due to the influence of the oligomer having a large molecular weight.
• the crosslink density is lowered, and the problem of water permeation remains in the thin film region.
• a (meth)acrylate compound (A) having an aromatic hydrocarbon skeleton a (meth)acrylate compound having an aromatic hydrocarbon skeleton other than the compound (A), and a (meth)acrylate compound having an alicyclic hydrocarbon skeleton
• At least one (meth)acrylate compound (B) selected from the group consisting of an acrylate compound and a (meth)acrylate compound having a heterocyclic skeleton, and a polymerization initiator (C) thereby improving sealing performance
• a resin composition with improved curability, visible light transmittance and cure shrinkage has been disclosed (see, for example, Patent Document 3).
• an object of the present invention is to provide an electronic device encapsulating composition, a method for forming an electronic device encapsulating film, and an electronic device encapsulating film that are excellent in luminous efficiency.
• the present inventors have found that, in addition to the metal-containing compound (C), a chain (meth)acrylate monomer ( By containing A1) and a chain-like (meth)acrylate monomer (A2) having a specific structure, it is possible to provide an electronic device encapsulating composition that is excellent in inkjet dischargeability, bending resistance, and encapsulating performance. I found that it can be done and arrived at the present invention. That is, the above problems related to the present invention are solved by the following means.
• An electronic device sealing composition containing a photocurable monomer (A) and a photopolymerization initiator (B),
• the photocurable monomer (A) contains at least a chain (meth)acrylate monomer (A1) and a chain (meth)acrylate monomer (A2), the chain (meth)acrylate monomer (A2) has at least one of a phenyl group, a heterocyclic group or a cycloalkyl group, Furthermore, it contains a metal-containing compound (C), A composition for sealing an electronic device, wherein the metal-containing compound (C) contains at least one of metal alkoxides, metal chelates, silane compounds, silazane compounds and metal halides.
• metals constituting the metal alkoxide, the metal chelate and the metal halide are selected from Ti, Si, Al and Zr. 1. Electronic device sealing composition according to item 1.
• An electronic device sealing film for sealing an electronic device, a first encapsulation layer containing silicon nitride, silicon oxide or silicon oxynitride; and a second sealing layer using the electronic device sealing composition according to any one of items 1 to 6.
• An electronic device sealing film for sealing an electronic device, a first encapsulation layer containing silicon nitride, silicon oxide or silicon oxynitride; and a second sealing layer using the electronic device sealing composition according to any one of items 1 to 6.
• the electronic device sealing film according to item 10 further comprising a third sealing layer containing silicon nitride, silicon oxide or silicon oxynitride on the second sealing layer.
• a composition for sealing an electronic device which has good ejection property by inkjet, excellent bending resistance, and excellent sealing performance by preventing moisture permeation, and as a result, excellent luminous efficiency
• a method for forming an electronic device sealing film and an electronic device sealing film can be provided.
• the metal and ligand contained in the metal-containing compound (C) react with water to suppress movement of water and prevent diffusion, thereby suppressing water permeation. Further, by using a combination of the chain-like (meth)acrylate monomers (A1) and (A2), the dispersibility of the metal-containing compound (C) is improved. It can be expressed uniformly. As a result, moisture permeation can be suppressed, and sealing performance is excellent.
• the interaction with the adjacent layer is strengthened.
• the interaction between the second sealing layer and the first and third sealing layers adjacent to the second sealing layer is strengthened and the adhesion is improved.
• the resistance to stress between layers generated by bending is increased, and the resistance to bending is improved.
• the metal-containing compound (C) prevents water from diffusing, reliability can be ensured even with a thin film, and if the film is thin, the stress when bent is low, and delamination is reduced. Also in this respect, the bending resistance is improved.
• the sealing layer containing the chain-like (meth)acrylate monomers (A1) and (A2) bends. Can give endurance.
• the electronic device sealing composition of the present invention is an electronic device sealing composition containing a photocurable monomer (A) and a photopolymerization initiator (B), wherein the photocurable monomer (A) is , containing at least a chain-like (meth)acrylate monomer (A1) and a chain-like (meth)acrylate monomer (A2), wherein the chain-like (meth)acrylate monomer (A2) is a phenyl group, a heterocyclic ring or a cycloalkyl group, and further contains a metal-containing compound (C), wherein the metal-containing compound (C) is a metal alkoxide, a metal chelate, a silane-based compound, a silazane-based compound and It contains at least one metal halide.
• This feature is a technical feature common to or corresponding to each of the following embodiments.
• At least one of the linear (meth)acrylate monomer (A1) and the linear (meth)acrylate monomer (A2) has a molecular weight within the range of 100 to 1000. preferable.
• the ink jetting property is excellent, and since the molecular weight is low in the range of 100 to 1,000, it is possible to form a high-density network with high crosslinkability, thereby improving the sealing performance.
• the chain-shaped (meth)acrylate monomer (A1) preferably has an alkylene skeleton or an ethylene oxide skeleton from the viewpoint of inkjet ejection property and bending resistance.
• the metals constituting the metal alkoxide, the metal chelate and the metal halide are selected from Ti, Si, Al and Zr. It is preferable in terms of suppressing permeation and having excellent sealing performance.
• the content of the chain-shaped (meth)acrylate monomer (A1) with respect to the entire electronic device sealing composition is in the range of 55 to 95% by mass. is preferable.
• the content of the chain (meth)acrylate monomer (A2) with respect to the entire electronic device sealing composition is in the range of 5 to 45% by mass. It is preferable in terms of bending resistance.
• 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, wherein the first sealing layer is formed on the 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.
• a step of forming a third sealing layer on the second sealing layer by a vapor phase method in terms of better sealing performance.
• the step of forming the second sealing layer uses an ink jet method in that the layer can be formed with high accuracy.
• the electronic device encapsulation film of the present invention is an electronic device encapsulation film for encapsulating an electronic device, comprising a first encapsulation layer containing silicon nitride, silicon oxide or silicon oxynitride; and a second encapsulation layer using the composition.
• a third sealing layer containing silicon nitride, silicon oxide, or silicon oxynitride on the second sealing layer from the viewpoint of excellent sealing performance.
• the photocurable monomer (A) is at least a chain (meth)acrylate monomer (A1). , and a chain (meth)acrylate monomer (A2), wherein the chain (meth)acrylate monomer (A2) has at least one of a phenyl group, a heterocyclic group, and a cycloalkyl group.
• the metal-containing compound (C) contains at least one of a metal alkoxide, a metal chelate, a silane-based compound, a silazane-based compound, and a metal halide.
• (meth)acrylate means at least one of acrylate and methacrylate.
• electronic device refers to an element that generates, amplifies, converts, or controls an electrical signal using the kinetic energy or potential energy of electrons. Examples thereof include active elements such as light-emitting diode elements, organic electroluminescence elements, photoelectric conversion elements, and transistors.
• electronic devices include passive elements such as resistors and capacitors that perform passive tasks such as “resisting" and "storing” in response to actions from others. Therefore, the sealing composition of the present invention is used to form a sealing film for sealing the electronic device described above.
• the photocurable monomer (A) means a photocurable monomer capable of undergoing a curing reaction with a photopolymerization initiator.
• a photocurable monomer a non-silicon monomer containing no silicon (Si) may be used, for example, a monomer consisting only of an element selected from C, H, O, N or S. Good, but not limited to this.
• the photo-curable monomer may be used after being synthesized by an ordinary synthesis method, or may be used by purchasing a commercially available product.
• the photocurable monomer (A) contains at least a chain (meth)acrylate monomer (A1) and a chain (meth)acrylate monomer (A2).
• chain-like (meth)acrylate monomer (A1) means that two or more carbon atoms are in a row when focusing on the longest continuous carbon atom in the molecule.
• chain (or acyclic) monomers monomers containing linear and branched structures linked to are free of cyclic structures.
• An atom selected from O, N, or S may be included in the chain skeleton.
• the chain skeleton may contain an ether bond, a sulfide bond, or the like.
• a chain (meth)acrylate monomer (A1) As such a chain (meth)acrylate monomer (A1) according to the present invention, a substituted or unsubstituted C2-C20 (having 2 to 20 carbon atoms) alkyl group, a substituted or unsubstituted C2-C20 alkyl mono(meth)acrylates, di(meth)acrylates, tri(meth)acrylates, tetra(meth)acrylates having silyl groups, substituted or unsubstituted C2-C20 alkylene groups, amine groups, ethylene oxide groups, etc.; .
• the chain-like (meth)acrylate monomer (A1) has an alkylene skeleton or an ethylene oxide skeleton from the viewpoint of inkjet dischargeability and bending resistance.
• the ethylene oxide skeleton is a unit of two carbon chains and one oxygen, and may have a ring or may be ring-opened.
• the chain (meth)acrylate monomer (A1) includes methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl ( Inhibitors containing (meth)acrylic acid esters such as meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decanyl (meth)acrylate, undecanyl (meth)acrylate, dodecyl (meth)acrylate, etc.
• saturated carboxylic acid esters 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; (meth)acrylonitrile Vinyl cyanide compounds such as; (meth) unsaturated amide compounds such as acrylamide; ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, Pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,10-decanediol diacrylate,
• the content of the linear (meth)acrylate monomer (A1) with respect to the entire sealing composition is preferably within the range of 55 to 95% by mass, more preferably within the range of 60 to 90% by mass.
• chain-like (meth)acrylate monomer (A2) means that two or more carbon atoms are in a row when focusing on where carbon atoms are continuously connected for the longest time in the molecule.
• it has a phenyl group it has one phenyl group and does not include the case of having two or more phenyl groups.
• an atom selected from O, N or S may be included in the chain skeleton.
• the chain skeleton may contain an ether bond, a sulfide bond, or the like.
• the heterocyclic group may be a heterocyclic group having aromaticity or a heterocyclic group having no aromaticity (e.g., having a heteroatom in the cycloalkyl skeleton). good.
• the (meth)acrylate monomers having a cycloalkyl group are mono(meth)acrylates, di(meth)acrylates having a substituted or unsubstituted C3 to C20 cycloalkyl group.
• ) acrylate, tri(meth)acrylate, tetra(meth)acrylate, etc. and refers to a monomer having a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, dicyclodecane structure, tricyclodecane ring, adamantane ring, or isobornyl ring in the skeleton. .
• alicyclic (meth)acrylate such as isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.
• Bifunctional or higher polyfunctional (meth)acrylate compounds may include, but are not limited to, alicyclic (meth)acrylates such as tricyclodecanedimethanol (meth)acrylate and mixtures thereof.
• the (meth)acrylate monomer having a heterocyclic group refers to a monomer having a heterocyclic (heterocyclic) skeleton.
• heterocyclic (heterocyclic) skeleton examples include a dioxane structure, a trioxane structure, an isocyanurate structure, and the like.
• the (meth)acrylate monomer having a heterocyclic group includes tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl acrylate caprolactone-modified tetrahydrofurfuryl (meth)acrylate, morpholine (meth)acrylate, isocyanuric acid EEO-modified Diacrylate (M-215), ⁇ -caprolactone-modified tris(acryloxyethyl) isocyanurate (M-327), isocyanuric acid EO-modified di- and triacrylates (M-313 or M-315), hydroxypivalaldehyde-modified tris Methylolpropane diacrylate (R-604), pentamethylpiperidinyl methacrylate (FA-711), tetramethylpiperidinyl methacrylate (FA-712HM), cyclic trimethylolpropane formal acrylate (SR531) or mixture
• the (meth)acrylate monomers having one phenyl group include benzyl (meth)acrylate, ethoxy-modified cresol (meth)acrylate, propoxy-modified cresol (meth)acrylate.
• 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-phthalate, neopentyl glycol-acrylic acid-benzoate, nonylphenol ethylene oxide acrylate, nonylphenol propylene oxide acrylate, or mixtures thereof.
• the content of the linear (meth)acrylate monomer (A2) with respect to the entire sealing composition is preferably in the range of 5 to 45% by mass, more preferably in the range of 10 to 40% by mass.
• At least one of the chain-like (meth)acrylate monomer (A1) and the chain-like (meth)acrylate monomer (A2) preferably has a molecular weight within the range of 100 to 1,000. It is more preferable to be within the range from the viewpoint of inkjet dischargeability and moisture permeability.
• Metal-containing compound (C) is used as a generic term for inorganic compounds and organic compounds containing metals.
• an organic compound containing a metal such as an organometallic compound and an organometallic complex.
• the metal-containing compound (C) used in the present invention includes metal alkoxides, metal chelates (also referred to as "(metal) chelate complexes"), silane-based compounds, silazane-based compounds and metal halogens. Selected from fossils.
• Examples of the metal M constituting the metal-containing compound (C) include Ti, Si, Al, Zr, silicon, bismuth, strontium, calcium, copper, sodium, and lithium. Also included are cesium, magnesium, barium, vanadium, niobium, chromium, tantalum, tungsten, chromium, indium, and iron. At least one of Ti, Si, Al and Zr is particularly preferable.
• metal-containing compound (C) examples include tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrichlorosilane, ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyl
• organic titanium compounds having structures represented by the following general formulas (II) to (IV) may be used.
• R represents an alkyl group.
• organic zirconium compounds having structures represented by the following general formulas (V) to (VII) may be used.
• R represents an alkyl group.
• organoaluminum compounds having structures represented by the following general formulas (VIII) to (X) may be used.
• R represents an alkyl group.
• zirconium tetra-normal propoxide zirconium tetra-normal butoxide, zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium monobutoxy acetylacetonate bis(ethylacetoacetate), zirconium dibutoxy bis(ethylacetoacetate)
• examples include organic zirconium compounds such as zirconium tetraacetylacetonate, zirconium tributoxy monostearate zirconium, (methyl 2-hydroxyisobutyrate), zirconium (cis-2-butene-1,4-diol), and the like.
• metal halides such as titanium dichloride, titanium trichloride, titanium tetrachloride, titanium fluoride, zirconium chloride, zirconium fluoride, aluminum chloride, aluminum fluoride and the like are included.
• metal-containing compound (C) examples include tetra(2-ethylhexyl) titanate (product name TA30, manufactured by Matsumoto Fine Chemicals Co., Ltd.), aluminum sec-butylate (manufactured by Kawaken Fine Chemicals Co., Ltd.), and cyclic aluminum oxide isopropylate (Kawaken Fine Chemicals Co., Ltd.).
• the content of the metal-containing compound (C) with respect to the entire sealing composition is not limited as long as the sealing composition maintains the function of photocuring, but is in the range of 0.1 to 15% by mass. It is preferably within the range of 5 to 10% by mass.
• the metal-containing compound (C) may be partially transformed into an oxide or hydroxide containing the metal M. From the viewpoint of transparency, the molar fraction of these metal M oxides or hydroxides with respect to the metal-containing compound (C) is in the range of 0.01 to 0.1 [mol/mol]. preferable.
• the photopolymerization initiator (B) is not particularly limited as long as it is a normal photopolymerization initiator capable of photocuring reaction.
• the photopolymerization initiator (B) may include, for example, triazine-based, acetophenone-based, benzophenone-based, thioxanthone-based, benzoin-based, phosphorus-based, oxime-based, or mixtures 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, 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
• Acetophenone initiators include 2,2′-diethoxyacetophenone, 2,2′-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-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.
• Benzophenone initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-dichlorobenzophenone, 3 , 3′-dimethyl-2-methoxybenzophenone or a mixture thereof.
• the thioxanthone-based initiator may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, or a mixture thereof.
• the benzoin-based initiator may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, or mixtures thereof.
• the phosphorus initiator may be bisbenzoylphenylphosphine oxide, benzoyldiphenylphosphine oxide, or a mixture thereof.
• the oxime series includes 2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(o-acetyloxime)-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, or mixtures thereof.
• the photopolymerization initiator (B) contains the photocurable monomer (A) (chain (meth)acrylate monomers (A1) and (A2)) and the photopolymerization initiator in the sealing composition of the present invention. It is preferably included in the range of about 0.1 to 20 parts by mass per 100 parts by mass of (B). Within the above range, sufficient photopolymerization occurs during exposure, and it is possible to prevent a decrease in transmittance due to the remaining unreacted initiator after photopolymerization. Specifically, the photopolymerization initiator is preferably contained in the range of 0.5 to 10 parts by weight, more specifically 1 to 8 parts by weight.
• the photopolymerization initiator is preferably contained in the sealing composition of the present invention within a range of 0.1 to 10% by mass based on the solid content, more preferably 0.1% by mass. It is within the range of ⁇ 8% by mass. By setting the content within the above range, photopolymerization can occur sufficiently, and a decrease in transmittance due to the remaining unreacted initiator can be prevented.
• a carbazole-based, diketone, sulfonium-based, iodonium-based, diazo-based, biimidazole-based photoacid generator or photopolymerization initiator may be used instead of the photopolymerization initiator.
• the sealing composition of the present invention contains other components including an antioxidant, a thermal stabilizer, a photosensitizer, a dispersant, a thermal cross-linking agent and a surfactant within the range in which the effects of the present invention can be obtained. It may contain further. These components may be contained singly or in combination of two or more in the sealing composition of the present invention.
• the antioxidant can improve the thermal stability of the sealing layer.
• the antioxidant may contain one or more selected from the group consisting of phenol, quinone, amine and phosphite, but is not limited thereto.
• antioxidants include tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, tris(2,4-di-tert-butylphenyl)phosphite, and the like. be able to.
• the antioxidant is contained in the sealing composition in a range of 0.01 to 3 parts by mass with respect to a total of 100 parts by mass of the photocurable monomer and the photopolymerization initiator. More preferably, it is contained within the range of 0.01 to 1 part by mass. By setting it within the above range, excellent thermal stability can be exhibited.
• the heat stabilizer is contained in the sealing composition and suppresses the change in viscosity of the sealing composition at room temperature
• ordinary heat stabilizers can be used without limitation.
• thermal stabilizers sterically hindered phenolic thermal stabilizers may be used, specifically 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'-thi
• the amount of the heat stabilizer in the sealing composition is 2000 ppm or less, preferably in the range of 0.01 to 2000 ppm with respect to the total of the photocurable monomer and the photopolymerization initiator based on the solid content. more preferably within the range of 100 to 1000 ppm. Within the above range, the heat stabilizer can further improve the storage stability and processability of the sealing composition in a liquid state.
• the photosensitizer has the function of transferring the energy of the absorbed light energy to the photopolymerization initiator, so even if the photopolymerization initiator used does not have absorption corresponding to the light from the light source, the original photopolymerization It is a compound that can have an initiator function.
• photosensitizers include 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, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4 ,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride and the like benzophenone derivatives; 2-isopropylthi
• the sealing composition of the present invention is preferably cured by irradiating ultraviolet rays within the range of 10 to 500 mW/cm 2 for 1 to 100 seconds, but is not limited thereto.
• the ultraviolet light it is preferable to use a 395 nm LED from the viewpoint of preventing deterioration of electronic devices.
• the viscosity of the sealing composition of the present invention is preferably within the range of 3 to 20 mPa ⁇ s from the viewpoint of further enhancing ejection properties from an inkjet head. It is preferable that the surface tension is 15 mN/m or more and less than 45 mN/m from the viewpoint of further enhancing the ejection performance from the inkjet head.
• the viscosity of the sealing composition of the present invention can be determined, for example, by measuring the temperature change of the dynamic viscoelasticity of the sealing composition with 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. Next, the sealing composition was heated to 100° C. and cooled to 20° C. under the conditions of a cooling rate of 0.1° C./s, a strain of 5%, and an angular frequency of 10 radian/s. to obtain the temperature change curve of dynamic viscoelasticity.
• the sealing composition of the present invention may contain pigment particles.
• the pigment particles should have an average particle diameter within the range of 0.08 to 0.5 ⁇ m from the viewpoint of enhancing ejection properties from an inkjet head. It is preferable that the maximum particle size is in the range of 0.3 to 10 ⁇ m.
• the average particle size of pigment particles in the present invention means a value obtained by a dynamic light scattering method using Datasizer Nano ZSP, manufactured by Malvern. Since the sealing composition containing the colorant has a high concentration and does not transmit light with this measuring instrument, the sealing composition is diluted 200 times before measurement. The measurement temperature is normal temperature (25°C).
• the sealing composition of the present invention has a density ⁇ , a surface tension ⁇ of the sealing composition, a viscosity ⁇ of the sealing composition, and an Ohnesorge It is preferable that the number (Oh) is within the range of 0.1 to 1 from the viewpoints of jetting properties of the inkjet and stabilization of droplets when the ink flies.
• the sealing composition of the present invention prefferably to 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, driving temperature, and reliability test.
• the method for forming an electronic device sealing film of the present invention is a method of forming a sealing film using the electronic device sealing composition of the present invention. forming a stop layer; and forming a second sealing layer by applying the electronic device sealing composition onto the first sealing layer.
• the first sealing layer forming step forms a first sealing layer on the electronic device by a vapor phase method.
• the gas phase method includes sputtering (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotary magnetron sputtering, including reactive sputtering), vapor deposition (for example, resistance heating).
• the first encapsulation layer contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
• the thickness of the first sealing layer is, for example, preferably in the range of 10-1000 nm, more preferably in the range of 100-500 nm.
• the second sealing layer is formed by applying the sealing composition of the present invention on the first sealing layer. Specifically, on the first sealing layer, the sealing composition is applied (coating step), and the obtained coating film is irradiated with vacuum ultraviolet rays in a nitrogen atmosphere to perform a modification treatment. may have.
• any appropriate method can be employed as a method for applying the sealing composition, and examples thereof include spin coating, roll coating, flow coating, ink jet, spray coating, printing, and dip coating. , a casting method, a bar coating method, a gravure printing method, and the like.
• the inkjet method is preferable in that fine patterning, which is required when sealing electronic devices such as organic EL elements, can be performed on demand.
• a known method can be used as the ink jet method.
• the inkjet method is roughly divided into two types, the drop-on-demand method and the continuous method, both of which can be used.
• Drop-on-demand methods include electro-mechanical conversion methods (e.g., single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.) and electro-thermal conversion methods (e.g., thermal inkjet type, bubble jet (registered trademark) type, etc.), electrostatic attraction type (eg, electric field control type, slit jet type, etc.), discharge type (eg, spark jet type, etc.), and the like.
• an electro-mechanical conversion type or an electro-thermal conversion type head From the viewpoint of the cost and productivity of the inkjet head, it is preferable to use an electro-mechanical conversion type or an electro-thermal conversion type head.
• a method of dropping liquid droplets (for example, a coating liquid) by an inkjet method is sometimes called an “inkjet method”.
• the sealing composition it is preferable to apply the sealing composition under a nitrogen atmosphere.
• Modification treatment process In the modification treatment step, after the coating step, the obtained coating film may be subjected to a modification treatment by irradiating vacuum ultraviolet rays in a nitrogen atmosphere.
• Modification treatment means conversion reaction of polysilazane to silicon oxide or silicon oxynitride.
• the reforming treatment is similarly performed in a nitrogen atmosphere such as in a glove box or under reduced pressure.
• a known method based on conversion reaction of polysilazane can be selected.
• the conversion reaction using plasma, ozone, or ultraviolet rays which enables the conversion reaction at a low temperature, is preferred. Conventionally known methods can be used for plasma and ozone.
• the second sealing layer according to the present invention it is preferable to form the second sealing layer according to the present invention by providing the coating film and subjecting it to modification treatment by irradiating it with vacuum ultraviolet light (also referred to as VUV) having a wavelength of 200 nm or less. .
• VUV vacuum ultraviolet light
• the thickness of the second sealing layer is preferably in the range of 0.5-20 ⁇ m, more preferably in the range of 3-10 ⁇ m.
• the entire layer may be modified, but the modified layer preferably has a thickness of 1 to 50 nm, more preferably 1 to 30 nm. More preferably within the range.
• the illuminance of the vacuum ultraviolet rays on the surface of the coating film that the coating film receives is preferably in the range of 30 to 200 mW/cm 2 , more preferably 50 to 160 mW/cm 2 . is more preferably within the range of
• the reforming efficiency can be sufficiently improved. It is preferable because it can also reduce the damage of
• the amount of irradiation energy of the vacuum ultraviolet rays on the coating film surface is preferably within the range of 1 to 10 J/cm 2 , and from the viewpoint of barrier properties and wet heat resistance for maintaining the desiccant function, 3. More preferably in the range of ⁇ 7 J/cm 2 .
• a rare gas excimer lamp is preferably used as the vacuum ultraviolet light source. Since the vacuum ultraviolet light is absorbed by oxygen, the efficiency of the vacuum ultraviolet irradiation step tends to decrease. Therefore, it is preferable to irradiate the vacuum ultraviolet light in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during vacuum ultraviolet light irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, still more preferably in the range of 80 to 4500 ppm, most preferably 100 to 1000 ppm. is within the range of
• the modification treatment can also be performed in combination with heat treatment.
• Heating conditions are preferably in the range of 50 to 300° C., more preferably in the range of 60 to 150° C., preferably 1 second to 60 minutes, more preferably 10 seconds to 10 minutes, in combination with heat treatment.
• the heat treatment for example, a method of heating the coating film by heat conduction by bringing the substrate into contact with a heating element such as a heat block, a method of heating the atmosphere with an external heater such as a resistance wire, and an infrared region such as an IR heater. and the like, but are not particularly limited. Moreover, a method that can maintain the smoothness of the coating film containing the silicon compound may be appropriately selected.
• the third sealing layer forming step forms a third sealing layer on the second sealing layer by a vapor phase method.
• a vapor phase method sputtering methods (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC flat plate magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.) are used in the same manner as the vapor phase method used in the first sealing layer forming step.
• the third encapsulation layer contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.) or silicon oxynitride.
• the thickness of the third sealing layer is, for example, preferably in the range of 10-1000 nm, more preferably in the range of 100-500 nm.
• a conductive film for a touch sensor may be further formed after forming the sealing film.
• the conductive film is, for example, a metal compound film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide), or a highly flexible graphene film or metal nanowire film (for example, silver nanowire or copper nanowire film). films containing wires), metal nanoparticle films (for example, films containing silver nanoparticles or copper nanoparticles).
• it may be composed of a laminated film of a plurality of metals such as Al film/Ti film/Al film.
• the electronic device sealing film of the present invention is an electronic device sealing film for sealing an electronic device, comprising a first sealing layer containing silicon nitride, silicon oxide or silicon oxynitride; and a second encapsulation layer using a device encapsulation composition.
• the electronic device sealing film of the present invention is formed by the method for forming an electronic device sealing film. That is, the second encapsulating layer is formed using the electronic device encapsulating composition of the present invention.
• the electronic device sealing film of the present invention preferably has 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 vapor phase method described above. Specifically, it contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.), or silicon oxynitride.
• a 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 at least a chain-like (meth)acrylate monomer (A1), a polymer composed of a chain-like (meth)acrylate monomer (A2), and a metal-containing compound (C).
• A1 chain-like (meth)acrylate monomer
• A2 polymer composed of a chain-like (meth)acrylate monomer
• C metal-containing compound
• the second sealing layer contains the polymer and the metal-containing compound (C)
• various conventionally known analytical methods such as chromatography, infrared spectroscopy, ultraviolet - Visible spectroscopy, nuclear magnetic resonance spectroscopy, X-ray diffraction, mass spectroscopy, X-ray photoelectron spectroscopy, etc. can be used.
• the content of the polymer in the second sealing layer is preferably within the range of 85 to 99.9% by mass, more preferably within the range of 90 to 95% by mass.
• the content of the metal-containing compound (C) in the second sealing layer is preferably within the range of 0.1 to 15% by mass, more preferably within the range of 5 to 10% by mass.
• the metal-containing compound (C) in the second sealing layer may partially transform into an oxide or hydroxide containing the metal M. From the viewpoint of transparency, the molar fraction of these metal M oxides or hydroxides with respect to the metal-containing compound (C) is in the range of 0.01 to 0.1 [mol/mol]. preferable.
• the third sealing layer is a layer provided adjacent to the second sealing layer and formed by the vapor phase method described above. Specifically, like the first sealing layer, it contains silicon nitride (SiN), silicon oxide (silicon monoxide, silicon dioxide, etc.), or silicon oxynitride.
• Examples of electronic devices to be sealed in the electronic device sealing film forming method and electronic device sealing film of the present invention include organic EL elements, LED elements, liquid crystal display elements (LCD), thin film transistors, touch panels, and electronic paper. , solar cells (PV), and the like. From the viewpoint that the effects of the present invention can be obtained more efficiently, an organic EL element, a solar cell, or an LED element is preferable, and an organic EL element is particularly preferable.
• the organic EL element employed as the electronic device according to the present invention may be of the bottom emission type, that is, one in which light is extracted from the transparent base material side.
• the bottom emission type is configured by laminating a transparent electrode as a cathode, a light emitting functional layer, and a counter electrode 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, one in which light is extracted from the side of the transparent electrode serving as the cathode opposite to the substrate.
• the top emission type has a configuration 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 in this order on the surface thereof.
• organic EL element Representative examples of the structure of the 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
• organic EL The device may have a non
• the intermediate layer may be a charge generation layer or may have a multiphoton unit structure.
• the organic EL element applicable to the present invention, for example, JP-A-2013-157634, JP-A-2013-168552, JP-A-2013-177361, JP-A-2013-187211, JP-A-2013-187211, 2013-191644, JP 2013-191804, JP 2013-225678, JP 2013-235994, JP 2013-243234, JP 2013-243236, JP 2013- 242366, JP 2013-243371, JP 2013-245179, JP 2014-003249, JP 2014-003299, JP 2014-013910, JP 2014-017493 Configurations described in Japanese Patent Laid-Open No. 2014-017494 and the like can be mentioned.
• the substrate (hereinafter also referred to as a supporting substrate, substrate, substrate, support, etc.) that can be used in the organic EL element, specifically, glass or resin film is preferably applied, and flexibility is required. It is preferable that it is a resin film. Moreover, it 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 polyester resins, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent fluororesins, polyimides, fluorinated polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, and cellulose acylate resins.
• polyurethane resin polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic modified polycarbonate resin, fluorene ring-modified
• substrates containing thermoplastic resins such as polyester resins and acryloyl compounds. These resins can be used alone or in combination of two or more.
• the substrate is preferably made of a heat-resistant material. Specifically, a substrate having a linear expansion coefficient of 15 ppm/K or more and 100 ppm/K or less and a glass transition temperature (Tg) of 100° C. or more and 300° C. or less is used.
• the base material satisfies the requirements for use in electronic parts and laminated films for displays. That is, when the sealing film of the present invention is used for these uses, the substrate may be exposed to a process at 150° C. or higher. In this case, if the coefficient of linear expansion of the substrate exceeds 100 ppm/K, the dimensions of the substrate will not be stable when the substrate is subjected to the temperature process as described above, and the thermal expansion and contraction will deteriorate the insulation performance. , or the problem of not being able to withstand the heat process is likely to occur. If it is less than 15 ppm/K, the film may crack like glass and the flexibility may deteriorate.
• the substrate is preferably transparent. That is, the light transmittance is usually 80% or higher, preferably 85% or higher, more preferably 90% or higher.
• the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.
• the substrates listed above may be unstretched films or stretched films.
• the base material can be produced by a conventionally known general method.
• the matters described in paragraphs "0051” to "0055” of International Publication No. 2013/002026 can be appropriately employed.
• the surface of the substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. may be Moreover, you may perform adhesion-facilitating treatment to a base material.
• the base material may be a single layer or may have a laminated structure of two or more layers.
• each substrate may be of the same type or of different types.
• the thickness of the substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m.
• a film substrate it is preferably a film substrate with a gas barrier layer.
• the gas barrier layer for the film substrate may have an inorganic coating, an organic coating, or a hybrid coating of both of them formed on the surface of the film substrate.
• it is preferably a barrier film with a water vapor transmission rate (25 ⁇ 0.5°C, relative humidity (90 ⁇ 2)% RH) of 0.01 g/m 2 ⁇ 24h or less.
• any material can be used as long as it has a function of suppressing the infiltration of substances that cause deterioration of the device, such as moisture and oxygen.
• Examples include silicon monoxide, silicon dioxide, silicon nitride, silicon oxynitride, Silicon carbide, silicon oxycarbide, etc. can be used.
• the gas barrier layer is not particularly limited.
• an inorganic material is sputtered (for example, , magnetron cathode sputtering, planar magnetron sputtering, bipolar AC planar magnetron sputtering, bipolar AC rotating magnetron sputtering, etc.), vapor deposition methods (e.g., resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition, etc.), thermal CVD method, catalytic chemical vapor deposition method (Cat-CVD), capacitively coupled plasma CVD method (CCP-CVD), optical CVD method, plasma CVD method (PE-CVD), epitaxial growth method, atomic layer deposition (ALD) method, reaction It is preferable to form the layer by a chemical vapor
• an inorganic gas barrier layer by applying a coating solution containing an inorganic precursor such as polysilazane or tetraethyl orthosilicate (TEOS) onto a support and then performing modification treatment 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 base material, adhesion of a metal foil to a resin base material, or the like.
• the inorganic gas barrier layer may contain an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.
• the organic layer is formed, for example, by applying an organic monomer or organic oligomer to a resin substrate to form a layer, followed by polymerization using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device. And it can be formed by cross-linking as necessary. It can also be formed, for example, by flash evaporation and vapor deposition of radiation crosslinkable organic monomers or oligomers, followed by forming a polymer from the organic monomers or organic oligomers. Coating efficiency can be improved by cooling the resin substrate.
• Examples of coating methods for organic monomers or organic oligomers include roll coating (eg, gravure roll coating) and spray coating (eg, electrostatic spray coating).
• Examples of laminates of inorganic layers and organic layers include laminates described in International Publication No. 2012/003198 and International Publication No. 2011/013341.
• the thickness of each layer may be the same or different.
• the thickness of the inorganic layer is preferably in the range of 3-1000 nm, more preferably in the range of 10-300 nm.
• the thickness of the organic layer is preferably in the range from 100 nm to 100 ⁇ m, more preferably in the range from 1 to 50 ⁇ m.
• Substrate Preparation A 15 ⁇ m polyimide film was prepared as a film substrate. Further, a gas barrier layer (SiO 2 film: 250 nm/SiNx film: 50 nm/SiO 2 film: 500 nm (upper layer/intermediate layer/lower layer)) for a film substrate was formed on this polyimide film by plasma CVD.
• SiO 2 film: 250 nm/SiNx film: 50 nm/SiO 2 film: 500 nm (upper layer/intermediate layer/lower layer) for a film substrate was formed on this polyimide film by plasma CVD.
• first electrode metal layer
• the thickness of the formed first electrode was 150 nm.
• the thickness of the first electrode is a value measured by a contact surface profiler (DECTAK).
• the Al film was formed by using a tungsten resistance heating crucible after reducing the pressure to a degree of vacuum of 1 ⁇ 10 ⁇ 4 Pa using a vacuum deposition apparatus.
• each vapor deposition crucible in a vacuum vapor deposition apparatus was filled with the following materials constituting each layer of the organic functional layer in the optimum amount for device fabrication.
• the crucible for vapor deposition was made of molybdenum or tungsten resistance heating material.
• silicon nitride SiN, Vickers hardness HV900 having a thickness of 500 nm is formed by plasma CVD. formed.
• Second Sealing Layer Formation of Second Sealing Layer
• the sealing composition 1 prepared above was filled into a cartridge-integrated head of an inkjet device in a nitrogen environment. Then, the organic EL element formed up to the first sealing layer was coated with the sealing composition 1 using an inkjet method in a nitrogen environment. After that, an air-cooled LED of 395 nm (manufactured by Phoseon Technology) was irradiated with UV with an accumulated energy of 1 J/cm 2 to form a second sealing layer.
• the thickness of the second sealing layer was set by adjusting the number of ink-jet coatings, and the following two types of thickness of the second sealing layer were formed. ⁇ 3 ⁇ m (one application) ⁇ 10 ⁇ m (applied 3 times)
• Organic EL elements 2 to 66 for evaluation in the same manner as in the preparation of the organic EL element 1, except that the sealing composition 1 in the formation of the second sealing layer was changed as shown in the table below. 101-132 and 201-209 were made.
• Each organic EL device was wrapped around a metal roller having a diameter of 10 mm and left in a constant temperature and humidity chamber under high temperature and high humidity conditions (temperature of 60° C., relative humidity of 90%) to conduct an accelerated deterioration test.
• the polyimide film which is the film substrate, is wound so as to be in contact with the metal roller.
• each organic EL device was taken out from the thermo-hygrostat and checked under a microscope and the luminous state (dark spot area ratio) at room temperature. ⁇ , ⁇ and ⁇ of the following evaluation criteria were regarded as acceptable.
• the light emission characteristics were evaluated by comparing the light emission efficiency with the organic EL device for comparison.
• a comparative organic EL device was prepared by using non-alkali glass instead of the film substrate in the organic EL device prepared above. Further, instead of forming the first sealing layer, the second sealing layer, and the third sealing layer, sealing was performed in a nitrogen atmosphere using a glass sealing can to which barium oxide was attached. An ultraviolet curable adhesive was used to bond the sealing can and the substrate of the organic EL element, and the two were bonded by irradiating ultraviolet rays to prepare a sealing element (an organic EL element for comparison).
• the percentage is 0.1% or more and less than 1% of the total number of nozzles ⁇ : The percentage of nozzle defects is less than 0.1% of the total number of nozzles
• the organic EL element having the sealing layer formed using the sealing composition of the present invention has higher sealing performance and bending resistance than the organic EL element of the comparative example.
• the luminous efficiency and the ink-jet ejection property are excellent.
• the present invention provides an electronic device encapsulating composition that has good ink jetting properties, excellent bending resistance, and excellent sealing performance by preventing moisture permeation, and as a result, has excellent luminous efficiency. It can be used for a sealing film forming method and an electronic device sealing film.

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