Classifications

• • 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
  • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
  • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
  • C08K7/18—Solid spheres inorganic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
• • 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
  • 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
  • H10K59/80—Constructional details
  • H10K59/87—Passivation; Containers; Encapsulations
  • H10K59/873—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
  • H10K59/80—Constructional details
  • H10K59/87—Passivation; Containers; Encapsulations
  • H10K59/871—Self-supporting sealing arrangements
  • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

• the present invention relates to a composition, a cured product and an organic EL display device.
• organic optical devices such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has progressed.
• organic EL organic electroluminescence
• An organic EL display element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. Electrons are injected into the organic light-emitting material layer from one electrode and holes are injected from the other electrode into the organic light-emitting material layer, whereby the electrons and the holes are combined in the organic light-emitting material layer to cause self-light emission.
• the organic EL display element has the advantage of being more visible, being able to be made thinner, and being driven by a DC low voltage, as compared with a liquid crystal display element or the like that requires a backlight.
• organic EL display element has a problem that when the organic light-emitting material layer and electrodes are exposed to the outside air, the light-emitting characteristics are rapidly deteriorated and the life is shortened. Therefore, in order to improve the stability and durability of organic EL display elements, a sealing technique for shielding organic light-emitting material layers and electrodes from moisture and oxygen in the air has become essential in organic EL display elements.
• Patent Document 1 discloses a method of filling a photocurable sealant between organic EL display element substrates in a top emission type organic EL display element or the like, and irradiating light for sealing. .
• the present invention relates to, for example, the following ⁇ 1> to ⁇ 18>.
• ⁇ 1> It contains a polymerizable compound, inorganic fine particles, and a photopolymerization initiator, the content of the inorganic fine particles is 30% by volume or more, and light irradiation is performed at a wavelength of 365 nm and an irradiation dose of 600 mJ/cm 2 . , a composition having a cure depth of 100 ⁇ m or more when left standing at 80° C. for 30 minutes.
• the polymerizable compound has at least one polymerizable group selected from the group consisting of carbon-carbon double bonds and cyclic ethers.
• the inorganic fine particles have a refractive index n 2 such that the absolute value (
• ⁇ 4> The composition according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic fine particles have a refractive index n2 of 1.4 or more .
• ⁇ 5> The composition according to any one of ⁇ 1> to ⁇ 4>, wherein the inorganic fine particles have an average circularity of 0.7 or more and 1.0 or less.
• ⁇ 6> The composition according to any one of ⁇ 1> to ⁇ 5>, wherein the inorganic fine particles include at least one selected from the group consisting of spherical silica and spherical alumina.
• T 0 (%) The sum of total light transmittance T 0 (%) and total light reflectance R 0 (%) per 100 ⁇ m thickness (T 0 +R 0 ) is 50% or more, ⁇ 1> to ⁇ 6
• ⁇ 8> The composition according to any one of ⁇ 1> to ⁇ 7>, wherein the photopolymerization initiator contains a compound represented by the following formula (1).
• R 1 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group
• X 2 ⁇ represents a monovalent anion. Multiple R 1 's may be the same or different.
• R 2 represents an optionally substituted alkyl group. Multiple R 2 may be the same or different.
• ⁇ 10> In accordance with JIS Z0208, for forming a cured body having a moisture permeability of 100 g / (m 2 24 hours) or less per 100 ⁇ m thickness measured under conditions of a temperature of 85 ° C. and a relative humidity of 85%
• composition according to any one of ⁇ 1> to ⁇ 11> which is a sealant for an organic EL display device.
• ⁇ 13> The composition according to any one of ⁇ 1> to ⁇ 12>, which is a sealant for dam-fill type dam formation.
• the content of the inorganic fine particles is 30% by volume or more, and the content of the photopolymerization initiator is 0.3 mass with respect to 100 parts by mass of the polymerizable compound part or more, and the inorganic fine particles have an average circularity of 0.7 or more and 1.0 or less.
• An organic EL display device comprising an organic EL display element and a sealing structure including a dam and a filler for sealing the organic EL display element, wherein the dam contains the cured body according to ⁇ 15>. display device.
• the organic EL display device according to ⁇ 16> which is an organic EL television.
• a composition capable of forming a sealing material with excellent moisture resistance and long-term reliability. Further, according to the present invention, an organic EL display device including a cured body of the composition and a sealing structure formed using the composition is provided.
• the composition of this embodiment contains a polymerizable compound, inorganic fine particles, and a photopolymerization initiator.
• the content of inorganic fine particles is 30% by volume or more.
• the composition of the present embodiment has a curing depth of 100 ⁇ m or more when it is irradiated with light having a wavelength of 365 nm and an irradiation dose of 600 mJ/cm 2 and allowed to stand at 80° C. for 30 minutes.
• the composition of the present embodiment it is possible to form a sealing material with excellent moisture resistance and long-term reliability. Therefore, the composition of the present embodiment can be suitably used as a sealant (preferably an organic EL display element sealant, particularly preferably an organic EL television sealant). Moreover, the composition of the present embodiment can be particularly preferably used as a dam-forming sealant for forming a dam in a dam-fill system (sealing structure composed of a dam and a filling agent).
• a sealant preferably an organic EL display element sealant, particularly preferably an organic EL television sealant.
• the composition of the present embodiment can be particularly preferably used as a dam-forming sealant for forming a dam in a dam-fill system (sealing structure composed of a dam and a filling agent).
• composition of the present embodiment exhibits the above effect is not necessarily limited, but is considered as follows.
• a cured body containing a large amount of inorganic fine particles having lower moisture permeability than resin materials is formed. Further, when the content of the inorganic fine particles in the composition is increased, the inorganic fine particles tend to inhibit light irradiation and increase the amount of unreacted monomer (unreacted polymerizable compound) in the cured product.
• the cured depth is as described above, unreacted monomers are sufficiently reduced by light irradiation at the time of sealing, and deterioration of moisture resistance and reliability due to unreacted monomers is suppressed.
• it is considered that excellent moisture resistance and long-term reliability can be achieved by forming a composition having a predetermined curing depth while incorporating a sufficient amount of inorganic fine particles.
• the polymerizable compound can be said to be a compound having a polymerizable group.
• Polymerizable compounds may be used singly or in combination of two or more.
• the polymerizable compound preferably has at least one polymerizable group selected from the group consisting of carbon-carbon double bonds and cyclic ethers.
• the carbon-carbon double bond may be any carbon-carbon double bond having radical polymerizability or cationic polymerizability.
• compounds having a carbon-carbon double bond include compounds having a polymerizable group such as a (meth)acryloyl group, a vinyl group, an allyl group, a vinyl ether group, and a vinyl ester group. ) compounds having an acryloyl group ((meth)acrylate compounds) are preferred.
• Examples of (meth)acrylate compounds include monofunctional (meth)acrylates having one (meth)acryloyl group and polyfunctional (meth)acrylates having two or more (meth)acryloyl groups.
• Monofunctional (meth)acrylates include, for example, alkyl (meth)acrylates (e.g., ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, etc.), benzyl (meth)acrylate, ethoxylated o-phenyl Phenol (meth)acrylate etc. are mentioned.
• alkyl (meth)acrylates e.g., ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, etc.
• benzyl (meth)acrylate ethoxylated o-phenyl Phenol (meth)acrylate etc. are mentioned.
• Polyfunctional (meth)acrylates include, for example, alkanediol di(meth)acrylates (eg, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, etc.), tricyclodecanedimethanol di(meth)acrylate, and the like.
• alkanediol di(meth)acrylates eg, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, etc.
• tricyclodecanedimethanol di(meth)acrylate tricyclodecanedimethanol di(meth)acrylate
• the cyclic ether may be a cationic polymerizable cyclic ether.
• Examples of compounds having cyclic ethers include epoxy compounds and oxetane compounds.
• epoxy compounds include alicyclic compounds having an epoxy group (alicyclic epoxy compounds), aromatic compounds having an epoxy group (aromatic epoxy compounds), and acyclic compounds having an epoxy group (acyclic epoxy compound) and the like. One or more of these compounds may be selected and used.
• alicyclic epoxy compound for example, a compound having at least one cycloalkene ring (e.g., cyclohexene ring, cyclopentene ring, pinene ring, etc.) is treated with a suitable oxidizing agent such as hydrogen peroxide or peracid.
• a suitable oxidizing agent such as hydrogen peroxide or peracid.
• a compound obtained by epoxidation or a derivative thereof can be mentioned.
• Alicyclic epoxy compounds also include, for example, hydrogenated epoxy compounds obtained by hydrogenating aromatic epoxy compounds (eg, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, etc.).
• Alicyclic epoxy compounds include 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylalkyl (meth)acrylate (e.g., 3,4-epoxycyclohexylmethyl (meth) ) acrylate, etc.), (3,3′,4,4′-diepoxy)bicyclohexyl, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and the like.
• alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure are preferred.
• alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure compounds represented by the following formula (A1-1) are preferred.
• X represents a single bond or a linking group (a divalent group having one or more atoms).
• the linking group is preferably a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked.
• X is preferably a linking group.
• a group having an ester bond is preferable.
• compounds having a group having an ester bond as a linking group include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
• the molecular weight of the alicyclic epoxy compound is preferably 1000 or less, more preferably 450 or less, and even more preferably 400 or less, in terms of further improving the moisture resistance of the cured product and further improving the storage stability of the composition. 300 or less is more preferable, and 100 to 280 is particularly preferable.
• the molecular weight of the cycloaliphatic epoxy compound may be, for example, 100-1000, 100-450, 100-400, 100-300 or 100-280.
• the number average molecular weight of the alicyclic epoxy compound is preferably within the above range.
• a number average molecular weight shows the value of polystyrene conversion measured by the following measurement conditions by a gel permeation chromatography (GPC).
• Any of monomers, oligomers, and polymers can be used as the aromatic epoxy compound.
• examples include S-type epoxy resins, biphenyl-type epoxy resins, naphthalene-type epoxy resins, fluorene-type epoxy resins, novolak phenol-type epoxy resins, cresol novolac-type epoxy resins, phenylglycidyl ether and modified products thereof.
• aromatic epoxy compound an aromatic epoxy compound having a bisphenol structure is preferable.
• aromatic epoxy compounds having a bisphenol structure compounds represented by the following formula (A2-1) are preferred.
• n 0 to 30, and R 21 , R 22 , R 23 and R 24 are each independently a hydrogen atom or a C 1 to 5 optionally substituted represents an alkyl group. 0.1 or more may be sufficient as n.
• R 21 , R 22 , R 23 and R 24 are preferably hydrogen atoms or methyl groups.
• R 21 , R 22 , R 23 and R 24 may be the same or different, but are preferably the same.
• the aromatic epoxy compound having a bisphenol structure is preferably at least one selected from the group consisting of bisphenol A type epoxy resins and bisphenol F type epoxy resins.
• the molecular weight of the aromatic epoxy compound is preferably from 100 to 5,000, more preferably from 150 to 1,000, and even more preferably from 200 to 450, in terms of further improving the moisture resistance of the cured product. That is, the molecular weight of the aromatic epoxy compound is, for example, 100 to 5000, 100 to 1000, 100 to 450, 150 to 5000, 150 to 1000, 150 to 450, 200 to 5000, 200 to 1000 or 200 to 450. good.
• the number average molecular weight of the aromatic epoxy compound is preferably within the above range.
• a number average molecular weight shows the value of polystyrene conversion measured by the measurement conditions mentioned above by a gel permeation chromatography (GPC).
• Acyclic epoxy compounds include, for example, diglycidyl ethers of alkylene glycol (e.g., ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), Polyglycidyl ethers of polyhydric alcohols (e.g., di- or triglycidyl ethers of glycerin or its alkylene oxide adducts), diglycidyl ethers of polyalkylene glycols (e.g., diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, polypropylene diglycidyl ether of glycol or its alkylene oxide adduct) and the like.
• the alkylene oxide includes ethylene oxide, propylene oxide, and the like.
• the oxetane compound is not particularly limited, but 3-ethyl-3-hydroxymethyloxetane (trade name Aronoxetane OXT-101 manufactured by Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl) ) methoxymethyl]benzene (OXT-121, etc.), 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211, etc.), di(1-ethyl-(3-oxetanyl)) methyl ether (OXT- 221 etc.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT-212 etc.) and the like.
• An oxetane compound is a compound having one or more oxetane rings in the molecule.
• a compound having both a carbon-carbon double bond and a cyclic ether can also be used as the polymerizable compound.
• Polymerizable compounds having a carbon-carbon double bond and a cyclic ether include, for example, glycidyl (meth)acrylate, epoxycyclohexyl (meth)acrylate, 3-ethyloxetan-3-ylmethyl (meth)acrylate, epoxy-4-vinylcyclohe xane, 3-ethyloxetane-3-ylmethyl vinyl ether and the like.
• photopolymerization initiators examples include photocationic polymerization initiators, photoradical polymerization initiators, and photoanion polymerization initiators.
• the photopolymerization initiator preferably contains a photoradical polymerization initiator.
• the photopolymerization initiator preferably contains a photocationic polymerization initiator.
• the photocationic polymerization initiator is not particularly limited, and examples thereof include arylsulfonium salt derivatives (e.g., Cyracure UVI-6990 and Cyracure UVI-6974 manufactured by Dow Chemical Company, Adeka Optomer SP-150 and Adeka Optomer SP manufactured by Adeka Co., Ltd.).
• arylsulfonium salt derivatives e.g., Cyracure UVI-6990 and Cyracure UVI-6974 manufactured by Dow Chemical Company, Adeka Optomer SP-150 and Adeka Optomer SP manufactured by Adeka Co., Ltd.
• Adeka Optomer SP-170 Adeka Optomer SP-172, San-Apro CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI-310FG, CPI-400S, LW -S1, Civacure 1190 manufactured by Double Bond, etc.
• aryliodonium salt derivatives e.g., Irgacure 250 manufactured by Ciba Specialty Chemicals, RP-2074 manufactured by Rhodia Japan
• allene-ion complex derivatives e.g., Irgacure 250 manufactured by Ciba Specialty Chemicals, RP-2074 manufactured by Rhodia Japan
• allene-ion complex derivatives e.g., diazonium salt derivatives , triazine-based initiators and other acid generators such as halides.
• Photocationic polymerization initiators include, for example, onium salts represented by formula (B-1).
• A represents an element of group VIA to VIIA with valence m, m represents 1 to 2, p represents 0 to 3, R represents an organic group attached to A;
• D is the following formula (B-1-1):
• E represents a divalent group
• G represents -O-, -S-, -SO-, -SO 2 -, -NH- , -NR'-, -CO-, -COO-, -CONH-, an alkylene or phenylene group having 1 to 3 carbon atoms
• R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms
• a represents 0 to 5.
• a + 1 E and a G may be the same or different.
• X ⁇ is the counterion of onium.
• the onium ion of formula (B-1) is not particularly limited, and examples thereof include 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4- ⁇ bis[4-(2 -hydroxyethoxy)phenyl]sulfonio ⁇ phenyl]sulfide, bis ⁇ 4-[bis(4-fluorophenyl)sulfonio]phenyl ⁇ sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl) Sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isoprop
• R is an organic group bonded to A.
• R is, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms. and these may have a substituent.
• substituents include alkyl groups, hydroxy groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, at least one selected from the group consisting of a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group, and a halogen; be done.
• R is m+p(m ⁇ 1)+1, which may be the same or different. Also, two or more R may be directly or A ring structure containing the element A may be formed by bonding through an alkylene or phenylene group having 1 to 3 carbon atoms.
• R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• aryl group having 6 to 30 carbon atoms examples include monocyclic aryl groups such as phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, benzanthracenyl group, anthraquinolyl group, Condensed polycyclic aryl groups such as fluorenyl group, naphthoquinone group and anthraquinone group can be mentioned.
• substituents include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; hydroxy group; linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
• Phenylthio 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromo phenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2 -naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenyl]phenylthio, 4-[4-(phen
• aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl and naphthyl; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathi heterocyclic groups having 4 to 20 carbon atoms such as inyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thi
• p in formula (B-1) represents the number of repeating units of the [DA + R m-1 ] bond, and is preferably an integer of 0-3.
• Preferred onium ions [A + ] in formula (B-1) are sulfonium, iodonium and selenium, and representative examples thereof include the following.
• Sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl ) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4 -(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenyl
• Sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4- ⁇ bis[4-(2- Hydroxyethoxy)phenyl]sulfonio ⁇ phenyl]sulfide, bis ⁇ 4-[bis(4-fluorophenyl)sulfonio]phenyl ⁇ sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium , 4-(4-benzoylphenylthio)phenyldiphenylsulfonium , 4-(4-benzoylphenylthio)phenyldiphenylsulfonium , 4-(4-benzoylphenylthi
• X - is a counter ion.
• the number is p+1 per molecule.
• the counter ion is not particularly limited, but examples thereof include boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, halides such as alkylsulfonic acid compounds, and methide compounds.
• Examples of X- include halogen ions such as F- , Cl- , Br- , I- ; OH- ; ClO4- ; FSO3- , ClSO3- , CH3SO3- , C6H5SO3 .
• fluorinated alkylfluorophosphate ions examples include fluorinated alkylfluorophosphate ions represented by formula (B-1-3) and the like. [(Rf) b PF 6-b ] - (B-1-3)
• Rf represents an alkyl group substituted with a fluorine atom.
• the number b of Rf is 1 to 5 and is preferably an integer.
• the b Rf's may be the same or different.
• the number b of Rf is more preferably 2-4, most preferably 2-3.
• Rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.
• Alkyl groups include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. and the like.
• Rf examples include CF 3 , CF 3 CF 2 , (CF 3 ) 2 CF, CF 3 CF 2 CF 2 , CF 3 CF 2 CF 2 CF 2 , (CF 3 ) 2 CFCF 2 and CF 3 CF 2 (CF 3 )CF, (CF 3 ) 3 C and the like.
• preferred fluorinated alkylfluorophosphate anions include [(CF 3 CF 2 ) 2 PF 4 ] ⁇ , [(CF 3 CF 2 ) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CF) 2 PF 4 ] ⁇ , [((CF 3 ) 2 CF) 3 PF 3 ] ⁇ , [(CF 3 CF 2 CF 2 ) 2 PF 4 ] ⁇ , [(CF 3 CF 2 CF 2 ) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CFCF 2 ) 2 PF 4 ] ⁇ , [((CF 3 ) 2 CFCF 2 ) 3 PF 3 ] ⁇ , [(CF 3 ) 2 CFCF 2 ) 3 PF 3 ] ⁇ , [(CF 3 ) 2 CFCF 2 ) 3 PF 3 ] ⁇ , [(CF 3 CF 2 CF 2 ) 2 PF 4 ] ⁇
• the photocationic polymerization initiator may be dissolved in a solvent in advance to facilitate mixing with the polymerizable compound.
• solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate.
• a compound represented by the formula (1) is preferable as the photocationic polymerization initiator.
• Examples of the compound represented by Formula (1) include triarylsulfonium tris(pentafluorophenyl)borate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, and the like.
• R 1 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and X 1 ⁇ represents a monovalent anion. Multiple R 1 's may be the same or different.
• Examples of the alkyl group for R 1 are the same as the alkyl group having 1 to 30 carbon atoms for R above.
• As the aryl group for R 1 the same aryl group having 6 to 30 carbon atoms as the above R can be exemplified.
• R 1 is preferably an optionally substituted alkyl group or an optionally substituted aryl group, more preferably an optionally substituted aryl group.
• the photoradical polymerization initiator is not particularly limited, Benzophenone and its derivatives; benzyl and its derivatives; anthraquinone and its derivatives; Benzoin-type photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal; Acetophenone-type photopolymerization initiators such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone; 2-dimethylaminoethyl benzoate; p-dimethylaminoethyl benzoate; diphenyl disulfide; thioxanthone and its derivatives; camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3
• the content of the photopolymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, with respect to 100 parts by mass of the polymerizable compound. 5 parts by mass or more is more preferable. Curability is thereby further improved.
• the content of the polymerization initiator is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. This makes it possible to form a sealing material with excellent reliability in long-term storage.
• the content of the photopolymerization initiator is, for 100 parts by mass of the polymerizable compound, for example, 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.1 to 5 parts by mass, 0.1 ⁇ 3 parts by weight, 0.3 to 5 parts by weight, 0.3 to 3 parts by weight, 0.5 to 5 parts by weight, or 0.5 to 3 parts by weight.
• inorganic fine particles examples include crystalline silica, amorphous silica, alumina, magnesia, zirconia, talc, mica, clay, kaolin, rutile titanium oxide, anatase titanium oxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, Magnesium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, etc. can be used.
• spherical inorganic fine particles such as spherical silica, spherical alumina, spherical magnesia and spherical zirconia can be preferably used.
• the irradiation light is irregularly reflected at the interface between the polymerizable compound and the inorganic fine particles in the composition, and the irradiation light can easily reach the deep part of the composition, and the above-mentioned suitable curing depth is further satisfied. tends to be easier.
• the average circularity (circularity) of the inorganic fine particles is preferably 0.7 or more, more preferably 0.8 or more, and still more preferably 0.85 or more. As a result, there is a tendency that the above-described effect of irregular reflection can be obtained more remarkably.
• the average circularity of the inorganic fine particles may be 1.0 or less.
• the inorganic fine particles preferably have a refractive index close to that of the polymerizable compound.
• ) between the refractive index n 1 of the polymer of the polymerizable compound and the refractive index n 2 of the inorganic fine particles may be, for example, 0.6 or less, preferably 0.6. It is 5 or less, more preferably 0.4 or less, still more preferably 0.3 or less, still more preferably 0.25 or less, and may be 0.2 or less, 0.15 or less, or 0.1 or less.
• the inorganic fine particles have a refractive index close to the refractive index of the polymerizable compound, the irradiation light is less likely to be reflected at the interface between the inorganic fine particles and the polymerizable compound, making it easier for the irradiation light to reach deep into the composition. It tends to make it easier to meet the preferred cure depth described above.
• the inorganic fine particles with the highest content is preferably within the above range, and more preferably
• the refractive index n2 of the inorganic fine particles is not particularly limited, and is, for example, 1.3 or more, preferably 1.4 or more.
• the refractive index n2 of the inorganic fine particles is, for example, 2.5 or less, preferably 2.3 or less, more preferably 2.0 or less, still more preferably 1.8 or less, and still more preferably 1.6 or less. Yes, and may be 1.5 or less.
• the refractive index n2 of the inorganic fine particles is measured by, for example, an Abbe refractometer. That is, the refractive index n 2 of the inorganic fine particles is, for example, 1.3-2.5, 1.3-2.3, 1.3-2.0, 1.3-1.8, 1.3-1. 6, 1.3-1.5, 1.4-2.5, 1.4-2.3, 1.4-2.0, 1.4-1.8, 1.4-1.6 or It may be from 1.4 to 1.5.
• the average particle size of the inorganic fine particles may be, for example, 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more.
• the average particle size of the inorganic fine particles may be, for example, 50 ⁇ m or less, preferably 30 ⁇ m or less, and more preferably 10 ⁇ m or less.
• the average particle diameter of the inorganic fine particles is small, the inorganic fine particles are less likely to separate in the composition, making it easier to obtain a more uniform cured body, and tending to further improve long-term reliability.
• the average particle diameter of the inorganic fine particles is, for example, 0.1 to 50 ⁇ m, 0.1 to 30 ⁇ m, 0.1 to 10 ⁇ m, 0.5 to 50 ⁇ m, 0.5 to 30 ⁇ m, 0.5 to 10 ⁇ m, 1 to It may be 50 ⁇ m, 1-30 ⁇ m or 1-10 ⁇ m.
• the average particle size of inorganic fine particles indicates a value measured by a laser diffraction/scattering method using a Microtrac particle size distribution device.
• the content of the inorganic fine particles is 30% by volume or more, preferably 32% by volume or more, more preferably 35% by volume or more, and may be 40% by volume or more or 45% by volume or more.
• the upper limit of the content of inorganic fine particles is not particularly limited as long as the above-described curing depth can be maintained.
• the content of the inorganic fine particles may be, for example, 80% by volume or less, preferably 70% by volume or less, more preferably 65% by volume or less, and 60% by volume or less, 55% by volume or less, or 50% by volume or less.
• the content of the inorganic fine particles is, for example, 30 to 80% by volume, 30 to 70% by volume, 30 to 65% by volume, 30 to 60% by volume, 30 to 55% by volume, 30 to 50% by volume, 32 to 80% by volume.
• % by volume 32 to 70% by volume, 32 to 65% by volume, 32 to 60% by volume, 32 to 55% by volume, 32 to 50% by volume, 35 to 80% by volume, 35 to 70% by volume, 35 to 65% by volume , 35-60% by volume, 35-55% by volume, 35-50% by volume, 40-80% by volume, 40-70% by volume, 40-65% by volume, 40-60% by volume, 40-55% by volume, 40 ⁇ 50% by volume, 45-80% by volume, 45-70% by volume, 45-65% by volume, 45-60% by volume, 45-55% by volume, or 45-50% by volume.
• composition of this embodiment may further contain a photosensitizer.
• the photosensitizer absorbs energy rays and efficiently generates reactive species (for example, cations generated from a photocationic polymerization initiator, radicals generated from a photoradical polymerization initiator) from a polymerization initiator. shows the compounds that can be
• Photosensitizers are not particularly limited, and examples include benzophenone derivatives, phenothiazine derivatives, phenylketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, Benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, tri Examples include allylmethane derivatives, phthalo
• phenylketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one
• anthracene derivatives such as 9,10-dibutoxyanthracene are preferred, and anthracene derivatives are more preferred.
• 9,10-dibutoxyanthracene is preferred.
• the photosensitizers may be used singly or in combination of two or more.
• Suitable photosensitizers include, for example, photosensitizers represented by the following formula (2).
• Examples of the photosensitizer represented by the following formula (2) include dibutoxyanthracene and the like.
• R2 represents an optionally substituted alkyl group.
• the number of carbon atoms in the alkyl group of R 2 may be, for example, 1-10, preferably 2-8, more preferably 2-6. That is, the number of carbon atoms in the alkyl group of R 2 may be, for example, 1-10, 1-8, 1-6, 2-10, 2-8 or 2-6.
• the content of the photosensitizer may be, for example, 0.01 parts by mass or more with respect to 100 parts by mass of the polymerizable compound, and 0.05 mass It may be more than part.
• the content of the photosensitizer may be, for example, 5 parts by mass or less, preferably 3 parts by mass or less, with respect to 100 parts by mass of the polymerizable compound. That is, the content of the photosensitizer is, for 100 parts by weight of the polymerizable compound, for example, 0.01 to 5 parts by weight, 0.01 to 3 parts by weight, 0.05 to 5 parts by weight or 0.05 It may be up to 3 parts by mass.
• composition of this embodiment may further contain components other than those described above.
• components for example, known additives used in the field of sealants can be used without particular limitation.
• Other components include, for example, silane coupling agents, antioxidants, resin particles, metal deactivators, fillers, stabilizers, neutralizers, lubricants, antibacterial agents, and the like.
• the content of other components is not particularly limited, and may be, for example, 10% by mass or less, 5% by mass or less, or 1% by mass or less based on the total amount of the composition.
• the method for producing the composition of the present embodiment is not particularly limited, and the above-described components may be mixed by a mixing method having a stirring capability that allows the above-described components to be sufficiently mixed.
• Mixing methods include, for example, a method of stirring by imparting a rotational force to a stirrer such as a stirring blade, a screw, and a magnetic stirrer; a method of stirring by rotating a container such as a tumbler mixer or a planetary stirrer; A method of stirring using the shearing force of a ball, a method of stirring using a compression force such as a roll mill, a method of stirring using a vibration force such as a shaker, and a method of stirring the mixture itself such as a vortex mixer.
• Examples include a method of using a known dispersing machine, such as a method of using agitation using an ultrasonic agitator and a method of agitating using an ultrasonic wave such as an ultrasonic agitator.
• a method of stirring by rotating a container such as a planetary stirrer is preferable from the viewpoint of being able to sufficiently and safely mix the above components and minimizing impurities such as stirrers.
• Examples of the method of stirring by rotating the container include a method using a vacuum rotation-revolution mixer.
• a cured product containing a polymer of a polymerizable compound and inorganic fine particles can be obtained.
• the cured product has low moisture permeability and can be suitably used as a sealing material (in particular, a sealing material for an organic EL display element and a dam of a dam-fill sealing structure).
• the composition of the present embodiment can be cured, for example, by irradiation with energy rays.
• energy rays ultraviolet light and visible light are preferably used from the viewpoint of reaction efficiency and safety.
• the light source used for curing the composition of the present embodiment is not particularly limited, but halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium or the like), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps. , xenon lamps, xenon excimer lamps, xenon flash lamps, light emitting diodes (hereinafter referred to as LEDs), and the like.
• Natural light can also be a reaction initiation light source.
• an LED light source is preferable because it can selectively irradiate a target wavelength.
• the wavelength of the light source is not particularly limited, and the light source is appropriately selected depending on the reaction wavelength of the polymerization initiator.
• the wavelength can be 400 nm or less, preferably 395 nm or less, more preferably 385 nm or less, and still more preferably 365 nm or less, in terms of reactivity efficiency.
• it can be 300 nm or more, preferably 320 nm or more, more preferably 340 nm or more, and still more preferably 365 nm or more.
• the wavelength of the light source is, for example, 300 to 400 nm, 300 to 395 nm, 300 to 385 nm, 300 to 365 nm, 320 to 400 nm, 320 to 395 nm, 320 to 385 nm, 320 to 365 nm, 340 to 400 nm, 340 to 395 nm, It may be 340-385 nm, 340-365 nm, 365-400 nm, 365-395 nm or 365-385 nm.
• the irradiation method using the light source may be direct irradiation or condensed irradiation using a reflecting mirror, fiber, or the like. Irradiation using a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like may also be used.
• the irradiation amount of the light source may be appropriately selected according to the thickness of the composition.
• the irradiation dose for a composition having a thickness of 100 ⁇ m is preferably 600 mJ/cm 2 or more, more preferably 1000 mJ/cm 2 or more.
• the irradiation dose may be appropriately adjusted according to the thickness (for example, proportional to the thickness).
• a post-heating treatment may be performed to accelerate curing after light irradiation.
• the post-heating temperature is preferably 150° C. or lower, more preferably 100° C. or lower, and may be 90° C. or lower or 80° C. or lower from the viewpoint of avoiding the influence on the organic EL display element.
• the post-heating temperature is preferably 40° C. or higher, and may be 50° C. or higher, 60° C. or higher, 70° C. or higher, or 80° C. or higher.
• the post-heating temperature is, for example, 40 to 150°C, 40 to 100°C, 40 to 90°C, 40 to 80°C, 50 to 150°C, 50 to 100°C, 50 to 90°C, 50 to 80°C, 60-150°C, 60-100°C, 60-90°C, 60-80°C, 70-150°C, 70-100°C, 70-90°C or 70-80°C.
• the post-treatment time is preferably 120 minutes or less, more preferably 60 minutes or less, and even more preferably 30 minutes or less, from the viewpoint of avoiding the influence on the organic EL display element.
• the post-treatment time may be 5 minutes or longer, 10 minutes or longer, preferably 20 minutes or longer, and more preferably 30 minutes or longer.
• the post-treatment time is, for example, 5 to 120 minutes, 5 to 60 minutes, 5 to 30 minutes, 10 to 120 minutes, 10 to 60 minutes, 10 to 30 minutes, 20 to 120 minutes, 20 to 60 minutes, It may be 20-30 minutes, 30-120 minutes or 30-60 minutes.
• composition of this embodiment can also be used as an adhesive.
• the composition of the present embodiment can be suitably used, for example, for adhesion of packages such as organic EL display elements.
• a step of applying the composition to the entire surface or a part of the first member for example, a step of applying the composition on the first member and a step of bonding the first member and the second member through the composition until the composition irradiated with light is cured.
• Such a method allows bonding onto the first member without exposing the second member to light and heat. Therefore, the above method can be suitably used for bonding the back plate and the organic EL display element.
• a method for manufacturing an organic EL display device using the composition of the present embodiment includes, for example, a step of applying the composition on the back plate, and a step of irradiating the composition applied on the back plate with light. and a step of blocking light and adhering the back plate and the substrate on which the organic EL display element is formed via the composition. According to such a method, the organic EL display element can be sealed without exposing it to light and heat.
• a step of applying the composition to one substrate, and one substrate and the other substrate are separated via the composition.
• a manufacturing method including a step of bonding and a step of irradiating the composition between the substrates with light to cure the composition is also included.
• the composition of the present embodiment has a curing depth of 100 ⁇ m or more when it is irradiated with light having a wavelength of 365 nm and an irradiation dose of 600 mJ/cm 2 and allowed to stand at 80° C. for 30 minutes.
• the curing depth is preferably 120 ⁇ m or more, more preferably 140 ⁇ m or more, still more preferably 160 ⁇ m or more, and still more preferably 180 ⁇ m or more, and is 200 ⁇ m or more, 250 ⁇ m or more, 300 ⁇ m or more, 350 ⁇ m or more, 400 ⁇ m or more, 450 ⁇ m or more, or 500 ⁇ m or more.
• the upper limit of the hardening depth is not particularly limited.
• the curing depth may be, for example, 1000 ⁇ m or less, preferably 800 ⁇ m or less, and more preferably 700 ⁇ m or less.
• the curing depth is, for example, 100 to 1000 ⁇ m, 100 to 800 ⁇ m, 100 to 700 ⁇ m, 120 to 1000 ⁇ m, 120 to 800 ⁇ m, 120 to 700 ⁇ m, 140 to 1000 ⁇ m, 140 to 800 ⁇ m, 140 to 700 ⁇ m, 160 to 1000 ⁇ m, 160 ⁇ 800 ⁇ m, 160-700 ⁇ m, 180-1000 ⁇ m, 180-800 ⁇ m, 180-700 ⁇ m, 200-1000 ⁇ m, 200-800 ⁇ m, 200-700 ⁇ m, 250-1000 ⁇ m, 250-800 ⁇ m, 250-700 ⁇ m, 300-1000 ⁇ m, 300-800 ⁇ m or It may be ⁇ 700 ⁇ m.
• the type and content of each component may be appropriately adjusted so that the curing depth is within the above range.
• the specific gravity of the cured body of the composition of the present embodiment (hereinafter also simply referred to as the cured body of the present embodiment) is, for example, 1.3 or more, preferably 1.5 or more, and more preferably 1.7. That's it.
• the specific gravity of the cured product of the present embodiment may be, for example, 5.0 or less, preferably 3.0 or less. That is, the specific gravity of the cured body of the present embodiment is, for example, 1.3 to 5.0, 1.3 to 3.0, 1.5 to 5.0, 1.5 to 3.0, 1.7 to It may be 5.0 or 1.7 to 3.0.
• the specific gravity of the hardened body is a value measured using water at 23°C as an immersion liquid in accordance with JIS K7112 B method.
• the type and content of each component may be appropriately adjusted so that the specific gravity of the cured product falls within the above range.
• the glass transition temperature of the polymer of the polymerizable compound may be, for example, 80° C. or higher, preferably 85° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C. or higher.
• the glass transition temperature of the polymer of the polymerizable compound may be, for example, 250° C. or lower.
• the glass transition temperature (Tg) of a polymer indicates a value obtained from dynamic viscoelasticity spectrum.
• the dynamic viscoelasticity spectrum when a polymer, which is solid at a certain temperature, is heated at a constant heating rate after applying stress and strain at that temperature, the storage modulus decreases and the loss tangent (hereinafter referred to as tan ⁇ ) can be taken as the glass transition temperature.
• the type and content of each component may be appropriately adjusted so that the glass transition temperature of the polymer falls within the above range.
• the viscosity of the composition of the present embodiment is, for example, 0.1 Pa ⁇ s or more, preferably 1 Pa ⁇ s or more, more preferably 10 Pa ⁇ s or more, and still more preferably 100 Pa ⁇ s or more.
• the viscosity of the composition of the present embodiment is, for example, 10000 Pa ⁇ s or less, preferably 1000 Pa ⁇ s or less.
• the low viscosity of the composition facilitates processing and handling of the composition.
• the viscosity of the composition of the present embodiment is 0.1 to 10000 Pa s, 0.1 to 1000 Pa s, 1 to 10000 Pa s, 1 to 1000 Pa s, 10 to 10000 Pa s, 10 to 1000 Pa s. s, 100-10000 Pa ⁇ s or 100-1000 Pa ⁇ s.
• the viscosity is a value measured at 23°C using a cone-plate viscometer method in accordance with JIS K5600 2-3 method.
• the cured body of the present embodiment has a moisture permeability per 100 ⁇ m thickness measured under conditions of a temperature of 85° C. and a relative humidity of 85% in accordance with JIS Z0208 of 150 g/(m 2 24 hours) or less. is preferably 130 g/(m 2 24 hours) or less, more preferably 100 g/(m 2 24 hours) or less, and 80 g/(m 2 24 hours) or less It is more preferably 60 g/(m 2 ⁇ 24 hours) or less, and may be 50 g/(m 2 ⁇ 24 hours) or less.
• the moisture permeability can also be said to be the moisture permeability (g/m 2 ) at a thickness of 100 ⁇ m measured by exposing to an environment of 85° C.
• the moisture permeability may be, for example, 0.01 (g/m 2 ⁇ 24 hours) or more, may be 0.1 (g/m 2 ⁇ 24 hours) or more, or may be 1 (g/m 2 ⁇ 24 hours) or more. 24 hours) or more, or 5 (g/m 2 ⁇ 24 hours) or more.
• the moisture permeability is, for example, 0.01 to 150 g/(m 2 ⁇ 24 hours), 0.01 to 130 g/(m 2 ⁇ 24 hours), 0.01 to 100 g/(m 2 ⁇ 24 hours) , 0.01 to 80 g/(m 2 24 hours), 0.01 to 60 g/(m 2 24 hours), 0.01 to 50 g/(m 2 24 hours), 0.1 to 150 g/( m 2 24 hours), 0.1 to 130 g/(m 2 24 hours), 0.1 to 100 g/(m 2 24 hours), 0.1 to 80 g/(m 2 24 hours), 0 .1-60 g/(m 2 ⁇ 24 hours), 0.1-50 g/(m 2 ⁇ 24 hours), 1-150 g/(m 2 ⁇ 24 hours), 1-130 g/(m 2 ⁇ 24 hours) , 1 to 100 g/(m 2 24 hours), 1 to 80 g/(m 2 24 hours), 1 to 60 g/(m 2 24 hours), 1 to 50 g/(m/(
• the type and content of each component may be appropriately adjusted so that the moisture permeability of the cured product is within the above range.
• the cured body of the present embodiment may have a water absorption rate of, for example, 15% or less, preferably 10% or less, more preferably 5% or less, and even more preferably 85° C. and 85% relative humidity for 24 hours. It is 3% or less, and may be 2% or less, 1.5% or less, or 1% or less. As a result, deterioration in moisture resistance and reliability due to residual moisture in the cured body is suppressed, and there is a tendency to realize better moisture resistance and long-term reliability.
• the type and content of each component may be appropriately adjusted so that the water absorption of the cured body is within the above range.
• the present invention may relate to a method of manufacturing an organic electroluminescence display device having a dam-fill sealing structure, including the steps of applying and curing the composition described above to form a dam.
• the present invention may also relate to an organic EL display device having a dam-fill sealing structure comprising a dam and a filling agent, and in this case, the dam may contain a cured body of the composition described above.
• the dam-fill sealing structure may be a known dam-fill sealing structure, and the filling agent may be a known filling agent.
• the configuration of the organic EL display device other than the dam-fill sealing structure may be the same as that of a known organic EL display device.
• the organic EL display element may be an organic EL television. According to the present invention, it is possible to provide a sealant capable of achieving sufficient moisture resistance and long-term reliability in organic EL televisions, which are becoming noticeably larger.
• A Polymerizable compound (A-1) Glycidyl methacrylate (“Light Ester G” manufactured by Kyoeisha Chemical Co., Ltd., specific gravity: 1.1, refractive index: 1.45, molecular weight: 142) (A-2) Neopentyl glycol diglycidyl ether ("ED523T” manufactured by Adeka, specific gravity: 1.1, refractive index: 1.48, molecular weight: 216) (A-3) Tetrabromobisphenol A diglycidyl ether (“Epiclon 152” manufactured by DIC, specific gravity: 1.7, refractive index: 1.60, molecular weight: 972) (A-4) 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("Celoxide 2021” manufactured by Daicel Chemical Industries, specific gravity: 1.2, refractive index: 1.52, molecular weight: 252) (A-5) 1,10-decanediol
• B Polymerization initiator (B-1) triarylsulfonium tris(pentafluorophenyl)borate ("CPI-310B” manufactured by San-Apro Co., Ltd.) (B-2) benzyl dimethyl ketal ("Irgacure TPO" manufactured by BASF)
• C Inorganic fine particles (C-1) Spherical silica (“FB-5SDC” manufactured by Denka, average particle size: 4 ⁇ m, circularity: 0.9, refractive index: 1.44, specific gravity: 2.1) (C-2) Spherical alumina (“DAW-05” manufactured by Denka, average particle size: 5 ⁇ m, circularity: 0.95, refractive index: 1.77, specific gravity: 3.9) (C-3) Tabular talc (Matsumura Sangyo "High Filler #17”, average particle size: 12 ⁇ m, circularity: 0.5, refractive index: 1.57, specific gravity: 2.7) (C-4) Rutile titanium oxide (Ishihara Sangyo “CR-EL”, average particle size: 0.25 ⁇ m, circularity: 0.7, refractive index: 2.13, specific gravity: 4.2)
• Examples 1 to 7 and Comparative Examples 1 to 4 The raw materials shown in Tables 1 to 3 were weighed in the proportions shown in Tables 1 to 3, and stirred and mixed at 600 rpm for 5 minutes with a vacuum rotation/revolution mixer (EME "UFO-S3") to obtain the compositions of Examples and Comparative Examples. prepared.
• the mixing ratio is shown in parts by mass.
• the content of the inorganic fine particles is expressed in volume % by calculating the volume ratio from the specific gravity.
• ⁇ Refractive index of polymer of polymerizable compound> A polymerizable compound and a polymerization initiator were weighed in proportions shown in Tables 1 to 3, and stirred and mixed at 2000 rpm for 5 minutes using a rotation/revolution mixer (Thinky "AR-250") to obtain a mixture. Next, the mixture was coated on a polyethylene terephthalate film to a thickness of 100 ⁇ m, irradiated with ultraviolet light at an irradiation dose of 600 mJ/cm 2 from an LED light source with a wavelength of 365 nm, and allowed to stand at 80° C. for 30 minutes. After that, the polyethylene terephthalate film was peeled off to obtain a measurement sample. The refractive index of the obtained measurement sample was measured with an Abbe refractometer (Atago "DR-M2").
• the composition was filled in a urethane tube with an inner diameter of 4 mm and a depth of 8 mm, the sides and bottom of which were covered with aluminum foil, and was irradiated from the top of the tube on a hot plate at 80 ° C. with an LED light source with a wavelength of 365 nm at an irradiation dose of 600 mJ / cm 2 . UV light was applied. After the irradiation, the tube was allowed to stand at 80°C for 30 minutes, then the uncured portion at the bottom of the tube was wiped off with gauze impregnated with ethanol, and the thickness of the remaining cured portion was measured with a micrometer (manufactured by Mitutoyo). .
• Total light transmittance, total light reflectance> The composition was applied on glass to a thickness of 100 ⁇ m, and further glass was layered thereon to form a three-layer structure of glass/composition/glass. After performing base correction using two sheets of uncoated glass with a haze meter (Nippon Denshoku "NDH-8000"), the total light transmittance and total light reflectance of the above three-layer structure sample were measured. .
• the composition was applied on a polyethylene terephthalate film to a thickness of 100 ⁇ m. Next, after irradiating ultraviolet light with an irradiation amount of 600 mJ/cm 2 from an LED light source with a wavelength of 365 nm, it was allowed to stand at 80° C. for 30 minutes. Thereafter, the polyethylene terephthalate film was peeled off to obtain a cured product.
• ⁇ Moisture permeability> The moisture permeability of the cured product was measured according to the moisture permeability cup method of JIS Z 0208, except that the test conditions were 85° C., 85% RH, and 24 hours.
• the positions of the first glass substrate and the second glass substrate were aligned so that the composition on the first glass substrate surrounded the metallic calcium on the second glass substrate. Then, after irradiating ultraviolet light with a wavelength of 365 nm and an irradiation amount of 600 mJ/cm 2 from the first glass substrate side, it was pressed with a vacuum press at 40° C. with a load of 0.1 MPa. Then, the substrate was heated in an oven at 80° C. for 30 minutes to obtain a side-sealed substrate whose side surfaces were sealed with a sealing material made of a cured product of the composition.

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