WO2023182283A1 - Sealing agent and sealing material for organic electroluminescent elements, organic electroluminescent display device, and method for producing sealing agent for organic electroluminescent elements - Google Patents

Sealing agent and sealing material for organic electroluminescent elements, organic electroluminescent display device, and method for producing sealing agent for organic electroluminescent elements Download PDF

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Publication number
WO2023182283A1
WO2023182283A1 PCT/JP2023/010936 JP2023010936W WO2023182283A1 WO 2023182283 A1 WO2023182283 A1 WO 2023182283A1 JP 2023010936 W JP2023010936 W JP 2023010936W WO 2023182283 A1 WO2023182283 A1 WO 2023182283A1
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Prior art keywords
mass
meth
acrylate
sealant
radically polymerizable
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PCT/JP2023/010936
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French (fr)
Japanese (ja)
Inventor
麻希子 佐々木
啓之 栗村
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デンカ株式会社
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    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • 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
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

Definitions

  • the present invention relates to a sealant for an organic electroluminescent device, a sealing material, an organic electroluminescent display device, and a method for manufacturing the sealant for an organic electroluminescent device.
  • Organic electroluminescent devices (hereinafter also referred to as organic EL devices) are attracting attention as device bodies that can emit light with high brightness.
  • organic EL elements have a problem in that they are degraded by oxygen and moisture, resulting in reduced light-emitting characteristics.
  • techniques for sealing organic EL elements and preventing deterioration are being considered.
  • Patent Document 1 describes a sealing method that contains a polymerizable compound and a polymerization initiator, has a viscosity of 5 to 50 mPa ⁇ s at 25°C, and has a surface tension of 15 to 35 mN/s at 25°C.
  • the encapsulant for organic EL elements is described, which has a water content of 1000 ppm or less at 25° C. after standing for 24 hours in an environment of 25° C. and 50% RH.
  • thermosetting encapsulants and photocurable encapsulants are known.
  • Photocurable encapsulants do not require heating during sealing, so they can form encapsulants without exposing organic EL elements to high heat, and have the advantage of suppressing deformation and deterioration of organic EL elements due to high heat. has.
  • an object of the present invention is to provide an encapsulant for organic EL elements that can significantly suppress the occurrence of dark spots under high temperature and high humidity conditions. Further, the present invention provides a sealant formed from the sealant for organic EL elements, an organic EL display device equipped with the sealant, and a method for manufacturing the sealant for organic EL elements. With the goal.
  • the present invention relates to, for example, the following ⁇ 1> to ⁇ 7>.
  • Organic electroluminescence containing a radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical, and having an acid value of 0.01 to 0.15 (mgKOH/g) Encapsulant for elements.
  • a sealing material comprising a cured product of the sealant according to ⁇ 1> or ⁇ 2>.
  • An organic electroluminescent display device comprising an organic electroluminescent element and the sealing material according to ⁇ 3>, which seals the organic electroluminescent element.
  • a method for producing a sealant for an organic electroluminescent device comprising:
  • an encapsulant for organic EL elements that can significantly suppress the occurrence of dark spots under high temperature and high humidity conditions. Further, according to the present invention, there is provided a sealant formed from the sealant for organic EL elements, an organic EL display device including the sealant, and a method for manufacturing the sealant for organic EL elements. be done.
  • X to Y in the description of numerical ranges means from X to Y, unless otherwise specified.
  • “1 to 5% by mass” means “1 to 5% by mass”.
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth)acrylic includes both acrylic and methacrylic.
  • the sealant of this embodiment contains a radically polymerizable compound, a photopolymerization initiator, and a stable radical type compound having a stable radical. Further, the sealant of this embodiment has an acid value of 0.01 to 0.15 (mgKOH/g).
  • the sealant of this embodiment is for sealing an organic electroluminescent element. That is, the sealant of this embodiment is used to seal an organic EL element and manufacture an organic EL display device.
  • the sealant of this embodiment is a photocurable sealant because it contains a photopolymerization initiator.
  • the reason why the sealant of this embodiment achieves the above effects is not necessarily limited, the following reasons can be considered.
  • conventional encapsulants contain a trace amount of acid component in the encapsulant formed by curing the encapsulant, and due to the presence of the acid component, the sealant is When moisture enters the sealing material, the sealing material may deteriorate due to hydrolysis, resulting in a decrease in reliability.
  • the encapsulant of this embodiment has an acid value of 0.15 mgKOH/g or less, there is little residual acid component in the encapsulant, and even if a small amount of moisture enters the encapsulant, the encapsulant will remain intact. Hydrolysis of the stopper material is less likely to occur. Therefore, according to the sealant of the present embodiment, it is possible to form a sealant that does not easily deteriorate even under high temperature and high humidity conditions, and it is possible to suppress the occurrence of dark spots due to deterioration of the sealant.
  • the sealant of this embodiment has an acid value of 0.01 mgKOH/g or more and contains an extremely small amount of acid component.
  • this extremely small amount of acid component acts as a polymerization inhibitor, making the sealant excellent in storage stability, and suppressing a decrease in reliability due to deterioration of the sealant during storage. it is conceivable that.
  • the sealant of this embodiment has excellent discharge properties from the coating device. Specifically, according to the sealant of this embodiment, when the sealant is discharged from the coating device, bending of the discharged liquid, variation in the amount of the discharged liquid, etc. are suppressed, and good dischargeability is maintained. As a result, according to the sealant of the present embodiment, a coating film with significantly less uneven thickness and excellent flatness can be formed. Moreover, according to the encapsulant of this embodiment, it is possible to form a encapsulant that contributes to improving the reliability of organic EL elements.
  • the reason why the sealant of this embodiment achieves the above effects is not necessarily limited, the following reasons can be considered. According to the findings of the present inventors, with conventional photocurable sealants, when the sealant is discharged from the coating device, bending of the discharged liquid, variations in the amount of discharged liquid, etc. occur, and this causes the coating to be applied. There were cases where the film became uneven in thickness and the flatness of the coating film decreased. The reason for this is that photocurable sealants tend to undergo unintentional polymerization before use (for example, during storage, transportation, etc.), and the fine particles generated by the polymerization may flow through the coating equipment.
  • the sealant of this embodiment contains a stable radical type compound, so that although it is a photocurable sealant, there is no possibility of unintentional polymerization before use (for example, during storage, transportation, etc.) or due to the polymerization. Generation of particles is significantly suppressed. Therefore, with the sealant of the present embodiment, coating defects caused by particles are suppressed, and excellent discharge properties from the coating device and high flatness of the coated film after coating are achieved.
  • the reliability of the organic EL device may be lowered due to the intrusion of water or oxygen through the cracks.
  • the sealant of this embodiment contains a stable radical type compound, the above-mentioned reaction points are unlikely to remain in the cured product, and further polymerization from the reaction points is also suppressed. Therefore, according to the encapsulant of this embodiment, deterioration due to reaction points is difficult to occur, damage to the inorganic protective film due to curing shrinkage can be suppressed, and the encapsulant contributes to improving the reliability of organic EL elements. Can be formed.
  • the radically polymerizable compound may be any compound that can be polymerized by active species generated from the photopolymerization initiator described below.
  • One type of radically polymerizable compound may be used alone, or two or more types may be used in combination.
  • a radically polymerizable compound can be said to be a compound having a radically polymerizable group.
  • the radically polymerizable group include a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, a vinyl ester group, a (meth)acrylamide group, and among these, a (meth)acryloyl group is particularly preferred.
  • the radically polymerizable compound preferably includes, for example, a polyfunctional compound having two or more radically polymerizable groups.
  • the number of radically polymerizable groups in the polyfunctional compound may be, for example, 2 to 6, preferably 2 to 4.
  • photocurability tends to be further improved.
  • the polyfunctional compound is preferably a bifunctional compound having two radically polymerizable groups.
  • the radically polymerizable compound may include a monofunctional compound having one radically polymerizable group. From the viewpoint of easy adjustment of the polymerization rate, physical properties of the cured product, etc., the radically polymerizable compound preferably contains a polyfunctional compound and a monofunctional compound.
  • the proportion of the polyfunctional compound in the radically polymerizable compound may be, for example, 30% by mass or more, preferably 50% by mass or more, and more preferably 60% by mass or more.
  • the content is at least 70% by mass, more preferably at least 80% by mass, and may be at least 85% by mass or at least 90% by mass.
  • the proportion of the polyfunctional compound in the polymerizable compound may be, for example, 100% by mass or less, and preferably 95% by mass or less.
  • the proportion of the polyfunctional compound in the radically polymerizable compound is, for example, 30 to 100% by mass, 30 to 95% by mass, 50 to 100% by mass, 50 to 95% by mass, 60 to 100% by mass, 60 to 95% by mass. %, 70-100% by mass, 70-95% by mass, 80-100% by mass, 80-95% by mass, 85-100% by mass, 85-95% by mass, 90-100% by mass or 90-95% by mass. There may be.
  • polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups is preferred.
  • polyfunctional (meth)acrylic compounds include: Bis(1-(meth)acryloxy-2-hydroxypropyl) phthalate, bis(2-(meth)acryloxyethyl) phosphate, bis((meth)acryloxy-2-hydroxypropyloxy) diethylene glycol, bisphenol A di(meth) acrylate, bisphenol A di-(3-(meth)acryloxyethyl) ether, bisphenol A di-(3-(meth)acryloxy-2-hydroxypropyl) ether, 1,3-butanediol di(meth)acrylate, 1 , 4-butanediol di-(3-(meth)acryloxy-2-hydroxypropyl) ether, 1,4-butanediol di(meth)acrylate, 1,3-butanediol bis((meth)acryloxypropionate
  • a monofunctional (meth)acrylic compound having one (meth)acryloyl group is preferable.
  • monofunctional (meth)acrylic compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and hexyl (meth)acrylate.
  • acrylate 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, n-octyl (meth)acrylate, 2 -Methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate (2-HPA), dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, Cyclopent
  • the radically polymerizable compound preferably contains a compound having an aromatic ring (hereinafter also referred to as an aromatic monomer). This tends to further reduce the moisture permeability of the cured product.
  • the proportion of the aromatic monomer in the radically polymerizable compound may be, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more. The content may be 5% by mass or more. Further, the proportion of the aromatic monomer in the radically polymerizable compound may be, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, It may be 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.
  • the proportion of the aromatic monomer in the radically polymerizable compound is, for example, 1 to 70% by mass, 1 to 60% by mass, 1 to 50% by mass, 1 to 40% by mass, 1 to 30% by mass, 1 to 20% by mass. %, 1-15% by mass, 1-10% by mass, 2-70% by mass, 2-60% by mass, 2-50% by mass, 2-40% by mass, 2-30% by mass, 2-20% by mass, 2-15% by mass, 2-10% by mass, 3-70% by mass, 3-60% by mass, 3-50% by mass, 3-40% by mass, 3-30% by mass, 3-20% by mass, 3- 15% by mass, 3-10% by mass, 5-70% by mass, 5-60% by mass, 5-50% by mass, 5-40% by mass, 5-30% by mass, 5-20% by mass, 5-15% by mass % or 5 to 10% by mass.
  • aromatic monomers examples include: Benzyl (meth)acrylate, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, Phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate (2-HPA), 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2- Hydroxypropylphthalic acid, EO-modified phenol (meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m - Compounds having one aromatic ring such
  • the aromatic monomer is preferably a compound having two or more aromatic rings.
  • the radically polymerizable compound is at least one selected from the group consisting of ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, and ethoxylated bisphenol A di(meth)acrylate as an aromatic monomer. It is more preferable to contain at least one selected from the group consisting of ethoxylated-o-phenylphenol (meth)acrylate and ethoxylated bisphenol A di(meth)acrylate.
  • the radically polymerizable compound includes an alicyclic monomer having a radically polymerizable group and an aliphatic hydrocarbon ring.
  • the aliphatic hydrocarbon ring possessed by the alicyclic monomer may be a monocyclic ring or a fused ring. Further, the aliphatic hydrocarbon ring may be a saturated hydrocarbon ring or an unsaturated hydrocarbon ring.
  • the saturated hydrocarbon ring may be a cycloalkane ring. Examples of the unsaturated aliphatic hydrocarbon ring include a cycloalkene ring, a cycloalkadiene ring, and a cycloalkatriene ring, with the cycloalkene ring being preferred.
  • cycloalkane ring examples include a cyclopentane ring, a cyclohexane ring, a tetrahydrodicyclopentadiene ring, a cycloheptane ring, a cyclooctene ring, a norbornane ring, and an adamantane ring.
  • Examples of the cycloalkene ring include a cyclopentene ring, a cyclohexene ring, a dihydrodicyclopentadiene ring, a cycloheptene ring, a cyclooctene ring, and a norbornene ring.
  • the cycloalkene ring is preferably a cyclopentene ring, a cyclohexene ring, or a dihydrodicyclopentadiene ring, which has a large ring strain, and is preferably a cyclopentene ring or a dihydrodicyclopentadiene ring. It is more preferable that there be.
  • the alicyclic monomer may be a monofunctional compound having one radically polymerizable group, or may be a polyfunctional compound having two or more radically polymerizable groups.
  • the number of radically polymerizable groups in the alicyclic monomer may be, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • the alicyclic monomer may be a compound having one aliphatic hydrocarbon ring, or may be a compound having two or more aliphatic hydrocarbon rings.
  • the number of aliphatic hydrocarbon rings in the alicyclic monomer may be, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2.
  • alicyclic monomer for example, Saturated alicyclic monomers such as tricyclodecane dimethanol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, cyclohexyl(meth)acrylate, dicyclopentanyl(meth)acrylate;
  • unsaturated alicyclic monomers such as dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate.
  • the proportion of the alicyclic monomer in the radically polymerizable compound may be, for example, 3% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. Further, the proportion of the alicyclic monomer in the radically polymerizable compound may be, for example, 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less. . That is, the proportion of the alicyclic monomer in the radically polymerizable compound is, for example, 3 to 90% by mass, 3 to 70% by mass, 3 to 50% by mass, 3 to 40% by mass, 5 to 90% by mass, 5 to 70% by mass. Mass%, 5-50 mass%, 5-40 mass%, 10-90 mass%, 10-70 mass%, 10-50 mass%, 10-40 mass%, 15-90 mass%, 15-70 mass% , 15 to 50% by weight, or 15 to 40% by weight.
  • the radically polymerizable compound preferably contains an acyclic monomer that has a radically polymerizable group and does not have a ring structure.
  • the number of radically polymerizable groups that the acyclic monomer has may be, for example, one or more, and preferably two or more.
  • the number of radically polymerizable groups that the acyclic monomer has may be, for example, 6 or less, preferably 4 or less, and more preferably 3 or less. It is particularly preferable that the acyclic monomer has two radically polymerizable groups. That is, the number of radically polymerizable groups that the acyclic monomer has may be, for example, 1 to 6, 1 to 4, 1 to 3, 2 to 6, 2 to 4, or 2 to 3.
  • Examples of the acyclic monomer include compounds having a radically polymerizable group and a chain saturated hydrocarbon group (hereinafter also referred to as a chain monomer).
  • the number of carbon atoms in the chain saturated hydrocarbon group contained in the chain monomer is, for example, 2 or more, and may be 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more.
  • the number of carbon atoms in the chain saturated hydrocarbon group contained in the chain monomer may be, for example, 16 or less, 15 or less, 14 or less, or 13 or less.
  • the number of carbon atoms in the chain saturated hydrocarbon group possessed by the chain monomer is, for example, 2 to 16, 2 to 15, 2 to 14, 2 to 13, 3 to 16, 3 to 15, 3 to 14, 3 to 13 , 4-16, 4-15, 4-14, 4-13, 6-16, 6-15, 6-14, 6-13, 8-16, 8-15, 8-14, 8-13, 10 -16, 10-15, 10-14 or 10-13.
  • the chain saturated hydrocarbon group possessed by the chain monomer is preferably an alkanediyl group.
  • the preferred range of the carbon number of the alkanediyl group is the same as the preferred range of the carbon number of the chain saturated hydrocarbon group.
  • the proportion of the chain monomer in the radically polymerizable compound may be, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more.
  • the content may be 40% by mass or more, 50% by mass or more, or 55% by mass or more.
  • the proportion of the chain monomer in the radically polymerizable compound may be, for example, 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less.
  • the proportion of the chain monomer in the radical polymerizable compound is, for example, 10 to 90% by mass, 10 to 85% by mass, 10 to 80% by mass, 20 to 90% by mass, 20 to 85% by mass, 20 to 80% by mass. %, 30-90 mass%, 30-85 mass%, 30-80 mass%, 40-90 mass%, 40-85 mass%, 40-80 mass%, 50-90 mass%, 50-85 mass%, It may be 50-80% by weight, 55-90% by weight, 55-85% by weight or 55-80% by weight.
  • chain monomers include: 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1, 9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14 -Tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, neopentyl glycol dimethacrylate, 1,12-dodecanediol di(meth)acrylate
  • the radically polymerizable compound preferably contains a compound having a fluoro group (hereinafter also referred to as a fluorine-containing monomer).
  • a fluorine-containing monomer a compound having a fluoro group
  • the proportion of the fluorine-containing monomer in the radically polymerizable compound may be, for example, 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0. .5% by mass or more, and may be 0.7% by mass or more, 0.9% by mass or more, or 1% by mass or more. Further, the proportion of the fluorine-containing monomer in the radically polymerizable compound may be, for example, 15% by mass or less, preferably 10% by mass or less, 7% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less. It may be less than % by mass.
  • the proportion of the fluorine-containing monomer in the radically polymerizable compound is, for example, 0.1 to 15% by mass, 0.1 to 10% by mass, 0.1 to 7% by mass, 0.1 to 5% by mass, 0. 1-3 mass%, 0.1-2 mass%, 0.3-15 mass%, 0.3-10 mass%, 0.3-7 mass%, 0.3-5 mass%, 0.3- 3% by mass, 0.3-2% by mass, 0.5-15% by mass, 0.5-10% by mass, 0.5-7% by mass, 0.5-5% by mass, 0.5-3% by mass %, 0.5-2% by mass, 0.7-15% by mass, 0.7-10% by mass, 0.7-7% by mass, 0.7-5% by mass, 0.7-3% by mass, 0.7-2% by mass, 0.9-15% by mass, 0.9-10% by mass, 0.9-7% by mass, 0.9-5% by mass, 0.9-3% by mass, 0. It may be 9-2% by weight, 1-15% by weight, 1-10% by weight, 1-7% by weight,
  • the number of fluoro groups that the fluorine-containing monomer has may be, for example, 1 or more, preferably 2 or more, and more preferably 3 or more. Further, the number of fluoro groups that the fluorine-containing monomer has is not particularly limited, but may be, for example, 40 or less, and preferably 30 or less. That is, the number of fluoro groups that the fluorine-containing monomer has may be, for example, 1 to 40, 1 to 30, 2 to 40, 2 to 30, 3 to 40, or 3 to 30.
  • the content of fluorine atoms based on the total amount of the fluorine-containing monomer may be, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 5% by mass or more.
  • a fluorine-containing monomer that satisfies such a content range exhibits the above-mentioned effects more markedly.
  • the content of fluorine atoms based on the total amount of the fluorine-containing monomer may be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less.
  • the content of fluorine atoms relative to the total amount of the fluorine-containing monomer is, for example, 1 to 75% by mass, 1 to 70% by mass, 1 to 65% by mass, 2 to 75% by mass, 2 to 70% by mass, 2 to 65% by mass. %, 5-75% by weight, 5-70% by weight or 5-65% by weight.
  • the number of radically polymerizable groups that the fluorine-containing monomer has may be one or more. From the viewpoint of easily obtaining a cured product with a low glass transition temperature, the number of radically polymerizable groups contained in the fluorine-containing monomer may be one. Further, from the viewpoint of easily obtaining a cured product having a high glass transition temperature, the number of radically polymerizable groups contained in the fluorine-containing monomer may be 2 or more. There is no particular upper limit to the number of radically polymerizable groups that the fluorine-containing monomer has. The number of radically polymerizable groups that the fluorine-containing monomer has is, for example, 4 or less, preferably 3 or less, more preferably 2 or less from the viewpoint of easily obtaining a cured product with excellent flexibility.
  • fluorine-containing monomer examples include 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and 1H,1H,5H-octafluoropentyl (meth)acrylate.
  • the photopolymerization initiator may be any initiator that can polymerize the above-mentioned radically polymerizable compound.
  • One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
  • photopolymerization initiator for example, 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, benzyl dimethyl ketal; Acetophenone type photopolymerization initiator such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone; 2-dimethylaminoethylbenzoate; p-dimethylaminoethylbenzoate; 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-dioxobicycl
  • an acylphosphine oxide type photopolymerization initiator is preferable because it can be cured using only visible light of 390 nm or more and can be cured without damaging the organic EL element.
  • an acylphosphine oxide type photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferred because it further improves the transparency of the cured product and can be cured using only light of 395 nm or more. is preferred.
  • Examples of the 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide include "Omnirad TPO" manufactured by IGM Resins.
  • the content of the photopolymerization initiator may be, for example, 0.05 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the radically polymerizable compound. Preferably it is 2 parts by mass or more. Further, the content of the photopolymerization initiator may be, for example, 10 parts by mass or less, preferably 8 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the radically polymerizable compound. Such a content tends to ensure sufficient transparency of the encapsulant while obtaining sufficient sensitivity and curing speed of the encapsulant.
  • the content of the photopolymerization initiator is, for example, 0.05 to 10 parts by mass, 0.05 to 8 parts by mass, 0.05 to 5 parts by mass, or 0.5 parts by mass with respect to 100 parts by mass of the radically polymerizable compound. ⁇ 10 parts by weight, 0.5 to 8 parts by weight, 0.5 to 5 parts by weight, 1 to 10 parts by weight, 1 to 8 parts by weight, 1 to 5 parts by weight, 2 to 10 parts by weight, 2 to 8 parts by weight Alternatively, it may be 2 to 5 parts by mass.
  • a stable radical type compound is a compound having a stable radical.
  • One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
  • a nitroxide radical (NO radical) is preferable. That is, as the stable radical type compound, a compound having a nitroxide radical is preferable. Since nitroxide radicals have excellent compatibility and reactivity with radically polymerizable compounds, they can quickly capture radical species.
  • organic EL elements are degraded by oxygen, they are managed at a low oxygen concentration of less than 1 ppm, and the sealant for organic EL elements is also used at a low oxygen concentration.
  • the general phenolic antioxidant used for inhibiting the polymerization of radically polymerizable compounds requires a reaction with oxygen in the process of exhibiting the polymerization inhibiting function. For this reason, it is difficult for phenolic antioxidants to exhibit a polymerization inhibiting function in sealants for organic EL elements.
  • stable radical-type compounds having stable radicals can capture radical species regardless of the presence or absence of oxygen, and therefore can significantly obtain the above-mentioned effects.
  • stable radical type compounds include 1-oxyl-2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and 4-(meth)acryloyl.
  • Examples include oxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-(meth)acryloyloxy-2,2,6,6 from the viewpoint of being less likely to be incorporated into the cured product and cause outgassing.
  • -Tetramethylpiperidine 1-oxyl is preferred, and 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl is more preferred.
  • the content of the stable radical type compound may be, for example, 1 mass ppm or more, preferably 10 mass ppm or more, more preferably 50 mass ppm or more, and even more preferably 100 mass ppm, based on 100 parts by mass of the radically polymerizable compound. ppm or more. Further, the content of the stable radical type compound may be, for example, 15,000 mass ppm or less, preferably 10,000 mass ppm or less, more preferably 8,000 mass ppm or less, and even more preferably It is 6000 mass ppm or less.
  • the content of the stable radical type compound is, for example, 1 to 15,000 mass ppm, 1 to 10,000 mass ppm, 1 to 8,000 mass ppm, 1 to 6,000 mass ppm, 10 to 15,000 mass ppm with respect to 100 parts by mass of the radically polymerizable compound.
  • the sealant of this embodiment may further contain other components than those mentioned above.
  • Other components include antioxidants, surfactants, sensitizers, and the like.
  • the content of other components is not particularly limited, and may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the radically polymerizable compound. It may be 2 parts by mass or less or 1 part by mass or less.
  • the viscosity of the sealant of this embodiment is preferably 3 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more. Further, the viscosity of the sealant of this embodiment is preferably 50 mPa ⁇ s or less, more preferably 30 mPa ⁇ s or less. When the viscosity of the sealant is within the above range, the ejection properties during application by an inkjet method tend to be further improved, and coating film formation tends to be easier. That is, the viscosity of the sealant may be, for example, 3 to 50 mPa ⁇ s, 3 to 30 mPa ⁇ s, 5 to 50 mPa ⁇ s, or 5 to 30 mPa ⁇ s.
  • the viscosity of the sealant indicates a value measured at 25° C. and 250 rpm using a cone-plate viscometer (manufactured by Eiko Seiki Co., Ltd., product number: HB DV3T, etc.).
  • the sulfur atom concentration of the sealant of this embodiment may be, for example, 100 ppm or less, preferably 50 ppm or less, and more preferably 40 ppm or more.
  • the sulfur atom concentration of the sealant of this embodiment may also be, for example, 0.1 ppm or more, or 1 ppm or more. That is, the sulfur atom concentration of the sealant of this embodiment may be, for example, 0.1 to 100 ppm, 0.1 to 50 ppm, 0.1 to 40 ppm, 1 to 100 ppm, 1 to 50 ppm, or 1 to 40 ppm. .
  • a sulfur atom concentration With such a sulfur atom concentration, deterioration of the organic EL element and generation of dark spots are more significantly suppressed, and reliability tends to be further improved.
  • the water concentration of the sealant of this embodiment may be, for example, 100 ppm or less, preferably 70 ppm or less, and more preferably 50 ppm or less.
  • the water concentration of the sealant of this embodiment may also be, for example, 0.5 ppm or more, or 1 ppm or more. That is, the moisture concentration of the sealant of this embodiment may be, for example, 0.5 to 100 ppm, 0.5 to 70 ppm, 0.5 to 50 ppm, 1 to 100 ppm, 1 to 70 ppm, or 1 to 50 ppm. At such a water concentration, the above-mentioned effects tend to be more pronounced.
  • the number of particles with a diameter of 1 ⁇ m or more existing in 1 mL of the sealant of this embodiment is a
  • the number of particles with a diameter of 1 ⁇ m or more existing in 1 mL of the sealant after heating at 80 ° C. for 16 hours is a.
  • ba is preferably 10 or less. According to such a sealant, coating defects caused by particles are suppressed, and excellent discharge performance from the coating device and high flatness of the coated film after coating are realized.
  • the above a is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and may be 0.
  • the above b is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and may be 0.
  • the sealant of this embodiment may contain particles of 1 ⁇ m or more, but preferably does not contain particles (that is, a is 0).
  • particles include particles derived from polymers of radically polymerizable compounds, particles derived from foreign substances such as dust, particles derived from dehydrating agents such as molecular sieves used in the manufacturing process of sealants, etc. .
  • the sealant of this embodiment may be a sealant that does not substantially contain these particles, and the particles may be removed using a filtration filter or the like.
  • the number of particles indicates a value measured using a particle counter (manufactured by Rion Corporation, light scattering particle detector in liquid, product number: KS-42B).
  • the acid value of the sealant of this embodiment is 0.15 (mgKOH/g) or less, preferably 0.13 (mgKOH/g) or less, more preferably 0.10 (mgKOH/g) or less. . Thereby, the above-mentioned effects are more prominently produced. Further, the acid value of the sealant of this embodiment is 0.01 (mgKOH/g) or more, preferably 0.015 (mgKOH/g) or more, more preferably 0.02 (mgKOH/g) or more. It is. Thereby, the effect of the acid component as a polymerization inhibitor is more prominently exhibited.
  • the acid value of the sealant of this embodiment is, for example, 0.01 to 0.15 (mgKOH/g), 0.01 to 0.13 (mgKOH/g), or 0.01 to 0.10 (mgKOH/g). /g), 0.015 to 0.15 (mgKOH/g), 0.015 to 0.13 (mgKOH/g), 0.015 to 0.10 (mgKOH/g), 0.02 to 0.15 (mgKOH/g), 0.02 to 0.13 (mgKOH/g), or 0.02 to 0.10 (mgKOH/g).
  • the acid value of the sealant of this embodiment shows the value measured by the following method. Weigh 2 g of the sample into a 50 mL tall beaker, add 40 mL of 2-propanol, and stir for 5 minutes. After confirming the stability of the potential, the end point was determined by potentiometric titration using a titrant 0.1 mol/L 2-propanolic potassium hydroxide standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) using an automatic titrator COM 550 manufactured by Hiranuma Seisakusho. demand.
  • the method for manufacturing the sealant of this embodiment is not particularly limited, it can be manufactured, for example, by the following method.
  • Method for manufacturing sealant In the method for producing a sealant of the present embodiment, at least a part of the radically polymerizable compound is added to the following (i) so that the acid value of the sealant is 0.01 to 0.15 (mgKOH/g). and a mixing step of mixing a radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical to obtain a sealant.
  • the pretreatment step may further include pretreatment by methods (ii) and (iii). (i) Degassing treatment in an environment of 10 to 100°C and 1000 Pa or less (ii) Distillation purification (iii) Column chromatography purification
  • the acid value of the sealant is due to a trace amount of acid component in the radically polymerizable compound. Therefore, in the manufacturing method of this embodiment, the acid value of the sealant is adjusted to a specific range by pretreating the radically polymerizable compound in the pretreatment step.
  • the pretreatment method in the pretreatment step includes (i) and may further include either (ii) or (iii).
  • the pretreatment method (i) is a method of degassing the radically polymerizable compound.
  • each radically polymerizable compound may be individually degassed, or multiple types of radically polymerizable compounds may be simultaneously degassed (multiple types of The mixture of radically polymerizable compounds may be subjected to deaeration treatment).
  • the temperature in the degassing treatment is 10 to 100°C, preferably 30 to 90°C, and more preferably 40 to 80°C.
  • the pressure in the degassing treatment is 1000 Pa or less, preferably 800 Pa or less, more preferably 500 Pa or less. Further, the pressure in the degassing process may be, for example, 1 Pa or more, or 10 Pa or more. That is, the pressure in the deaeration process may be, for example, 1 to 1000 Pa, 1 to 800 Pa, 1 to 500 Pa, 10 to 1000 Pa, 10 to 800 Pa, or 10 to 500 Pa.
  • the degassing treatment can be carried out, for example, in a container equipped with a stirring means and connected to a vacuum pump and a vacuum gauge.
  • air bubbling air blowing
  • the degassing treatment may be carried out, for example, in a container equipped with a stirring means and connected to a vacuum pump and a vacuum gauge.
  • air bubbling air blowing
  • the pretreatment method (ii) is a method of purifying the radically polymerizable compound by distillation.
  • Suitable conditions for distillation purification include, for example, a temperature of 10 to 100°C and a pressure of 0.1 MPa or less.
  • distillation purification include the following methods. Note that the distillation purification method is not limited to the following method, and may be appropriately selected from known distillation purification methods.
  • the radically polymerizable compound was heated at a pressure of 0.05 MPa and a rotational speed of 50 r/min in a hot bath adjusted to 65°C using a rotary distillation apparatus (manufactured by Tokyo Rika Kikai Co., Ltd., "Rotary Evaporator N-1000S"). Distill for 3 hours.
  • the pretreatment method (iii) is a method of purifying a radically polymerizable compound by column chromatography.
  • column chromatography purification examples include column chromatography purification using silica gel as an adsorbent.
  • column chromatography purification examples include the following method.
  • the column chromatography purification method is not limited to the following method, and may be appropriately selected from known column chromatography purification methods.
  • pretreatment is performed so that the acid value of the sealant is 0.01 to 0.15 (mgKOH/g).
  • the pretreatment conditions may be adjusted as appropriate depending on the amount of the radically polymerizable compound in the sealant. That is, in the pretreatment step, the pretreatment conditions and the like may be adjusted as appropriate depending on the predetermined composition of the sealant.
  • the mixing step is a step of mixing a radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical to obtain a sealant.
  • the mixing method in the mixing step is not particularly limited, and examples thereof include methods such as mixing using a stirrer such as a three-one motor and mixing using a mix rotor.
  • Suitable mixing conditions in the mixing step include, for example, mixing at a temperature of 15 to 40° C. for 1 hour or more.
  • a cured product containing a polymer of a radically polymerizable compound can be obtained.
  • This cured product may contain a stable radical as a stable radical type compound or a reactant thereof.
  • This cured product can be suitably used as a sealing material for organic EL elements.
  • the sealant of this embodiment can be cured by light irradiation.
  • the light source used for curing the sealant of this embodiment is not particularly limited. Examples of light sources include halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium, etc.), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, LEDs, etc. can be mentioned.
  • the above light sources have different emission wavelengths and energy distributions. Therefore, the light source may be appropriately selected depending on the reaction wavelength of the photopolymerization initiator. Natural light (sunlight) can also be a light source for initiating the reaction.
  • Irradiation by a light source may be direct irradiation, or may be focused irradiation using a reflecting mirror, fiber, etc. Alternatively, irradiation may be performed using a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like.
  • Examples of the method for sealing an organic EL element using the sealant of this embodiment include the following sealing method.
  • a substrate on which an organic EL element is installed is prepared, and a sealant is applied on the surface of the substrate on which the organic EL element is installed to form a coating film of the sealant.
  • the coating film is irradiated with light to form a sealant made of a cured sealant.
  • the organic EL element is sealed with the sealing material.
  • an inkjet method for applying the sealant.
  • an organic EL display device it is necessary to apply a sealant onto a large-area substrate on which a plurality of organic EL elements are installed.
  • the sealant of this embodiment can be applied while maintaining high ejection properties even when using an inkjet method, so that a coating film can be uniformly formed on a large-area substrate.
  • the thickness of the coating film of the sealant may be, for example, 1 ⁇ m or more, and preferably 3 ⁇ m or more. This makes it easier to form a sealing material having sufficient sealing ability. Further, the thickness of the coating film of the sealant may be, for example, 10 ⁇ m or less, and preferably 9 ⁇ m or less. This is expected to reduce the size of organic EL display devices and reduce manufacturing costs. That is, the thickness of the coating film of the sealant may be, for example, 1 to 10 ⁇ m, 1 to 9 ⁇ m, 3 to 10 ⁇ m, or 3 to 9 ⁇ m.
  • the present invention is not limited to the above embodiments.
  • the present invention can adopt various configurations other than those described above.
  • the present invention may be modified or improved from the above embodiments within the scope that can achieve the object of the present invention.
  • the present invention may relate to an organic EL display device that includes an organic EL element and a sealing material that seals the organic EL element.
  • the sealant includes a cured product of the above-mentioned sealant.
  • the organic EL element may be a known organic EL element.
  • the configuration other than the organic EL element and the sealing material may be the same as that of a known organic EL display device.
  • A) Radical polymerizable compound (A-1) SR262 (1,12-dodecanediol dimethacrylate, manufactured by Arkema) (chain monomer) (A-2) BPE200 (ethoxylated bisphenol A dimethacrylate (compound represented by the following formula (m+n 4), manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (aromatic monomer) (A-3) LINC-162A (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-de Candiacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) (fluorine-containing monomer) (A-4) FA-512AS (dicyclopentenyloxyethyl acrylate, manufactured by Showa Denko Materials) (unsaturated alicyclic monomer) (A-5) DCP (dimethylol-tricyclode
  • B Polymerization initiator (B-1) TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by IGM Resins)
  • C Stable radical type compound (C-1) TEMPO methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, manufactured by Tokyo Kasei Kogyo Co., Ltd.)
  • ITO 150nm Hole injection layer (polymer HIL): 60nm Hole transport layer ( ⁇ -NPD): 30nm Light-emitting layer (Ir(ppy) 3 +CBP [6%]): 30 nm Hole blocking layer (BAlq): 10nm Electron transport layer (Alq 3 ): 30 nm Electron injection layer (LiF): 0.8nm Cathode (MgAg/IZO): 10nm/100nm ITO is indium tin oxide, HIL is Hole Injection Layer, ⁇ -NPD is N,N'-diphenyl-N,N'-dinaphthylbenzidine, and Ir(ppy) 3 is an iridium complex [tris(2 -phenylpyridine)iridium], CBP is 4,4'-N,N'-dicarbazole-biphenyl, and BAlq is bis(2-methyl-8-quinolinolato)(p-phenyl, ⁇
  • Alq 3 is tris(8-hydroxyquinolinolato)aluminum
  • LiF is lithium fluoride
  • IZO is indium zinc oxide.
  • a cured film was thus obtained.
  • a mask (cover) having an opening of 10 mm x 10 mm was placed so as to cover the entire cured film, and a SiN film was formed by plasma CVD.
  • the thickness of the formed SiN (inorganic film) was about 1 ⁇ m.
  • a sealed body of an organic EL element was obtained.
  • the obtained sealed body was bonded to a 30 mm x 30 mm x 0.7 mm thick alkali-free glass (Eagle XG manufactured by Corning) using a 30 mm x 30 mm x 25 ⁇ m thick transparent base material-less double-sided tape. In this way, an organic EL display device for evaluation was manufactured.
  • the organic EL display device for evaluation was left standing in a high temperature and high humidity environment of 85° C. and 85% RH for 500 hours. Before and after this high-temperature, high-humidity treatment, a current was applied to the organic EL display device for evaluation, and the light-emitting surface was photographed. The photographed images (images before high-temperature, high-humidity treatment and images after high-temperature, high-humidity treatment) were analyzed using Innotek's image analysis software "Quick Grain" to determine the luminescent area. Then, the luminescent area reduction rate (%) before and after the high temperature and high humidity treatment was calculated.
  • Examples 1-2 Comparative Example 1
  • the radically polymerizable compounds shown in Table 1 were mixed in the composition shown in Table 1, and deaeration treatment was performed in an environment of 60° C. and 800 Pa for the time shown in Table 1.
  • each component was mixed with the composition shown in Table 1 to create a sealant.
  • the above measurements and evaluations were performed on the obtained sealant. The results are shown in Table 1.
  • Examples 3-4 Comparative Example 2
  • the radical polymerizable compounds shown in Table 2 were mixed in the composition shown in Table 2, and deaeration treatment was performed in an environment of 60° C. and 800 Pa for the time shown in Table 2.
  • each component was mixed with the composition shown in Table 2 to create a sealant.
  • the above measurements and evaluations were performed on the obtained sealant. The results are shown in Table 2.

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Abstract

Provided is a sealing agent for organic electroluminescent elements, which comprises a radical-polymerizable compound, a photopolymerization initiator, and a persistent radical-type compound having a persistent radical and which has an acid value of 0.01-0.15 (mgKOH/g).

Description

有機エレクトロルミネッセンス素子用封止剤、封止材及び有機エレクトロルミネッセンス表示装置、及び、有機エレクトロルミネッセンス素子用封止剤の製造方法Encapsulant for organic electroluminescent elements, encapsulant, organic electroluminescent display device, and method for producing encapsulant for organic electroluminescent elements
　本発明は、有機エレクトロルミネッセンス素子用封止剤、封止材及び有機エレクトロルミネッセンス表示装置、及び、有機エレクトロルミネッセンス素子用封止剤の製造方法に関する。 The present invention relates to a sealant for an organic electroluminescent device, a sealing material, an organic electroluminescent display device, and a method for manufacturing the sealant for an organic electroluminescent device.
　有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子ともいう）は、高い輝度の発光が可能な素子体として注目を集めている。しかし、有機ＥＬ素子には、酸素や水分により劣化し、発光特性が低下するという課題があった。これを解決するため、有機ＥＬ素子を封止し、劣化を防止する技術が検討されている。 Organic electroluminescent devices (hereinafter also referred to as organic EL devices) are attracting attention as device bodies that can emit light with high brightness. However, organic EL elements have a problem in that they are degraded by oxygen and moisture, resulting in reduced light-emitting characteristics. In order to solve this problem, techniques for sealing organic EL elements and preventing deterioration are being considered.
　封止方法の一つとして、例えば特許文献１には、重合性化合物と重合開始剤とを含有し、２５℃における粘度が５～５０ｍＰａ・ｓであり、２５℃における表面張力が１５～３５ｍＮ／ｍであり、かつ、２５℃、５０％ＲＨの環境下に２４時間静置した後の２５℃における含水率が１０００ｐｐｍ以下である、有機ＥＬ素子用封止剤が記載されている。 As one of the sealing methods, for example, Patent Document 1 describes a sealing method that contains a polymerizable compound and a polymerization initiator, has a viscosity of 5 to 50 mPa·s at 25°C, and has a surface tension of 15 to 35 mN/s at 25°C. The encapsulant for organic EL elements is described, which has a water content of 1000 ppm or less at 25° C. after standing for 24 hours in an environment of 25° C. and 50% RH.
特開２０１９－０４０８７２号公報Japanese Patent Application Publication No. 2019-040872
　有機ＥＬ素子用封止剤としては、熱硬化性封止剤と光硬化性封止剤とが知られている。光硬化性封止剤は、封止時に加熱を必要としないため、有機ＥＬ素子を高熱に曝すことなく封止材を形成でき、高熱による有機ＥＬ素子の変形・変質等が抑制されるという利点を有する。 As encapsulants for organic EL elements, thermosetting encapsulants and photocurable encapsulants are known. Photocurable encapsulants do not require heating during sealing, so they can form encapsulants without exposing organic EL elements to high heat, and have the advantage of suppressing deformation and deterioration of organic EL elements due to high heat. has.
　近年、電子デバイスの要求特性が高まり、例えば、有機ＥＬ素子に対するより高い信頼性を実現可能な封止材が求められている。 In recent years, the required characteristics of electronic devices have increased, and for example, there is a demand for a sealing material that can realize higher reliability for organic EL elements.
　しかし、従来の光硬化性封止剤では、高温高湿下の耐久試験において、ダークスポットの発生を十分に抑制することが困難であった。 However, with conventional photocurable sealants, it was difficult to sufficiently suppress the occurrence of dark spots in durability tests under high temperature and high humidity conditions.
　そこで本発明は、高温高湿下でのダークスポットの発生を顕著に抑制可能な、有機ＥＬ素子用封止剤を提供することを目的とする。また、本発明は、当該有機ＥＬ素子用封止剤から形成される封止材、当該封止材を備える有機ＥＬ表示装置、及び、当該有機ＥＬ素子用封止剤の製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide an encapsulant for organic EL elements that can significantly suppress the occurrence of dark spots under high temperature and high humidity conditions. Further, the present invention provides a sealant formed from the sealant for organic EL elements, an organic EL display device equipped with the sealant, and a method for manufacturing the sealant for organic EL elements. With the goal.
　本発明は、例えば、下記＜１＞～＜７＞に関する。
＜１＞　ラジカル重合性化合物と、光重合開始剤と、安定ラジカルを有する安定ラジカル型化合物と、を含有し、酸価が０．０１～０．１５（ｍｇＫＯＨ／ｇ）である、有機エレクトロルミネッセンス素子用封止剤。
＜２＞　前記安定ラジカルがニトロキシドラジカルである、＜１＞に記載の封止剤。
＜３＞　＜１＞又は＜２＞に記載の封止剤の硬化体を含む、封止材。
＜４＞　有機エレクトロルミネッセンス素子と、前記有機エレクトロルミネッセンス素子を封止する、＜３＞に記載の封止材と、を備える、有機エレクトロルミネッセンス表示装置。
＜５＞　＜１＞又は＜２＞に記載の封止剤の製造方法であって、
　前記封止剤の酸価が０．０１～０．１５（ｍｇＫＯＨ／ｇ）となるように、ラジカル重合性化合物の少なくとも一部を、１０～１００℃、１０００Ｐａ以下の環境下で脱気処理する前処理工程と、
　前記ラジカル重合性化合物と、光重合開始剤と、安定ラジカルを有する安定ラジカル型化合物と、を混合して、前記封止剤を得る混合工程と、
を含む、有機エレクトロルミネッセンス素子用封止剤の製造方法。 The present invention relates to, for example, the following <1> to <7>.
<1> Organic electroluminescence containing a radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical, and having an acid value of 0.01 to 0.15 (mgKOH/g) Encapsulant for elements.
<2> The sealant according to <1>, wherein the stable radical is a nitroxide radical.
<3> A sealing material comprising a cured product of the sealant according to <1> or <2>.
<4> An organic electroluminescent display device comprising an organic electroluminescent element and the sealing material according to <3>, which seals the organic electroluminescent element.
<5> A method for manufacturing the sealant according to <1> or <2>, comprising:
At least a portion of the radically polymerizable compound is degassed in an environment of 10 to 100°C and 1000 Pa or less so that the acid value of the sealant is 0.01 to 0.15 (mgKOH/g). a pretreatment step;
A mixing step of obtaining the sealant by mixing the radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical;
A method for producing a sealant for an organic electroluminescent device, comprising:
　本発明によれば、高温高湿下でのダークスポットの発生を顕著に抑制可能な、有機ＥＬ素子用封止剤が提供される。また、本発明によれば、当該有機ＥＬ素子用封止剤から形成される封止材、当該封止材を備える有機ＥＬ表示装置、及び、当該有機ＥＬ素子用封止剤の製造方法が提供される。 According to the present invention, an encapsulant for organic EL elements is provided that can significantly suppress the occurrence of dark spots under high temperature and high humidity conditions. Further, according to the present invention, there is provided a sealant formed from the sealant for organic EL elements, an organic EL display device including the sealant, and a method for manufacturing the sealant for organic EL elements. be done.
　以下、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
　本明細書中、数値範囲の説明における「Ｘ～Ｙ」との表記は、特に断らない限り、Ｘ以上Ｙ以下を意味する。例えば、「１～５質量％」とは「１質量％以上５質量％以下」を意味する。 In this specification, the expression "X to Y" in the description of numerical ranges means from X to Y, unless otherwise specified. For example, "1 to 5% by mass" means "1 to 5% by mass".
　本明細書における基（原子団）の表記において、置換か無置換かを記していない表記は、置換基を有しないものと置換基を有するものの両方を包含するものである。例えば「アルキル基」とは、置換基を有しないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。 In the description of groups (atomic groups) in this specification, descriptions that do not indicate whether they are substituted or unsubstituted include both those without a substituent and those with a substituent. For example, the term "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
　本明細書における「（メタ）アクリル」との表記は、アクリルとメタクリルの両方を包含する。「（メタ）アクリレート」等の類似の表記についても同様である。 In this specification, the expression "(meth)acrylic" includes both acrylic and methacrylic. The same applies to similar expressions such as "(meth)acrylate".
＜封止剤＞
　本実施形態の封止剤は、ラジカル重合性化合物と、光重合開始剤と、安定ラジカルを有する安定ラジカル型化合物と、を含有する。また、本実施形態の封止剤は、酸価が０．０１～０．１５（ｍｇＫＯＨ／ｇ）である。 <Sealant>
The sealant of this embodiment contains a radically polymerizable compound, a photopolymerization initiator, and a stable radical type compound having a stable radical. Further, the sealant of this embodiment has an acid value of 0.01 to 0.15 (mgKOH/g).
　本実施形態の封止剤は、有機エレクトロルミネッセンス素子封止用である。すなわち、本実施形態の封止剤は、有機ＥＬ素子を封止して有機ＥＬ表示装置を製造するために用いられる。本実施形態の封止剤は、光重合開始剤を含むため、光硬化性封止剤である。 The sealant of this embodiment is for sealing an organic electroluminescent element. That is, the sealant of this embodiment is used to seal an organic EL element and manufacture an organic EL display device. The sealant of this embodiment is a photocurable sealant because it contains a photopolymerization initiator.
　本実施形態の封止剤で有機ＥＬ素子を封止することにより、高温高湿下でのダークスポットの発生が顕著に抑制される。 By sealing the organic EL element with the sealant of this embodiment, the occurrence of dark spots under high temperature and high humidity is significantly suppressed.
　本実施形態の封止剤により上記効果が奏される理由は必ずしも限定されないが、以下の理由が考えられる。
　本発明者らの知見によれば、従来の封止剤は、封止剤の硬化により形成される封止材中に微量の酸成分が存在しており、当該酸成分の存在によって、封止材中に水分が侵入したとき、封止材の加水分解による劣化が生じて、信頼性が低下する場合があった。本実施形態の封止剤は、酸価が０．１５ｍｇＫＯＨ／ｇ以下であるため、封止材中への酸成分の残存が少なく、封止材中に微量の水分が侵入した場合でも、封止材の加水分解が生じにくい。このため、本実施形態の封止剤によれば、高温高湿下であっても劣化し難い封止材を形成でき、封止材の劣化に起因するダークスポットの発生を抑制できる。 Although the reason why the sealant of this embodiment achieves the above effects is not necessarily limited, the following reasons can be considered.
According to the findings of the present inventors, conventional encapsulants contain a trace amount of acid component in the encapsulant formed by curing the encapsulant, and due to the presence of the acid component, the sealant is When moisture enters the sealing material, the sealing material may deteriorate due to hydrolysis, resulting in a decrease in reliability. Since the encapsulant of this embodiment has an acid value of 0.15 mgKOH/g or less, there is little residual acid component in the encapsulant, and even if a small amount of moisture enters the encapsulant, the encapsulant will remain intact. Hydrolysis of the stopper material is less likely to occur. Therefore, according to the sealant of the present embodiment, it is possible to form a sealant that does not easily deteriorate even under high temperature and high humidity conditions, and it is possible to suppress the occurrence of dark spots due to deterioration of the sealant.
　また、本実施形態の封止剤は、酸価が０．０１ｍｇＫＯＨ／ｇ以上であり、極めて微量の酸成分を含有する。本実施形態では、この極めて微量の酸成分が重合禁止剤として働き、封止剤が貯蔵安定性に優れたものとなり、保管時の封止剤の劣化に起因する信頼性の低下が抑制されると考えられる。 Furthermore, the sealant of this embodiment has an acid value of 0.01 mgKOH/g or more and contains an extremely small amount of acid component. In this embodiment, this extremely small amount of acid component acts as a polymerization inhibitor, making the sealant excellent in storage stability, and suppressing a decrease in reliability due to deterioration of the sealant during storage. it is conceivable that.
　また、本実施形態の封止剤は、塗布装置からの吐出性に優れる。具体的には、本実施形態の封止剤によれば、塗布装置からの吐出時に、吐出液の曲がり、吐出液量のばらつき等が抑制され、良好な吐出性が維持される。これにより、本実施形態の封止剤によれば、厚みムラが顕著に少ない、平坦性に優れた塗膜を形成できる。また、本実施形態の封止剤によれば、有機ＥＬ素子の信頼性向上に寄与する封止材を形成することができる。 Furthermore, the sealant of this embodiment has excellent discharge properties from the coating device. Specifically, according to the sealant of this embodiment, when the sealant is discharged from the coating device, bending of the discharged liquid, variation in the amount of the discharged liquid, etc. are suppressed, and good dischargeability is maintained. As a result, according to the sealant of the present embodiment, a coating film with significantly less uneven thickness and excellent flatness can be formed. Moreover, according to the encapsulant of this embodiment, it is possible to form a encapsulant that contributes to improving the reliability of organic EL elements.
　本実施形態の封止剤により上記効果が奏される理由は必ずしも限定されないが、以下の理由が考えられる。
　本発明者らの知見によれば、従来の光硬化性封止剤では、塗布装置から封止剤を吐出する際に、吐出液の曲がり、吐出液量のばらつき等が生じて、これにより塗膜に厚みムラ生じ、塗膜の平坦性が低下する場合があった。この原因として、光硬化性封止剤は、封止剤の使用前（例えば保管中、運搬中、等）に意図しない重合が生じやすく、当該重合によって生じた微細なパーティクルが、塗布装置の流路を狭めて、吐出液の曲がり、吐出液量のばらつき等を生じさせると考えられる。
　本実施形態の封止剤では、安定ラジカル型化合物を含有することで、光硬化性封止剤でありながら、使用前（例えば保管中、運搬中、等）の意図しない重合、及び当該重合によるパーティクルの発生が顕著に抑制される。このため、本実施形態の封止剤では、パーティクルに起因する塗布不良が抑制されて、塗布装置からの優れた吐出性、及び、塗布後の塗膜の高い平坦性が実現される。 Although the reason why the sealant of this embodiment achieves the above effects is not necessarily limited, the following reasons can be considered.
According to the findings of the present inventors, with conventional photocurable sealants, when the sealant is discharged from the coating device, bending of the discharged liquid, variations in the amount of discharged liquid, etc. occur, and this causes the coating to be applied. There were cases where the film became uneven in thickness and the flatness of the coating film decreased. The reason for this is that photocurable sealants tend to undergo unintentional polymerization before use (for example, during storage, transportation, etc.), and the fine particles generated by the polymerization may flow through the coating equipment. It is thought that this narrows the path, causing bending of the ejected liquid, variations in the amount of ejected liquid, and the like.
The sealant of this embodiment contains a stable radical type compound, so that although it is a photocurable sealant, there is no possibility of unintentional polymerization before use (for example, during storage, transportation, etc.) or due to the polymerization. Generation of particles is significantly suppressed. Therefore, with the sealant of the present embodiment, coating defects caused by particles are suppressed, and excellent discharge properties from the coating device and high flatness of the coated film after coating are achieved.
　また、従来の光硬化性封止剤では、光照射時に、塗膜の厚みムラ、照射量のばらつき等に起因して、光重合開始剤、光重合開始剤から生成したラジカル種、重合過程で生じるラジカル種等の反応点が硬化体中に残存する場合があった。そして、このような反応点の残存があることで、封止作業後の硬化体中で更なる重合が起こり、硬化体が硬化収縮する場合があった。通常、有機ＥＬ素子と封止材（封止剤の硬化体）との間には、膜厚１μｍ程度の無機保護膜が設けられるが、硬化収縮が生じると無機保護膜に負荷がかかってクラックを発生しやすく、クラックからの水又は酸素の侵入によって有機ＥＬ素子の信頼性が低下する場合があった。
　本実施形態の封止剤は、安定ラジカル型化合物を含有することで、硬化体中に上述の反応点が残存しにくく、また、反応点からの更なる重合も抑制される。このため、本実施形態の封止剤によれば、反応点に起因する変質が生じ難く、硬化収縮による無機保護膜の損傷を抑制でき、有機ＥＬ素子の信頼性向上に寄与する封止材を形成できる。 In addition, with conventional photocurable encapsulants, during light irradiation, due to uneven coating film thickness, variations in irradiation amount, etc., the photopolymerization initiator, radical species generated from the photopolymerization initiator, and the like during the polymerization process. Reaction points such as generated radical species may remain in the cured product. When such reaction points remain, further polymerization occurs in the cured product after the sealing operation, and the cured product may harden and shrink. Normally, an inorganic protective film with a thickness of about 1 μm is provided between the organic EL element and the encapsulant (hardened encapsulant), but when curing shrinkage occurs, stress is applied to the inorganic protective film and cracks occur. The reliability of the organic EL device may be lowered due to the intrusion of water or oxygen through the cracks.
Since the sealant of this embodiment contains a stable radical type compound, the above-mentioned reaction points are unlikely to remain in the cured product, and further polymerization from the reaction points is also suppressed. Therefore, according to the encapsulant of this embodiment, deterioration due to reaction points is difficult to occur, damage to the inorganic protective film due to curing shrinkage can be suppressed, and the encapsulant contributes to improving the reliability of organic EL elements. Can be formed.
（ラジカル重合性化合物）
　ラジカル重合性化合物は、後述の光重合開始剤から発生する活性種により重合可能な化合物であればよい。ラジカル重合性化合物は１種を単独で用いてよく、２種以上を組み合わせて用いてもよい。 (Radical polymerizable compound)
The radically polymerizable compound may be any compound that can be polymerized by active species generated from the photopolymerization initiator described below. One type of radically polymerizable compound may be used alone, or two or more types may be used in combination.
　ラジカル重合性化合物は、ラジカル重合性基を有する化合物ということができる。ラジカル重合性基としては、例えばビニル基、（メタ）アクリロイル基、アリル基、ビニルエーテル基、ビニルエステル基、（メタ）アクリルアミド基等が挙げられ、これらのうち、（メタ）アクリロイル基が特に好ましい。 A radically polymerizable compound can be said to be a compound having a radically polymerizable group. Examples of the radically polymerizable group include a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, a vinyl ester group, a (meth)acrylamide group, and among these, a (meth)acryloyl group is particularly preferred.
　ラジカル重合性化合物は、例えば、ラジカル重合性基を２つ以上有する多官能化合物を含むことが好ましい。多官能化合物におけるラジカル重合性基の数は、例えば２～６であってよく、好ましくは２～４である。多官能化合物を用いることで、光硬化性がより向上する傾向がある。 The radically polymerizable compound preferably includes, for example, a polyfunctional compound having two or more radically polymerizable groups. The number of radically polymerizable groups in the polyfunctional compound may be, for example, 2 to 6, preferably 2 to 4. By using a polyfunctional compound, photocurability tends to be further improved.
　封止材としての諸特性がバランス良く得られる観点からは、多官能化合物としては、ラジカル重合性基を２つ有する二官能化合物が好ましい。 From the viewpoint of obtaining well-balanced properties as a sealing material, the polyfunctional compound is preferably a bifunctional compound having two radically polymerizable groups.
　ラジカル重合性化合物は、ラジカル重合性基を１つ有する単官能化合物を含んでいてもよい。重合速度、硬化体の物性等の調整が容易となる観点から、ラジカル重合性化合物は、多官能化合物と単官能化合物とを含むことが好ましい。 The radically polymerizable compound may include a monofunctional compound having one radically polymerizable group. From the viewpoint of easy adjustment of the polymerization rate, physical properties of the cured product, etc., the radically polymerizable compound preferably contains a polyfunctional compound and a monofunctional compound.
　ラジカル重合性化合物が多官能化合物及び単官能化合物を含む場合、ラジカル重合性化合物に占める多官能化合物の割合は、例えば３０質量％以上であってよく、好ましくは５０質量％以上、より好ましくは６０質量％以上、更に好ましくは７０質量％以上、一層好ましくは８０質量％以上であり、８５質量％以上又は９０質量％以上であってもよい。また、重合性化合物に占める多官能化合物の割合は、例えば１００質量％以下であってよく、好ましくは９５質量％以下である。
　すなわち、ラジカル重合性化合物に占める多官能化合物の割合は、例えば３０～１００質量％、３０～９５質量％、５０～１００質量％、５０～９５質量％、６０～１００質量％、６０～９５質量％、７０～１００質量％、７０～９５質量％、８０～１００質量％、８０～９５質量％、８５～１００質量％、８５～９５質量％、９０～１００質量％又は９０～９５質量％であってもよい。 When the radically polymerizable compound includes a polyfunctional compound and a monofunctional compound, the proportion of the polyfunctional compound in the radically polymerizable compound may be, for example, 30% by mass or more, preferably 50% by mass or more, and more preferably 60% by mass or more. The content is at least 70% by mass, more preferably at least 80% by mass, and may be at least 85% by mass or at least 90% by mass. Further, the proportion of the polyfunctional compound in the polymerizable compound may be, for example, 100% by mass or less, and preferably 95% by mass or less.
That is, the proportion of the polyfunctional compound in the radically polymerizable compound is, for example, 30 to 100% by mass, 30 to 95% by mass, 50 to 100% by mass, 50 to 95% by mass, 60 to 100% by mass, 60 to 95% by mass. %, 70-100% by mass, 70-95% by mass, 80-100% by mass, 80-95% by mass, 85-100% by mass, 85-95% by mass, 90-100% by mass or 90-95% by mass. There may be.
　多官能化合物としては、（メタ）アクリロイル基を２つ以上有する多官能（メタ）アクリル化合物が好ましい。多官能（メタ）アクリル化合物の具体例としては、
　ビス（１－（メタ）アクリロキシ－２－ヒドロキシプロピル）フタレート、ビス（２－（メタ）アクリロキシエチル）ホスフェート、ビス（（メタ）アクリロキシ－２－ヒドロキシプロピルオキシ）ジエチレングリコール、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡジ－（３－（メタ）アクリロキシエチル）エーテル、ビスフェノールＡジ－（３－（メタ）アクリロキシ－２－ヒドロキシプロピル）エーテル、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ－（３－（メタ）アクリロキシ－２－ヒドロキシプロピル）エーテル、１，４－ブタンジオールジ（メタ）アクリレート、１，３－ブタンジオールビス（（メタ）アクリロキシプロピオネート）、１，４－ブタンジオールビス（（メタ）アクリロキシプロピオネート）、２－ブテン－１，４－ジオールジ（メタ）アクリレート、１，４－シクロヘキサンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、２，２－ジメチル－１，３－プロパンジオールジ（メタ）アクリレート、ジペンタエリスリトールエーテルジ（メタ）アクリレート、ジフェノール酸ジ－（３－（メタ）アクリロキシ－２－ヒドロキシプロピル）エーテル、ジプロピレングリコールジ（メタ）アクリレート、７，７，９－トリメチル－３，１３－ジオキソ－３，１４－ジオキサ－５，１２－ジアザヘキサデカン－１，１６－ジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、１，２－エタンジオールジ（メタ）アクリレート、１，２－エタンジオールビス（（メタ）アクリロキシプロピオネート）、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，５－ペンタンジオールジ（メタ）アクリレート、１，４－フェニレンジ（メタ）アクリレート、１－フェニル－１，２－エタンジオールジ（メタ）アクリレート、ポリオキシエチル－２，２－ジ（ｐ－ヒドロキシフェニル）プロパンジ（メタ）アクリレート、１，２－プロパンジオールジ（メタ）アクリレート、１，３－プロパンジオールジ（メタ）アクリレート、プロポキシ化ビスフェノールＡジ（メタ）アクリレート、テトラブロモビスフェノールＡジ－（３－（メタ）アクリロキシ－２－ヒドロキシプロピル）エーテル、テトラクロロビスフェノールＡジ－（３－（メタ）アクリロキシ－２－ヒドロキシプロピル）エーテル、テトラエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、２，２，４－トリメチル－１，３－ペンタンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート。ジメチロール－トリシクロデカンジ（メタ）アクリレート、エトキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化エトキシ化ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡエポキシジ（メタ）アクリレート、２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９－ヘキサデカフルオロ－１，１０－デカンジアクリレート等の二官能（メタ）アクリル化合物；
　１，２，４－ブタントリオールトリ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ポリオキシプロピルトリメチロールプロパントリ（メタ）アクリレート、シリコーントリ（メタ）アクリレート、１，３，５－トリ（メタ）アクリロイルヘキサヒドロ－ｓ－トリアジン、トリメチロールエタントリ（メタ）アクリレート、１，１，１－トリメチロールプロパントリ（メタ）アクリレート、１，２，３－トリメチロールプロパントリ（メタ）アクリレート、１，１，１－トリメチロールプロパントリス（（メタ）アクリロキシプロピオネート）、１，２，３－トリメチロールプロパントリス（（メタ）アクリロキシプロピオネート）、トリス－（２－（メタ）アクリロキシエチル）イソシアヌレート等の三官能（メタ）アクリル化合物；
　ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールテトラキス（（メタ）アクリロキシプロピオネート）等の四官能（メタ）アクリル化合物；
等が挙げられる。 As the polyfunctional compound, a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups is preferred. Specific examples of polyfunctional (meth)acrylic compounds include:
Bis(1-(meth)acryloxy-2-hydroxypropyl) phthalate, bis(2-(meth)acryloxyethyl) phosphate, bis((meth)acryloxy-2-hydroxypropyloxy) diethylene glycol, bisphenol A di(meth) acrylate, bisphenol A di-(3-(meth)acryloxyethyl) ether, bisphenol A di-(3-(meth)acryloxy-2-hydroxypropyl) ether, 1,3-butanediol di(meth)acrylate, 1 , 4-butanediol di-(3-(meth)acryloxy-2-hydroxypropyl) ether, 1,4-butanediol di(meth)acrylate, 1,3-butanediol bis((meth)acryloxypropionate ), 1,4-butanediol bis((meth)acryloxypropionate), 2-butene-1,4-diol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,10- Decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 2,2-dimethyl-1,3-propanediol di(meth)acrylate, dipentaerythritol ether di(meth)acrylate, diphenolic acid di(3 -(meth)acryloxy-2-hydroxypropyl) ether, dipropylene glycol di(meth)acrylate, 7,7,9-trimethyl-3,13-dioxo-3,14-dioxa-5,12-diazahexadecane- 1,16-diol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-ethanediol di(meth)acrylate, 1,2-ethanediol bis((meth)acryloxypropionate ), 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,4-phenylenedi(meth)acrylate, 1 -Phenyl-1,2-ethanediol di(meth)acrylate, polyoxyethyl-2,2-di(p-hydroxyphenyl)propane di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1, 3-propanediol di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, tetrabromobisphenol A di-(3-(meth)acryloxy-2-hydroxypropyl) ether, tetrachlorobisphenol A di-(3- (meth)acryloxy-2-hydroxypropyl) ether, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, Tripropylene glycol di(meth)acrylate. Dimethylol-tricyclodecane di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxy di(meth)acrylate , 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decane diacrylate, etc. ) acrylic compound;
1,2,4-butanetriol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, polyoxypropyltrimethylolpropane tri(meth)acrylate, silicone tri(meth)acrylate, 1, 3,5-tri(meth)acryloylhexahydro-s-triazine, trimethylolethane tri(meth)acrylate, 1,1,1-trimethylolpropane tri(meth)acrylate, 1,2,3-trimethylolpropane tri (meth)acrylate, 1,1,1-trimethylolpropane tris ((meth)acryloxypropionate), 1,2,3-trimethylolpropane tris ((meth)acryloxypropionate), tris-( Trifunctional (meth)acrylic compounds such as 2-(meth)acryloxyethyl)isocyanurate;
Tetrafunctional (meth)acrylic compounds such as pentaerythritol tetra(meth)acrylate, pentaerythritol tetrakis ((meth)acryloxypropionate);
etc.
　単官能化合物としては、（メタ）アクリロイル基を１つ有する単官能（メタ）アクリル化合物が好ましい。単官能（メタ）アクリル化合物の具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、ベンジル（メタ）アクリレート、グリシジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、メトキシテトラエチレングリコール（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート（２－ＨＰＡ）、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、４－ブチルフェニル（メタ）アクリレート、フェニル（メタ）アクリレート、２，４，５－テトラメチルフェニル（メタ）アクリレート、４－クロロフェニル（メタ）アクリレート、フェノキシメチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２－（メタ）アクリロイロキシヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル－２－ヒドロキシプロピルフタル酸、ＥＯ変性フェノール（メタ）アクリレート、ＥＯ変性クレゾール（メタ）アクリレート、ＥＯ変性ノニルフェノール（メタ）アクリレート、ＰＯ変性ノニルフェノール（メタ）アクリレート、エトキシ化－ｏ－フェニルフェノール（メタ）アクリレート、ｍ－フェノキシベンジル（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロオクチル（メタ）アクリレート等が挙げられる。 As the monofunctional compound, a monofunctional (meth)acrylic compound having one (meth)acryloyl group is preferable. Specific examples of monofunctional (meth)acrylic compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and hexyl (meth)acrylate. ) acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, n-octyl (meth)acrylate, 2 -Methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate (2-HPA), dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, Cyclopentanyl (meth)acrylate, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate Acrylate, phenoxyethyl (meth)acrylate, 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalic acid, EO-modified phenol (meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 2,2,2-trifluoro Ethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate ) acrylate, etc.
　ラジカル重合性化合物は、芳香環を有する化合物（以下、芳香族モノマーともいう。）を含むことが好ましい。これにより、硬化体の透湿度がより低下する傾向がある。 The radically polymerizable compound preferably contains a compound having an aromatic ring (hereinafter also referred to as an aromatic monomer). This tends to further reduce the moisture permeability of the cured product.
　ラジカル重合性化合物が芳香族モノマーを含む場合、ラジカル重合性化合物に占める芳香族モノマーの割合は、例えば１質量％以上であってよく、好ましくは２質量％以上、より好ましくは３質量％以上であり、５質量％以上であってもよい。また、ラジカル重合性化合物に占める芳香族モノマーの割合は、例えば７０質量％以下であってよく、好ましくは６０質量％以下、より好ましくは５０質量％以下、更に好ましくは４０質量％以下であり、３０質量％以下、２０質量％以下、１５質量％以下又は１０質量％以下であってもよい。
　すなわち、ラジカル重合性化合物に占める芳香族モノマーの割合は、例えば１～７０質量％、１～６０質量％、１～５０質量％、１～４０質量％、１～３０質量％、１～２０質量％、１～１５質量％、１～１０質量％、２～７０質量％、２～６０質量％、２～５０質量％、２～４０質量％、２～３０質量％、２～２０質量％、２～１５質量％、２～１０質量％、３～７０質量％、３～６０質量％、３～５０質量％、３～４０質量％、３～３０質量％、３～２０質量％、３～１５質量％、３～１０質量％、５～７０質量％、５～６０質量％、５～５０質量％、５～４０質量％、５～３０質量％、５～２０質量％、５～１５質量％又は５～１０質量％であってもよい。 When the radically polymerizable compound contains an aromatic monomer, the proportion of the aromatic monomer in the radically polymerizable compound may be, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more. The content may be 5% by mass or more. Further, the proportion of the aromatic monomer in the radically polymerizable compound may be, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, It may be 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.
That is, the proportion of the aromatic monomer in the radically polymerizable compound is, for example, 1 to 70% by mass, 1 to 60% by mass, 1 to 50% by mass, 1 to 40% by mass, 1 to 30% by mass, 1 to 20% by mass. %, 1-15% by mass, 1-10% by mass, 2-70% by mass, 2-60% by mass, 2-50% by mass, 2-40% by mass, 2-30% by mass, 2-20% by mass, 2-15% by mass, 2-10% by mass, 3-70% by mass, 3-60% by mass, 3-50% by mass, 3-40% by mass, 3-30% by mass, 3-20% by mass, 3- 15% by mass, 3-10% by mass, 5-70% by mass, 5-60% by mass, 5-50% by mass, 5-40% by mass, 5-30% by mass, 5-20% by mass, 5-15% by mass % or 5 to 10% by mass.
　芳香族モノマーとしては、例えば、
　ベンジル（メタ）アクリレート、４－ブチルフェニル（メタ）アクリレート、フェニル（メタ）アクリレート、２，４，５－テトラメチルフェニル（メタ）アクリレート、４－クロロフェニル（メタ）アクリレート、フェノキシメチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート（２－ＨＰＡ）、２－（メタ）アクリロイロキシヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル－２－ヒドロキシプロピルフタル酸、ＥＯ変性フェノール（メタ）アクリレート、ＥＯ変性クレゾール（メタ）アクリレート、ＥＯ変性ノニルフェノール（メタ）アクリレート、ＰＯ変性ノニルフェノール（メタ）アクリレート、エトキシ化－ｏ－フェニルフェノール（メタ）アクリレート、ｍ－フェノキシベンジル（メタ）アクリレート等の芳香環を１つ有する化合物；
　エトキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化ビスフェノールＡジ（メタ）アクリレート、プロポキシ化エトキシ化ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡエポキシジ（メタ）アクリレート等の芳香環を２つ以上有する化合物；
等が挙げられる。 Examples of aromatic monomers include:
Benzyl (meth)acrylate, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, Phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate (2-HPA), 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2- Hydroxypropylphthalic acid, EO-modified phenol (meth)acrylate, EO-modified cresol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m - Compounds having one aromatic ring such as phenoxybenzyl (meth)acrylate;
Compounds having two or more aromatic rings such as ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxy di(meth)acrylate;
etc.
　硬化体の透湿性がより低下し、有機ＥＬ素子の信頼性がより向上する観点からは、芳香族モノマーとしては、芳香環を２つ以上有する化合物が好ましい。ラジカル重合性化合物は、芳香族モノマーとして、エトキシ化－ｏ－フェニルフェノール（メタ）アクリレート、ｍ－フェノキシベンジル（メタ）アクリレート及びエトキシ化ビスフェノールＡジ（メタ）アクリレートからなる群より選択される少なくとも一種を含むことが好ましく、エトキシ化－ｏ－フェニルフェノール（メタ）アクリレート及びエトキシ化ビスフェノールＡジ（メタ）アクリレートからなる群より選択される少なくとも一種を含むことがより好ましい。 From the viewpoint of further reducing the moisture permeability of the cured product and further improving the reliability of the organic EL device, the aromatic monomer is preferably a compound having two or more aromatic rings. The radically polymerizable compound is at least one selected from the group consisting of ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, and ethoxylated bisphenol A di(meth)acrylate as an aromatic monomer. It is more preferable to contain at least one selected from the group consisting of ethoxylated-o-phenylphenol (meth)acrylate and ethoxylated bisphenol A di(meth)acrylate.
　ラジカル重合性化合物は、ラジカル重合性基と脂肪族炭化水素環とを有する脂環式モノマーを含む。 The radically polymerizable compound includes an alicyclic monomer having a radically polymerizable group and an aliphatic hydrocarbon ring.
　脂環式モノマーが有する脂肪族炭化水素環は、単環であっても縮合環であってもよい。また、脂肪族炭化水素環は、飽和炭化水素環であっても不飽和炭化水素環であってもよい。飽和炭化水素環はシクロアルカン環であってよい。不飽和脂肪族炭化水素環としては、例えば、シクロアルケン環、シクロアルカジエン環、シクロアルカトリエン環等が挙げられ、好ましくはシクロアルケン環である。 The aliphatic hydrocarbon ring possessed by the alicyclic monomer may be a monocyclic ring or a fused ring. Further, the aliphatic hydrocarbon ring may be a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. The saturated hydrocarbon ring may be a cycloalkane ring. Examples of the unsaturated aliphatic hydrocarbon ring include a cycloalkene ring, a cycloalkadiene ring, and a cycloalkatriene ring, with the cycloalkene ring being preferred.
　シクロアルカン環としては、例えば、シクロペンタン環、シクロヘキサン環、テトラヒドロジシクロペンタジエン環、シクロヘプタン環、シクロオクテン環、ノルボルナン環、アダマンタン環等が挙げられる。 Examples of the cycloalkane ring include a cyclopentane ring, a cyclohexane ring, a tetrahydrodicyclopentadiene ring, a cycloheptane ring, a cyclooctene ring, a norbornane ring, and an adamantane ring.
　シクロアルケン環としては、例えば、シクロペンテン環、シクロヘキセン環、ジヒドロジシクロペンタジエン環、シクロへプテン環、シクロオクテン環、ノルボルネン環等が挙げられる。シクロアルケン環は、不飽和結合部の酸素トラップ機能に優れる観点からは、環歪みの大きい、シクロペンテン環、シクロヘキセン環又はジヒドロジシクロペンタジエン環であることが好ましく、シクロペンテン環又はジヒドロジシクロペンタジエン環であることがより好ましい。 Examples of the cycloalkene ring include a cyclopentene ring, a cyclohexene ring, a dihydrodicyclopentadiene ring, a cycloheptene ring, a cyclooctene ring, and a norbornene ring. The cycloalkene ring is preferably a cyclopentene ring, a cyclohexene ring, or a dihydrodicyclopentadiene ring, which has a large ring strain, and is preferably a cyclopentene ring or a dihydrodicyclopentadiene ring. It is more preferable that there be.
　脂環式モノマーは、ラジカル重合性基を１つ有する単官能化合物であってよく、ラジカル重合性基を２つ以上有する多官能化合物であってもよい。脂環式モノマー中のラジカル重合性基の数は、例えば１～６であってよく、好ましくは１～４、より好ましくは１～３、更に好ましくは１～２である。 The alicyclic monomer may be a monofunctional compound having one radically polymerizable group, or may be a polyfunctional compound having two or more radically polymerizable groups. The number of radically polymerizable groups in the alicyclic monomer may be, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
　脂環式モノマーは、脂肪族炭化水素環を１つ有する化合物であってよく、脂肪族炭化水素環を２つ以上有する化合物であってもよい。脂環式モノマー中の脂肪族炭化水素環の数は、例えば１～６であってよく、好ましくは１～４、より好ましくは１～３、更に好ましくは１～２である。 The alicyclic monomer may be a compound having one aliphatic hydrocarbon ring, or may be a compound having two or more aliphatic hydrocarbon rings. The number of aliphatic hydrocarbon rings in the alicyclic monomer may be, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2.
　脂環式モノマーとしては、例えば、
　トリシクロデカンジメタノールジ（メタ）アクリレート、１，４－シクロヘキサンジオールジ（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の飽和脂環式モノマー；
　ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート等の不飽和脂環式モノマーなどが挙げられる。 As the alicyclic monomer, for example,
Saturated alicyclic monomers such as tricyclodecane dimethanol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, cyclohexyl(meth)acrylate, dicyclopentanyl(meth)acrylate;
Examples include unsaturated alicyclic monomers such as dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate.
　ラジカル重合性化合物に占める脂環式モノマーの割合は、例えば３質量％以上であってよく、好ましくは５質量％以上、より好ましくは１０質量％以上、更に好ましくは１５質量％以上である。また、ラジカル重合性化合物に占める脂環式モノマーの割合は、例えば９０質量％以下であってよく、好ましくは７０質量％以下、より好ましくは５０質量％以下、更に好ましくは４０質量％以下である。
　すなわち、ラジカル重合性化合物に占める脂環式モノマーの割合は、例えば３～９０質量％、３～７０質量％、３～５０質量％、３～４０質量％、５～９０質量％、５～７０質量％、５～５０質量％、５～４０質量％、１０～９０質量％、１０～７０質量％、１０～５０質量％、１０～４０質量％、１５～９０質量％、１５～７０質量％、１５～５０質量％又は１５～４０質量％であってもよい。 The proportion of the alicyclic monomer in the radically polymerizable compound may be, for example, 3% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. Further, the proportion of the alicyclic monomer in the radically polymerizable compound may be, for example, 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less. .
That is, the proportion of the alicyclic monomer in the radically polymerizable compound is, for example, 3 to 90% by mass, 3 to 70% by mass, 3 to 50% by mass, 3 to 40% by mass, 5 to 90% by mass, 5 to 70% by mass. Mass%, 5-50 mass%, 5-40 mass%, 10-90 mass%, 10-70 mass%, 10-50 mass%, 10-40 mass%, 15-90 mass%, 15-70 mass% , 15 to 50% by weight, or 15 to 40% by weight.
　ラジカル重合性化合物は、ラジカル重合性基を有し、環構造を有しない非環式モノマーを含むことが好ましい。 The radically polymerizable compound preferably contains an acyclic monomer that has a radically polymerizable group and does not have a ring structure.
　非環式モノマーが有するラジカル重合性基の数は、例えば１以上であってよく、２以上であることが好ましい。非環式モノマーが有するラジカル重合性基の数は、例えば６以下であってよく、好ましくは４以下、より好ましくは３以下である。非環式モノマーが有するラジカル重合性基の数は、２であることが特に好ましい。
　すなわち、非環式モノマーが有するラジカル重合性基の数は、例えば１～６、１～４、１～３、２～６、２～４又は２～３であってもよい。 The number of radically polymerizable groups that the acyclic monomer has may be, for example, one or more, and preferably two or more. The number of radically polymerizable groups that the acyclic monomer has may be, for example, 6 or less, preferably 4 or less, and more preferably 3 or less. It is particularly preferable that the acyclic monomer has two radically polymerizable groups.
That is, the number of radically polymerizable groups that the acyclic monomer has may be, for example, 1 to 6, 1 to 4, 1 to 3, 2 to 6, 2 to 4, or 2 to 3.
　非環式モノマーとしては、例えば、ラジカル重合性基と鎖状飽和炭化水素基とを有する化合物（以下、鎖状モノマーともいう。）が挙げられる。 Examples of the acyclic monomer include compounds having a radically polymerizable group and a chain saturated hydrocarbon group (hereinafter also referred to as a chain monomer).
　鎖状モノマーが有する鎖状飽和炭化水素基の炭素数は、例えば２以上であり、３以上、４以上、６以上、８以上又は１０以上であってもよい。鎖状モノマーが有する鎖状飽和炭化水素基の炭素数は、例えば１６以下であってよく、１５以下、１４以下又は１３以下であってもよい。
　すなわち、鎖状モノマーが有する鎖状飽和炭化水素基の炭素数は、例えば２～１６、２～１５、２～１４、２～１３、３～１６、３～１５、３～１４、３～１３、４～１６、４～１５、４～１４、４～１３、６～１６、６～１５、６～１４、６～１３、８～１６、８～１５、８～１４、８～１３、１０～１６、１０～１５、１０～１４又は１０～１３であってもよい。 The number of carbon atoms in the chain saturated hydrocarbon group contained in the chain monomer is, for example, 2 or more, and may be 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the chain saturated hydrocarbon group contained in the chain monomer may be, for example, 16 or less, 15 or less, 14 or less, or 13 or less.
That is, the number of carbon atoms in the chain saturated hydrocarbon group possessed by the chain monomer is, for example, 2 to 16, 2 to 15, 2 to 14, 2 to 13, 3 to 16, 3 to 15, 3 to 14, 3 to 13 , 4-16, 4-15, 4-14, 4-13, 6-16, 6-15, 6-14, 6-13, 8-16, 8-15, 8-14, 8-13, 10 -16, 10-15, 10-14 or 10-13.
　鎖状モノマーが有する鎖状飽和炭化水素基は、アルカンジイル基であることが好ましい。アルカンジイル基の炭素数の好適な範囲は、鎖状飽和炭化水素基の炭素数の好適な範囲と同じである。 The chain saturated hydrocarbon group possessed by the chain monomer is preferably an alkanediyl group. The preferred range of the carbon number of the alkanediyl group is the same as the preferred range of the carbon number of the chain saturated hydrocarbon group.
　ラジカル重合性化合物が鎖状モノマーを含む場合、ラジカル重合性化合物に占める鎖状モノマーの割合は、例えば１０質量％以上であってよく、好ましくは２０質量％以上、より好ましくは３０質量％以上であり、４０質量％以上、５０質量％以上又は５５質量％以上であってもよい。また、ラジカル重合性化合物に占める鎖状モノマーの割合は、例えば９０質量％以下であってよく、好ましくは８５質量％以下、より好ましくは８０質量％以下である。
　すなわち、ラジカル重合性化合物に占める鎖状モノマーの割合は、例えば１０～９０質量％、１０～８５質量％、１０～８０質量％、２０～９０質量％、２０～８５質量％、２０～８０質量％、３０～９０質量％、３０～８５質量％、３０～８０質量％、４０～９０質量％、４０～８５質量％、４０～８０質量％、５０～９０質量％、５０～８５質量％、５０～８０質量％、５５～９０質量％、５５～８５質量％又は５５～８０質量％であってもよい。 When the radically polymerizable compound contains a chain monomer, the proportion of the chain monomer in the radically polymerizable compound may be, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more. The content may be 40% by mass or more, 50% by mass or more, or 55% by mass or more. Further, the proportion of the chain monomer in the radically polymerizable compound may be, for example, 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less.
That is, the proportion of the chain monomer in the radical polymerizable compound is, for example, 10 to 90% by mass, 10 to 85% by mass, 10 to 80% by mass, 20 to 90% by mass, 20 to 85% by mass, 20 to 80% by mass. %, 30-90 mass%, 30-85 mass%, 30-80 mass%, 40-90 mass%, 40-85 mass%, 40-80 mass%, 50-90 mass%, 50-85 mass%, It may be 50-80% by weight, 55-90% by weight, 55-85% by weight or 55-80% by weight.
　鎖状モノマーとしては、例えば、
　１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，７－ヘプタンジオールジ（メタ）アクリレート、１，８－オクタンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、１，１３－トリデカンジオールジ（メタ）アクリレート、１，１４－テトラデカンジオールジ（メタ）アクリレート、１，１５－ペンタデカンジオールジ（メタ）アクリレート、１，１６－ヘキサデカンジオールジ（メタ）アクリレート、ネオペンチルグリコールジメタクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート等のアルカンジオールジ（メタ）アクリレート；
　ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート等のポリエチレングリコールジ（メタ）アクリレート；
　ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等のポリプロピレングリコールジ（メタ）アクリレート；
等が挙げられる。 Examples of chain monomers include:
1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1, 9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14 -Tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, neopentyl glycol dimethacrylate, 1,12-dodecanediol di(meth)acrylate alkanediol di(meth)acrylates such as;
Polyethylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate and triethylene glycol di(meth)acrylate;
Polypropylene glycol di(meth)acrylate such as dipropylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate;
etc.
　ラジカル重合性化合物は、フルオロ基を有する化合物（以下、含フッ素モノマーともいう）を含むことが好ましい。これにより、封止剤の表面自由エネルギーが低くなって、微細な凹凸に追従しやすくなり、塗膜の平坦性がより向上する傾向がある。 The radically polymerizable compound preferably contains a compound having a fluoro group (hereinafter also referred to as a fluorine-containing monomer). As a result, the surface free energy of the sealant decreases, making it easier to follow minute irregularities, and the flatness of the coating film tends to be further improved.
　ラジカル重合性化合物が含フッ素モノマーを含む場合、ラジカル重合性化合物に占める含フッ素モノマーの割合は、例えば０．１質量％以上であってよく、好ましくは０．３質量％以上、より好ましくは０．５質量％以上であり、０．７質量％以上、０．９質量％以上又は１質量％以上であってもよい。また、ラジカル重合性化合物に占める含フッ素モノマーの割合は、例えば１５質量％以下であってよく、好ましくは１０質量％以下であり、７質量％以下、５質量％以下、３質量％以下又は２質量％以下であってもよい。
　すなわち、ラジカル重合性化合物に占める含フッ素モノマーの割合は、例えば０．１～１５質量％、０．１～１０質量％、０．１～７質量％、０．１～５質量％、０．１～３質量％、０．１～２質量％、０．３～１５質量％、０．３～１０質量％、０．３～７質量％、０．３～５質量％、０．３～３質量％、０．３～２質量％、０．５～１５質量％、０．５～１０質量％、０．５～７質量％、０．５～５質量％、０．５～３質量％、０．５～２質量％、０．７～１５質量％、０．７～１０質量％、０．７～７質量％、０．７～５質量％、０．７～３質量％、０．７～２質量％、０．９～１５質量％、０．９～１０質量％、０．９～７質量％、０．９～５質量％、０．９～３質量％、０．９～２質量％、１～１５質量％、１～１０質量％、１～７質量％、１～５質量％、１～３質量％又は１～２質量％であってもよい。 When the radically polymerizable compound contains a fluorine-containing monomer, the proportion of the fluorine-containing monomer in the radically polymerizable compound may be, for example, 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 0. .5% by mass or more, and may be 0.7% by mass or more, 0.9% by mass or more, or 1% by mass or more. Further, the proportion of the fluorine-containing monomer in the radically polymerizable compound may be, for example, 15% by mass or less, preferably 10% by mass or less, 7% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less. It may be less than % by mass.
That is, the proportion of the fluorine-containing monomer in the radically polymerizable compound is, for example, 0.1 to 15% by mass, 0.1 to 10% by mass, 0.1 to 7% by mass, 0.1 to 5% by mass, 0. 1-3 mass%, 0.1-2 mass%, 0.3-15 mass%, 0.3-10 mass%, 0.3-7 mass%, 0.3-5 mass%, 0.3- 3% by mass, 0.3-2% by mass, 0.5-15% by mass, 0.5-10% by mass, 0.5-7% by mass, 0.5-5% by mass, 0.5-3% by mass %, 0.5-2% by mass, 0.7-15% by mass, 0.7-10% by mass, 0.7-7% by mass, 0.7-5% by mass, 0.7-3% by mass, 0.7-2% by mass, 0.9-15% by mass, 0.9-10% by mass, 0.9-7% by mass, 0.9-5% by mass, 0.9-3% by mass, 0. It may be 9-2% by weight, 1-15% by weight, 1-10% by weight, 1-7% by weight, 1-5% by weight, 1-3% by weight or 1-2% by weight.
　含フッ素モノマーが有するフルオロ基の数は、例えば１以上であればよく、好ましくは２以上、より好ましくは３以上である。また、含フッ素モノマーが有するフルオロ基の数は特に限定されないが、例えば４０以下であってよく、好ましくは３０以下である。すなわち、含フッ素モノマーが有するフルオロ基の数は、例えば１～４０、１～３０、２～４０、２～３０、３～４０又は３～３０であってもよい。 The number of fluoro groups that the fluorine-containing monomer has may be, for example, 1 or more, preferably 2 or more, and more preferably 3 or more. Further, the number of fluoro groups that the fluorine-containing monomer has is not particularly limited, but may be, for example, 40 or less, and preferably 30 or less. That is, the number of fluoro groups that the fluorine-containing monomer has may be, for example, 1 to 40, 1 to 30, 2 to 40, 2 to 30, 3 to 40, or 3 to 30.
　含フッ素モノマーの全量に対するフッ素原子の含有量は、例えば１質量％以上であってよく、好ましくは２質量％以上、より好ましくは５質量％以上である。このような含有量範囲を満たす含フッ素モノマーによれば、上述の効果がより顕著に奏される。また、含フッ素モノマーの全量に対するフッ素原子の含有量は、例えば７５質量％以下であってよく、好ましくは７０質量％以下、より好ましくは６５質量％以下である。
　すなわち、含フッ素モノマーの全量に対するフッ素原子の含有量は、例えば１～７５質量％、１～７０質量％、１～６５質量％、２～７５質量％、２～７０質量％、２～６５質量％、５～７５質量％、５～７０質量％又は５～６５質量％であってもよい。 The content of fluorine atoms based on the total amount of the fluorine-containing monomer may be, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 5% by mass or more. A fluorine-containing monomer that satisfies such a content range exhibits the above-mentioned effects more markedly. Further, the content of fluorine atoms based on the total amount of the fluorine-containing monomer may be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less.
That is, the content of fluorine atoms relative to the total amount of the fluorine-containing monomer is, for example, 1 to 75% by mass, 1 to 70% by mass, 1 to 65% by mass, 2 to 75% by mass, 2 to 70% by mass, 2 to 65% by mass. %, 5-75% by weight, 5-70% by weight or 5-65% by weight.
　含フッ素モノマーが有するラジカル重合性基の数は、１以上であればよい。ガラス転移温度の低い硬化体が得られやすくなる観点からは、含フッ素モノマーが有するラジカル重合性基の数は、１であってよい。また、ガラス転移温度の高い硬化体が得られやすくなる観点からは、含フッ素モノマーが有するラジカル重合性基の数は、２以上であってよい。含フッ素モノマーが有するラジカル重合性基の数の上限は特に限定されない。含フッ素モノマーが有するラジカル重合性基の数は、例えば４以下であり、柔軟性に優れる硬化体が得られやすくなる観点からは、好ましくは３以下、より好ましくは２以下である。 The number of radically polymerizable groups that the fluorine-containing monomer has may be one or more. From the viewpoint of easily obtaining a cured product with a low glass transition temperature, the number of radically polymerizable groups contained in the fluorine-containing monomer may be one. Further, from the viewpoint of easily obtaining a cured product having a high glass transition temperature, the number of radically polymerizable groups contained in the fluorine-containing monomer may be 2 or more. There is no particular upper limit to the number of radically polymerizable groups that the fluorine-containing monomer has. The number of radically polymerizable groups that the fluorine-containing monomer has is, for example, 4 or less, preferably 3 or less, more preferably 2 or less from the viewpoint of easily obtaining a cured product with excellent flexibility.
　含フッ素モノマーとしては、例えば、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロオクチル（メタ）アクリレート、２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９－ヘキサデカフルオロ－１，１０－デカンジ（メタ）アクリレート等が挙げられる。 Examples of the fluorine-containing monomer include 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and 1H,1H,5H-octafluoropentyl (meth)acrylate. Acrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9 -hexadecafluoro-1,10-decane di(meth)acrylate and the like.
（光重合開始剤）
　光重合開始剤は、上述のラジカル重合性化合物を重合させることが可能な開始剤であればよい。光重合開始剤は１種を単独で用いてよく、２種以上を組み合わせて用いてもよい。 (Photopolymerization initiator)
The photopolymerization initiator may be any initiator that can polymerize the above-mentioned radically polymerizable compound. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
　光重合開始剤としては、例えば、
　ベンゾフェノン及びその誘導体；
　ベンジル及びその誘導体；
　アントラキノン及びその誘導体；
　ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン型光重合開始剤；
　ジエトキシアセトフェノン、４－ｔｅｒｔ－ブチルトリクロロアセトフェノン等のアセトフェノン型光重合開始剤；
　２－ジメチルアミノエチルベンゾエート；
　ｐ－ジメチルアミノエチルベンゾエート；
　ジフェニルジスルフィド；
　チオキサントン及びその誘導体；
　カンファーキノン、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボン酸、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボキシ－２－ブロモエチルエステル、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボキシ－２－メチルエステル、７，７－ジメチル－２，３－ジオキソビシクロ［２．２．１］ヘプタン－１－カルボン酸クロライド等のカンファーキノン型光重合開始剤；
　２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１等のα－アミノアルキルフェノン型光重合開始剤；
　ベンゾイルジフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド、ベンゾイルジエトキシホスフィンオキサイド、２，４，６－トリメチルベンゾイルジメトキシフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジエトキシフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド等のアシルホスフィンオキサイド型光重合開始剤；
　フェニル－グリオキシリックアシッド－メチルエステル；
　オキシ－フェニル－アセチックアシッド２－［２－オキソ－２－フェニル－アセトキシ－エトキシ］－エチルエステル；
　オキシ－フェニル－アセチックアシッド２－［２－ヒドロキシ－エトキシ］－エチルエステル；等が挙げられる。 As the photopolymerization initiator, for example,
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, benzyl dimethyl ketal;
Acetophenone type photopolymerization initiator such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone;
2-dimethylaminoethylbenzoate;
p-dimethylaminoethylbenzoate;
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-dioxobicyclo[2.2.1] Heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2 , 3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid chloride and other camphorquinone type photopolymerization initiators;
α of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, etc. -Aminoalkylphenone type photoinitiator;
Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, an acylphosphine oxide type photoinitiator such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide;
Phenyl-glyoxylic acid-methyl ester;
Oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester;
Oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester; and the like.
　光重合開始剤としては、３９０ｎｍ以上の可視光線のみを用いて硬化させることができ、有機ＥＬ素子にダメージを与えずに硬化可能であることから、アシルホスフィンオキサイド型光重合開始剤が好ましい。アシルホスフィンオキサイド型光重合開始剤としては、硬化体の透明性がより向上する点及び３９５ｎｍ以上の光のみを用いて硬化可能である点で、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドが好ましい。２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドとしては、ＩＧＭ　Ｒｅｓｉｎｓ社製「Ｏｍｎｉｒａｄ　ＴＰＯ」等が挙げられる。 As the photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator is preferable because it can be cured using only visible light of 390 nm or more and can be cured without damaging the organic EL element. As an acylphosphine oxide type photopolymerization initiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferred because it further improves the transparency of the cured product and can be cured using only light of 395 nm or more. is preferred. Examples of the 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide include "Omnirad TPO" manufactured by IGM Resins.
　光重合開始剤の含有量は、ラジカル重合性化合物１００質量部に対して、例えば０．０５質量部以上であってよく、好ましくは０．５質量部以上、より好ましくは１質量部以上、更に好ましくは２質量部以上である。また、光重合開始剤の含有量は、ラジカル重合性化合物１００質量部に対して、例えば１０質量部以下であってよく、好ましくは８質量部以下、より好ましくは５質量部以下である。このような含有量であると、封止剤の十分な感度及び硬化速度を得つつ、封止材の十分な透明度を確保しやすい傾向がある。
　すなわち、光重合開始剤の含有量は、ラジカル重合性化合物１００質量部に対して、例えば０．０５～１０質量部、０．０５～８質量部、０．０５～５質量部、０．５～１０質量部、０．５～８質量部、０．５～５質量部、１～１０質量部、１～８質量部、１～５質量部、２～１０質量部、２～８質量部又は２～５質量部であってもよい。 The content of the photopolymerization initiator may be, for example, 0.05 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the radically polymerizable compound. Preferably it is 2 parts by mass or more. Further, the content of the photopolymerization initiator may be, for example, 10 parts by mass or less, preferably 8 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the radically polymerizable compound. Such a content tends to ensure sufficient transparency of the encapsulant while obtaining sufficient sensitivity and curing speed of the encapsulant.
That is, the content of the photopolymerization initiator is, for example, 0.05 to 10 parts by mass, 0.05 to 8 parts by mass, 0.05 to 5 parts by mass, or 0.5 parts by mass with respect to 100 parts by mass of the radically polymerizable compound. ~10 parts by weight, 0.5 to 8 parts by weight, 0.5 to 5 parts by weight, 1 to 10 parts by weight, 1 to 8 parts by weight, 1 to 5 parts by weight, 2 to 10 parts by weight, 2 to 8 parts by weight Alternatively, it may be 2 to 5 parts by mass.
（安定ラジカル型化合物）
　安定ラジカル型化合物は、安定ラジカルを有する化合物である。光重合開始剤は１種を単独で用いてよく、２種以上を組み合わせて用いてもよい。 (Stable radical type compound)
A stable radical type compound is a compound having a stable radical. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
　安定ラジカルとしては、ニトロキシドラジカル（ＮＯラジカル）が好ましい。すなわち、安定ラジカル型化合物としては、ニトロキシドラジカルを有する化合物が好ましい。ニトロキシドラジカルは、ラジカル重合性化合物との相溶性及び反応性に優れるため、ラジカル種をすばやく捕捉することができる。 As the stable radical, a nitroxide radical (NO radical) is preferable. That is, as the stable radical type compound, a compound having a nitroxide radical is preferable. Since nitroxide radicals have excellent compatibility and reactivity with radically polymerizable compounds, they can quickly capture radical species.
　有機ＥＬ表示装置の製造工程では、有機ＥＬ素子が酸素によって劣化することから、１ｐｐｍ未満の低酸素濃度で管理され、有機ＥＬ素子用封止剤も低酸素濃度で使用される。ここで、ラジカル重合性化合物の重合抑制のために用いられる一般的なフェノール系酸化防止剤は、重合抑制機能を発揮する過程で酸素との反応を要する。このため、フェノール系酸化防止剤は、有機ＥＬ素子用封止剤において重合抑制機能を発揮することが難しい。これに対して、安定ラジカル（特にニトロキシドラジカル）を有する安定ラジカル型化合物は、酸素の有無に関わらずラジカル種を捕捉できるため、上述の効果を顕著に得ることができる。 In the manufacturing process of organic EL display devices, since organic EL elements are degraded by oxygen, they are managed at a low oxygen concentration of less than 1 ppm, and the sealant for organic EL elements is also used at a low oxygen concentration. Here, the general phenolic antioxidant used for inhibiting the polymerization of radically polymerizable compounds requires a reaction with oxygen in the process of exhibiting the polymerization inhibiting function. For this reason, it is difficult for phenolic antioxidants to exhibit a polymerization inhibiting function in sealants for organic EL elements. On the other hand, stable radical-type compounds having stable radicals (particularly nitroxide radicals) can capture radical species regardless of the presence or absence of oxygen, and therefore can significantly obtain the above-mentioned effects.
　安定ラジカル型化合物としては、例えば、１－オキシル－２，２，６，６－テトラメチルピペリジン、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシル、４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン１－オキシル等が挙げられ、硬化体中に取り込まれてアウトガスとなりにくい観点からは、４－（メタ）アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン１－オキシルが好ましく、４－メタクリロイルオキシ－２，２，６，６－テトラメチルピペリジン１－オキシルがより好ましい。 Examples of stable radical type compounds include 1-oxyl-2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and 4-(meth)acryloyl. Examples include oxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-(meth)acryloyloxy-2,2,6,6 from the viewpoint of being less likely to be incorporated into the cured product and cause outgassing. -Tetramethylpiperidine 1-oxyl is preferred, and 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl is more preferred.
　安定ラジカル型化合物の含有量は、ラジカル重合性化合物１００質量部に対して、例えば１質量ｐｐｍ以上であってよく、好ましくは１０質量ｐｐｍ以上、より好ましくは５０質量ｐｐｍ以上、更に好ましくは１００質量ｐｐｍ以上である。また、安定ラジカル型化合物の含有量は、ラジカル重合性化合物１００質量部に対して、例えば１５０００質量ｐｐｍ以下であってよく、好ましくは１００００質量ｐｐｍ以下、より好ましくは８０００質量ｐｐｍ以下、更に好ましくは６０００質量ｐｐｍ以下である。適量の安定ラジカル型化合物を用いることで、上述の効果がより顕著に奏される。
　すなわち、安定ラジカル型化合物の含有量は、ラジカル重合性化合物１００質量部に対して、例えば１～１５０００質量ｐｐｍ、１～１００００質量ｐｐｍ、１～８０００質量ｐｐｍ、１～６０００質量ｐｐｍ、１０～１５０００質量ｐｐｍ、１０～１００００質量ｐｐｍ、１０～８０００質量ｐｐｍ、１０～６０００質量ｐｐｍ、５０～１５０００質量ｐｐｍ、５０～１００００質量ｐｐｍ、５０～８０００質量ｐｐｍ、５０～６０００質量ｐｐｍ、１００～１５０００質量ｐｐｍ、１００～１００００質量ｐｐｍ、１００～８０００質量ｐｐｍ又は１００～６０００質量ｐｐｍであってもよい。 The content of the stable radical type compound may be, for example, 1 mass ppm or more, preferably 10 mass ppm or more, more preferably 50 mass ppm or more, and even more preferably 100 mass ppm, based on 100 parts by mass of the radically polymerizable compound. ppm or more. Further, the content of the stable radical type compound may be, for example, 15,000 mass ppm or less, preferably 10,000 mass ppm or less, more preferably 8,000 mass ppm or less, and even more preferably It is 6000 mass ppm or less. By using an appropriate amount of a stable radical type compound, the above-mentioned effects can be more pronounced.
That is, the content of the stable radical type compound is, for example, 1 to 15,000 mass ppm, 1 to 10,000 mass ppm, 1 to 8,000 mass ppm, 1 to 6,000 mass ppm, 10 to 15,000 mass ppm with respect to 100 parts by mass of the radically polymerizable compound. Mass ppm, 10-10000 mass ppm, 10-8000 mass ppm, 10-6000 mass ppm, 50-15000 mass ppm, 50-10000 mass ppm, 50-8000 mass ppm, 50-6000 mass ppm, 100-15000 mass ppm , 100 to 10,000 mass ppm, 100 to 8,000 mass ppm, or 100 to 6,000 mass ppm.
（他の成分）
　本実施形態の封止剤は、上記以外の他の成分を更に含有していてもよい。他の成分としては、酸化防止剤、界面活性剤、増感剤等が挙げられる。 (other ingredients)
The sealant of this embodiment may further contain other components than those mentioned above. Other components include antioxidants, surfactants, sensitizers, and the like.
　他の成分の含有量は特に限定されず、ラジカル重合性化合物１００質量部に対して、例えば１０質量部以下であってよく、好ましくは５質量部以下、より好ましくは３質量部以下であり、２質量部以下又は１質量部以下であってもよい。 The content of other components is not particularly limited, and may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the radically polymerizable compound. It may be 2 parts by mass or less or 1 part by mass or less.
　本実施形態の封止剤の粘度は、好ましくは３ｍＰａ・ｓ以上、より好ましくは５ｍＰａ・ｓ以上である。また、本実施形態の封止剤の粘度は、好ましくは５０ｍＰａ・ｓ以下、より好ましくは３０ｍＰａ・ｓ以下である。封止剤の粘度が上記範囲であると、インクジェット法による塗布時の吐出性がより向上し、塗膜形成がより容易となる傾向がある。すなわち、封止剤の粘度は、例えば３～５０ｍＰａ・ｓ、３～３０ｍＰａ・ｓ、５～５０ｍＰａ・ｓ又は５～３０ｍＰａ・ｓであってもよい。 The viscosity of the sealant of this embodiment is preferably 3 mPa·s or more, more preferably 5 mPa·s or more. Further, the viscosity of the sealant of this embodiment is preferably 50 mPa·s or less, more preferably 30 mPa·s or less. When the viscosity of the sealant is within the above range, the ejection properties during application by an inkjet method tend to be further improved, and coating film formation tends to be easier. That is, the viscosity of the sealant may be, for example, 3 to 50 mPa·s, 3 to 30 mPa·s, 5 to 50 mPa·s, or 5 to 30 mPa·s.
　なお、本明細書中、封止剤の粘度は、コーンプレート型粘度計（英弘精機社製、品番：ＨＢ　ＤＶ３Ｔなど）を用いて、２５℃、２５０ｒｐｍの条件で測定される値を示す。 In this specification, the viscosity of the sealant indicates a value measured at 25° C. and 250 rpm using a cone-plate viscometer (manufactured by Eiko Seiki Co., Ltd., product number: HB DV3T, etc.).
　本実施形態の封止剤の硫黄原子濃度は、例えば１００ｐｐｍ以下であってよく、好ましくは５０ｐｐｍ以下、より好ましくは４０ｐｐｍ以上である。本実施形態の封止剤の硫黄原子濃度はまた、例えば０．１ｐｐｍ以上であってよく、１ｐｐｍ以上であってもよい。すなわち、本実施形態の封止剤の硫黄原子濃度は、例えば０．１～１００ｐｐｍ、０．１～５０ｐｐｍ、０．１～４０ｐｐｍ、１～１００ｐｐｍ、１～５０ｐｐｍ又は１～４０ｐｐｍであってもよい。このような硫黄原子濃度であると、有機ＥＬ素子の劣化、ダークスポットの発生がより顕著に抑制され、信頼性がより向上する傾向がある。 The sulfur atom concentration of the sealant of this embodiment may be, for example, 100 ppm or less, preferably 50 ppm or less, and more preferably 40 ppm or more. The sulfur atom concentration of the sealant of this embodiment may also be, for example, 0.1 ppm or more, or 1 ppm or more. That is, the sulfur atom concentration of the sealant of this embodiment may be, for example, 0.1 to 100 ppm, 0.1 to 50 ppm, 0.1 to 40 ppm, 1 to 100 ppm, 1 to 50 ppm, or 1 to 40 ppm. . With such a sulfur atom concentration, deterioration of the organic EL element and generation of dark spots are more significantly suppressed, and reliability tends to be further improved.
　本実施形態の封止剤の水分濃度は、例えば１００ｐｐｍ以下であってよく、好ましくは７０ｐｐｍ以下、より好ましくは５０ｐｐｍ以下である。本実施形態の封止剤の水分濃度はまた、例えば０．５ｐｐｍ以上であってよく、１ｐｐｍ以上であってもよい。すなわち、本実施形態の封止剤の水分濃度は、例えば０．５～１００ｐｐｍ、０．５～７０ｐｐｍ、０．５～５０ｐｐｍ、１～１００ｐｐｍ、１～７０ｐｐｍ又は１～５０ｐｐｍであってもよい。このような水分濃度であると、上述の効果がより顕著に奏される傾向がある。 The water concentration of the sealant of this embodiment may be, for example, 100 ppm or less, preferably 70 ppm or less, and more preferably 50 ppm or less. The water concentration of the sealant of this embodiment may also be, for example, 0.5 ppm or more, or 1 ppm or more. That is, the moisture concentration of the sealant of this embodiment may be, for example, 0.5 to 100 ppm, 0.5 to 70 ppm, 0.5 to 50 ppm, 1 to 100 ppm, 1 to 70 ppm, or 1 to 50 ppm. At such a water concentration, the above-mentioned effects tend to be more pronounced.
　本実施形態の封止剤の１ｍＬ中に存在する直径１μｍ以上のパーティクルの数をａとし、８０℃で１６時間加熱した後の封止剤の１ｍＬ中に存在する直径１μｍ以上のパーティクルの数をｂとしたとき、ｂ－ａは、１０以下であることが好ましい。このような封止剤によれば、パーティクルに起因する塗布不良が抑制されて、塗布装置からの優れた吐出性、及び、塗布後の塗膜の高い平坦性が実現される。 The number of particles with a diameter of 1 μm or more existing in 1 mL of the sealant of this embodiment is a, and the number of particles with a diameter of 1 μm or more existing in 1 mL of the sealant after heating at 80 ° C. for 16 hours is a. When b is represented by b, ba is preferably 10 or less. According to such a sealant, coating defects caused by particles are suppressed, and excellent discharge performance from the coating device and high flatness of the coated film after coating are realized.
　上記ａは、好ましくは１０以下、より好ましくは５以下、更に好ましくは３以下であり、０であってもよい。 The above a is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and may be 0.
　上記ｂは、好ましくは１０以下、より好ましくは５以下、更に好ましくは３以下であり、０であってもよい。 The above b is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and may be 0.
　本実施形態の封止剤は、１μｍ以上のパーティクルを含んでいてもよいが、含まない（すなわち、ａが０である）ことが好ましい。なお、パーティクルとしては、ラジカル重合性化合物の重合体由来のパーティクル、塵、埃等の異物由来のパーティクル、封止剤の製造工程で使用されたモレキュラーシーブス等の脱水剤由来のパーティクル等が挙げられる。本実施形態の封止剤は、これらのパーティクルを実質的に含まない封止剤として、濾過フィルター等でパーティクルを除去したものであってよい。 The sealant of this embodiment may contain particles of 1 μm or more, but preferably does not contain particles (that is, a is 0). Examples of particles include particles derived from polymers of radically polymerizable compounds, particles derived from foreign substances such as dust, particles derived from dehydrating agents such as molecular sieves used in the manufacturing process of sealants, etc. . The sealant of this embodiment may be a sealant that does not substantially contain these particles, and the particles may be removed using a filtration filter or the like.
　なお、本明細書中、パーティクルの数は、パーティクルカウンター（リオン社製、光散乱式液中粒子検出器、品番：ＫＳ－４２Ｂ）を用いて測定される値を示す。 In this specification, the number of particles indicates a value measured using a particle counter (manufactured by Rion Corporation, light scattering particle detector in liquid, product number: KS-42B).
　本実施形態の封止剤の酸価は、０．１５（ｍｇＫＯＨ／ｇ）以下であり、好ましくは０．１３（ｍｇＫＯＨ／ｇ）以下、より好ましくは０．１０（ｍｇＫＯＨ／ｇ）以下である。これにより、上述の効果がより顕著に奏される。また、本実施形態の封止剤の酸価は、０．０１（ｍｇＫＯＨ／ｇ）以上であり、好ましくは０．０１５（ｍｇＫＯＨ／ｇ）以上、より好ましくは０．０２（ｍｇＫＯＨ／ｇ）以上である。これにより、酸成分の重合禁止剤としての効果がより顕著に奏される。
　すなわち、本実施形態の封止剤の酸価は、例えば０．０１～０．１５（ｍｇＫＯＨ／ｇ）、０．０１～０．１３（ｍｇＫＯＨ／ｇ）、０．０１～０．１０（ｍｇＫＯＨ／ｇ）、０．０１５～０．１５（ｍｇＫＯＨ／ｇ）、０．０１５～０．１３（ｍｇＫＯＨ／ｇ）、０．０１５～０．１０（ｍｇＫＯＨ／ｇ）、０．０２～０．１５（ｍｇＫＯＨ／ｇ）、０．０２～０．１３（ｍｇＫＯＨ／ｇ）又は０．０２～０．１０（ｍｇＫＯＨ／ｇ）であってもよい。 The acid value of the sealant of this embodiment is 0.15 (mgKOH/g) or less, preferably 0.13 (mgKOH/g) or less, more preferably 0.10 (mgKOH/g) or less. . Thereby, the above-mentioned effects are more prominently produced. Further, the acid value of the sealant of this embodiment is 0.01 (mgKOH/g) or more, preferably 0.015 (mgKOH/g) or more, more preferably 0.02 (mgKOH/g) or more. It is. Thereby, the effect of the acid component as a polymerization inhibitor is more prominently exhibited.
That is, the acid value of the sealant of this embodiment is, for example, 0.01 to 0.15 (mgKOH/g), 0.01 to 0.13 (mgKOH/g), or 0.01 to 0.10 (mgKOH/g). /g), 0.015 to 0.15 (mgKOH/g), 0.015 to 0.13 (mgKOH/g), 0.015 to 0.10 (mgKOH/g), 0.02 to 0.15 (mgKOH/g), 0.02 to 0.13 (mgKOH/g), or 0.02 to 0.10 (mgKOH/g).
　本実施形態の封止剤の酸価は、以下の方法で測定される値を示す。
　試料２ｇを５０ｍＬトールビーカーに秤取り、２－プロパノールを４０ｍＬ加え、５分間撹拌する。電位の安定を確認後、平沼製作所製　自動滴定装置　ＣＯＭ　５５０にて、滴定液０．１ｍｏｌ／Ｌ　２－プロパノール性水酸化カリウム標準液（和光純薬製）を用いて、電位差滴定法で終点を求める。 The acid value of the sealant of this embodiment shows the value measured by the following method.
Weigh 2 g of the sample into a 50 mL tall beaker, add 40 mL of 2-propanol, and stir for 5 minutes. After confirming the stability of the potential, the end point was determined by potentiometric titration using a titrant 0.1 mol/L 2-propanolic potassium hydroxide standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) using an automatic titrator COM 550 manufactured by Hiranuma Seisakusho. demand.
　本実施形態の封止剤の製造方法は特に限定されないが、例えば、以下の方法で製造することができる。 Although the method for manufacturing the sealant of this embodiment is not particularly limited, it can be manufactured, for example, by the following method.
（封止剤の製造方法）
　本実施形態の封止剤の製造方法は、封止剤の酸価が０．０１～０．１５（ｍｇＫＯＨ／ｇ）となるように、ラジカル重合性化合物の少なくとも一部を下記（ｉ）の方法で前処理する前処理工程と、ラジカル重合性化合物と、光重合開始剤と、安定ラジカルを有する安定ラジカル型化合物と、を混合して、封止剤を得る混合工程と、を含む。また、前処理工程は、（ｉｉ）、（ｉｉｉ）の方法による前処理を更に含んでいてもよい。
（ｉ）１０～１００℃、１０００Ｐａ以下の環境下での脱気処理
（ｉｉ）蒸留精製
（ｉｉｉ）カラムクロマトグラフィー精製 (Method for manufacturing sealant)
In the method for producing a sealant of the present embodiment, at least a part of the radically polymerizable compound is added to the following (i) so that the acid value of the sealant is 0.01 to 0.15 (mgKOH/g). and a mixing step of mixing a radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical to obtain a sealant. Moreover, the pretreatment step may further include pretreatment by methods (ii) and (iii).
(i) Degassing treatment in an environment of 10 to 100°C and 1000 Pa or less (ii) Distillation purification (iii) Column chromatography purification
　本発明者らの知見によれば、封止剤の酸価は、ラジカル重合性化合物中の微量な酸成分に起因する。このため、本実施形態の製造方法では、前処理工程でラジカル重合性化合物を前処理することで、封止剤の酸価を特定の範囲に調整している。 According to the findings of the present inventors, the acid value of the sealant is due to a trace amount of acid component in the radically polymerizable compound. Therefore, in the manufacturing method of this embodiment, the acid value of the sealant is adjusted to a specific range by pretreating the radically polymerizable compound in the pretreatment step.
　前処理工程における前処理方法は、（ｉ）を含み、更に（ｉｉ）及び（ｉｉｉ）のいずれを含んでもよい。 The pretreatment method in the pretreatment step includes (i) and may further include either (ii) or (iii).
＜前処理方法（ｉ）＞
　前処理方法（ｉ）は、ラジカル重合性化合物を脱気処理する方法である。 <Pretreatment method (i)>
The pretreatment method (i) is a method of degassing the radically polymerizable compound.
　ラジカル重合性化合物が複数種存在する場合、前処理方法（ｉ）では、各ラジカル重合性化合物を個別に脱気処理してよく、複数種のラジカル重合性化合物を同時に脱気処理（複数種のラジカル重合性化合物の混合物を脱気処理）してもよい。 When multiple types of radically polymerizable compounds exist, in the pretreatment method (i), each radically polymerizable compound may be individually degassed, or multiple types of radically polymerizable compounds may be simultaneously degassed (multiple types of The mixture of radically polymerizable compounds may be subjected to deaeration treatment).
　脱気処理における温度は、１０～１００℃であり、好ましくは３０～９０℃であり、より好ましくは４０～８０℃である。 The temperature in the degassing treatment is 10 to 100°C, preferably 30 to 90°C, and more preferably 40 to 80°C.
　脱気処理における圧力は、１０００Ｐａ以下であり、好ましくは８００Ｐａ以下、より好ましくは５００Ｐａ以下である。また、脱気処理における圧力は、例えば１Ｐａ以上であってよく、１０Ｐａ以上であってもよい。すなわち、脱気処理における圧力は、例えば１～１０００Ｐａ、１～８００Ｐａ、１～５００Ｐａ、１０～１０００Ｐａ、１０～８００Ｐａ又は１０～５００Ｐａであってもよい。 The pressure in the degassing treatment is 1000 Pa or less, preferably 800 Pa or less, more preferably 500 Pa or less. Further, the pressure in the degassing process may be, for example, 1 Pa or more, or 10 Pa or more. That is, the pressure in the deaeration process may be, for example, 1 to 1000 Pa, 1 to 800 Pa, 1 to 500 Pa, 10 to 1000 Pa, 10 to 800 Pa, or 10 to 500 Pa.
　脱気処理は、例えば、攪拌手段を備え、真空ポンプ及び真空計に繋いだ容器中で行うことができる。脱気処理中には、適切な真空度を保つ観点、及び、重合性化合物の重合を抑制する観点から、エアーによるバブリング（エアーの吹込み）を行ってもよい。 The degassing treatment can be carried out, for example, in a container equipped with a stirring means and connected to a vacuum pump and a vacuum gauge. During the degassing process, air bubbling (air blowing) may be performed from the viewpoint of maintaining an appropriate degree of vacuum and suppressing polymerization of the polymerizable compound.
＜前処理方法（ｉｉ）＞
　前処理方法（ｉｉ）は、ラジカル重合性化合物を蒸留精製する方法である。 <Pretreatment method (ii)>
The pretreatment method (ii) is a method of purifying the radically polymerizable compound by distillation.
　蒸留精製の好適な条件としては、例えば、温度１０～１００℃、圧力０．１ＭＰａ以下等が挙げられる。 Suitable conditions for distillation purification include, for example, a temperature of 10 to 100°C and a pressure of 0.1 MPa or less.
　蒸留精製の具体例としては、例えば、以下の方法が挙げられる。なお、蒸留精製の方法は以下の方法に限定されず、公知の蒸留精製の方法から、適宜選択してよい。
　ラジカル重合性化合物を、回転式蒸留装置（東京理化器械株式会社製、「ロータリーエバポレーター　Ｎ－１０００Ｓ」）を用いて、６５℃に調整した温浴中、０．０５ＭＰａの圧力で、回転数５０ｒ／ｍｉｎで３時間、蒸留する。 Specific examples of distillation purification include the following methods. Note that the distillation purification method is not limited to the following method, and may be appropriately selected from known distillation purification methods.
The radically polymerizable compound was heated at a pressure of 0.05 MPa and a rotational speed of 50 r/min in a hot bath adjusted to 65°C using a rotary distillation apparatus (manufactured by Tokyo Rika Kikai Co., Ltd., "Rotary Evaporator N-1000S"). Distill for 3 hours.
＜前処理方法（ｉｉｉ）＞
　前処理方法（ｉｉｉ）は、ラジカル重合性化合物をカラムクロマトグラフィー精製する方法である。 <Pretreatment method (iii)>
The pretreatment method (iii) is a method of purifying a radically polymerizable compound by column chromatography.
　カラムクロマトグラフィー精製としては、例えば、シリカゲルを吸着材としたカラムクロマトグラフィー精製等が挙げられる。 Examples of column chromatography purification include column chromatography purification using silica gel as an adsorbent.
　カラムクロマトグラフィー精製の具体例としては、例えば、以下の方法が挙げられる。なお、カラムクロマトグラフィー精製の方法は以下の方法に限定されず、公知のカラムクロマトグラフィー精製の方法から、適宜選択してよい。
　ガラスカラムにシリカゲルを充填し、酢酸エチル：ヘプタン＝２：９８の展開溶媒にてラジカル重合性化合物を溶いてシリカゲル上に置き、同展開溶媒で分離精製する。得られた溶液中の溶媒を除去し、精製されたラジカル重合性化合物を得る。 Specific examples of column chromatography purification include the following method. Note that the column chromatography purification method is not limited to the following method, and may be appropriately selected from known column chromatography purification methods.
A glass column is filled with silica gel, a radically polymerizable compound is dissolved in a developing solvent of ethyl acetate:heptane=2:98, placed on the silica gel, and separated and purified using the same developing solvent. The solvent in the obtained solution is removed to obtain a purified radically polymerizable compound.
　前処理工程では、封止剤の酸価が０．０１～０．１５（ｍｇＫＯＨ／ｇ）となるように前処理を行う。前処理の条件等は、封止剤におけるラジカル重合性化合物の配合量等に応じて適宜調整してよい。すなわち、前処理工程では、予め決定された封止剤の組成に応じて、前処理の条件等を適宜調整してよい。 In the pretreatment step, pretreatment is performed so that the acid value of the sealant is 0.01 to 0.15 (mgKOH/g). The pretreatment conditions may be adjusted as appropriate depending on the amount of the radically polymerizable compound in the sealant. That is, in the pretreatment step, the pretreatment conditions and the like may be adjusted as appropriate depending on the predetermined composition of the sealant.
　混合工程は、ラジカル重合性化合物と、光重合開始剤と、安定ラジカルを有する安定ラジカル型化合物と、を混合して、封止剤を得る工程である。 The mixing step is a step of mixing a radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical to obtain a sealant.
　混合工程における混合方法は特に限定されず、例えば、スリーワンモーター等の撹拌機による混合、ミックスローターによる混合等の方法が挙げられる。 The mixing method in the mixing step is not particularly limited, and examples thereof include methods such as mixing using a stirrer such as a three-one motor and mixing using a mix rotor.
　混合工程における好適な混合条件としては、例えば、温度１５～４０℃、１時間以上の混合等が挙げられる。 Suitable mixing conditions in the mixing step include, for example, mixing at a temperature of 15 to 40° C. for 1 hour or more.
＜封止材＞
　本実施形態の封止剤を硬化することで、ラジカル重合性化合物の重合体を含有する硬化体を得ることができる。この硬化体は、安定ラジカル型化合物又はその反応物として、安定ラジカルを含んでいてよい。この硬化体は、有機ＥＬ素子用封止材として好適に用いることができる。 <Sealing material>
By curing the sealant of this embodiment, a cured product containing a polymer of a radically polymerizable compound can be obtained. This cured product may contain a stable radical as a stable radical type compound or a reactant thereof. This cured product can be suitably used as a sealing material for organic EL elements.
　本実施形態の封止剤は、光照射により硬化することができる。本実施形態の封止剤の硬化に用いられる光源は特に限定されない。光源としては、例えば、ハロゲンランプ、メタルハライドランプ、ハイパワーメタルハライドランプ（インジウム等を含有する）、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、キセノンエキシマランプ、キセノンフラッシュランプ、ＬＥＤ等が挙げられる。 The sealant of this embodiment can be cured by light irradiation. The light source used for curing the sealant of this embodiment is not particularly limited. Examples of light sources include halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium, etc.), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, LEDs, etc. can be mentioned.
　上記光源は、各々放射波長やエネルギー分布が異なる。そのため、上記光源は光重合開始剤の反応波長等により適宜選択されてよい。また、自然光（太陽光）も反応開始光源になり得る。 The above light sources have different emission wavelengths and energy distributions. Therefore, the light source may be appropriately selected depending on the reaction wavelength of the photopolymerization initiator. Natural light (sunlight) can also be a light source for initiating the reaction.
　光源による照射は、直接照射であってもよく、反射鏡、ファイバー等による集光照射であってもよい。また、低波長カットフィルター、熱線カットフィルター、コールドミラー等を用いた照射であってもよい。 Irradiation by a light source may be direct irradiation, or may be focused irradiation using a reflecting mirror, fiber, etc. Alternatively, irradiation may be performed using a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like.
　本実施形態の封止剤を用いて有機ＥＬ素子を封止する方法としては、例えば、下記の封止方法等が挙げられる。 Examples of the method for sealing an organic EL element using the sealant of this embodiment include the following sealing method.
・封止方法
　有機ＥＬ素子が設置された基板を準備し、当該基板の有機ＥＬ素子が設置された面の上に、封止剤を塗布し、封止剤の塗膜を形成する。次いで、塗膜に光を照射して、封止剤の硬化体からなる封止材を形成する。これにより、有機ＥＬ素子が封止材により封止される。 - Sealing method A substrate on which an organic EL element is installed is prepared, and a sealant is applied on the surface of the substrate on which the organic EL element is installed to form a coating film of the sealant. Next, the coating film is irradiated with light to form a sealant made of a cured sealant. Thereby, the organic EL element is sealed with the sealing material.
　封止剤の塗布には、インクジェット方式を採用することが好ましい。有機ＥＬ表示装置の製造では、複数の有機ＥＬ素子が設置された大面積の基板上に封止剤を塗布する必要がある。本実施形態の封止剤は、インクジェット方式であっても高い吐出性を維持しつつ塗布を行うことができるため、大面積の基板上に均一に塗膜を形成できる。 It is preferable to use an inkjet method for applying the sealant. In manufacturing an organic EL display device, it is necessary to apply a sealant onto a large-area substrate on which a plurality of organic EL elements are installed. The sealant of this embodiment can be applied while maintaining high ejection properties even when using an inkjet method, so that a coating film can be uniformly formed on a large-area substrate.
　封止剤の塗膜の膜厚は、例えば１μｍ以上であってよく、好ましくは３μｍ以上である。これにより、十分な封止能を有する封止材が形成されやすくなる。また、封止剤の塗膜の膜厚は、例えば１０μｍ以下であってよく、好ましくは９μｍ以下である。これにより、有機ＥＬ表示装置の小型化、製造コストの削減等が期待される。すなわち、封止剤の塗膜の膜厚は、例えば１～１０μｍ、１～９μｍ、３～１０μｍ又は３～９μｍであってもよい。 The thickness of the coating film of the sealant may be, for example, 1 μm or more, and preferably 3 μm or more. This makes it easier to form a sealing material having sufficient sealing ability. Further, the thickness of the coating film of the sealant may be, for example, 10 μm or less, and preferably 9 μm or less. This is expected to reduce the size of organic EL display devices and reduce manufacturing costs. That is, the thickness of the coating film of the sealant may be, for example, 1 to 10 μm, 1 to 9 μm, 3 to 10 μm, or 3 to 9 μm.
　以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。例えば本発明は、上記以外の様々な構成を採用できる。また、本発明は本発明の目的を達成できる範囲で上記実施形態を変形、改良等したものであってもよい。 Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. For example, the present invention can adopt various configurations other than those described above. Furthermore, the present invention may be modified or improved from the above embodiments within the scope that can achieve the object of the present invention.
　例えば、本発明は、有機ＥＬ素子と、有機ＥＬ素子を封止する封止材と、を備える有機ＥＬ表示装置に関するものであってよい。封止材は、上述の封止剤の硬化体を含む。この有機ＥＬ表示装置において、有機ＥＬ素子は公知の有機ＥＬ素子であってよい。また、有機ＥＬ素子及び封止材以外の構成は、公知の有機ＥＬ表示装置と同様であってよい。 For example, the present invention may relate to an organic EL display device that includes an organic EL element and a sealing material that seals the organic EL element. The sealant includes a cured product of the above-mentioned sealant. In this organic EL display device, the organic EL element may be a known organic EL element. Further, the configuration other than the organic EL element and the sealing material may be the same as that of a known organic EL display device.
　以下、実施例によって本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
　実施例及び比較例では、以下の成分を使用した。
（Ａ）ラジカル重合性化合物
（Ａ－１）ＳＲ２６２（１，１２－ドデカンジオールジメタクリレート、アルケマ社製）（鎖状モノマー）
（Ａ－２）ＢＰＥ２００（エトキシ化ビスフェノールＡジメタクリレート（下記式で表される化合物（ｍ＋ｎ＝４）、新中村化学工業社製）（芳香族モノマー）
Figure JPOXMLDOC01-appb-C000001
 （Ａ－３）ＬＩＮＣ－１６２Ａ（２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９－ヘキサデカフルオロ－１，１０－デカンジアクリレート、共栄社化学社製）（含フッ素モノマー）
（Ａ－４）ＦＡ－５１２ＡＳ（ジシクロペンテニルオキシエチルアクリレート、昭和電工マテリアルズ社製）（不飽和脂環式モノマー）
（Ａ－５）ＤＣＰ（ジメチロール－トリシクロデカンジメタクリレート、新中村化学工業社製）（飽和脂環式モノマー） In the Examples and Comparative Examples, the following components were used.
(A) Radical polymerizable compound (A-1) SR262 (1,12-dodecanediol dimethacrylate, manufactured by Arkema) (chain monomer)
(A-2) BPE200 (ethoxylated bisphenol A dimethacrylate (compound represented by the following formula (m+n=4), manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (aromatic monomer)
Figure JPOXMLDOC01-appb-C000001
 (A-3) LINC-162A (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-de Candiacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) (fluorine-containing monomer)
(A-4) FA-512AS (dicyclopentenyloxyethyl acrylate, manufactured by Showa Denko Materials) (unsaturated alicyclic monomer)
(A-5) DCP (dimethylol-tricyclodecane dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) (saturated alicyclic monomer)
（Ｂ）重合開始剤
（Ｂ－１）ＴＰＯ（２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド、ＩＧＭ　Ｒｅｓｉｎｓ社製） (B) Polymerization initiator (B-1) TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by IGM Resins)
（Ｃ）安定ラジカル型化合物
（Ｃ－１）ＴＥＭＰＯメタクリラート（４－メタクリロイルオキシ－２，２，６，６－テトラメチルピペリジン１－オキシル、東京化成工業社製） (C) Stable radical type compound (C-1) TEMPO methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, manufactured by Tokyo Kasei Kogyo Co., Ltd.)
　実施例及び比較例では、以下の測定及び評価を行った。 In the Examples and Comparative Examples, the following measurements and evaluations were performed.
（酸価の測定）
　試料２ｇを５０ｍＬトールビーカーに秤取り、２－プロパノールを４０ｍＬ加え、５分間撹拌した。電位の安定を確認後、平沼製作所製　自動滴定装置　ＣＯＭ　５５０にて、滴定液０．１ｍｏｌ／Ｌ　２－プロパノール性水酸化カリウム標準液（和光純薬製）を用いて、電位差滴定法で終点を求めた。 (Measurement of acid value)
2 g of the sample was weighed into a 50 mL tall beaker, 40 mL of 2-propanol was added, and the mixture was stirred for 5 minutes. After confirming the stability of the potential, the end point was determined by potentiometric titration using a titrant 0.1 mol/L 2-propanolic potassium hydroxide standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) using an automatic titrator COM 550 manufactured by Hiranuma Seisakusho. I asked for it.
（有機ＥＬ表示装置の信頼性評価（有機ＥＬ信頼性））
・評価用の有機ＥＬ表示装置の作製
　３０ｍｍ角のＩＴＯ電極付きガラス基板（厚さ７００μｍ）を、アセトン及びイソプロパノールそれぞれを用いて洗浄した。その後、真空蒸着法にて以下の化合物を薄膜となるように順次蒸着し、陽極／正孔注入層／正孔輸送層／発光層／Ｈｏｌｅ　Ｂｌｏｃｋｉｎｇ層／電子輸送層／電子注入層／陰極からなる２ｍｍ角の有機ＥＬ素子を有する基板を得た。各層の構成は以下の通りである。
　　　陽極（ＩＴＯ）：１５０ｎｍ
　　　正孔注入層（高分子ＨＩＬ）：６０ｎｍ
　　　正孔輸送層（α－ＮＰＤ）：３０ｎｍ
　　　発光層（Ｉｒ（ｐｐｙ）３＋ＣＢＰ［６％］）：３０ｎｍ
　　　Ｈｏｌｅ　Ｂｌｏｃｋｉｎｇ層（ＢＡｌｑ）：１０ｎｍ
　　　電子輸送層（Ａｌｑ３）：３０ｎｍ
　　　電子注入層（ＬｉＦ）：０．８ｎｍ
　　　陰極（ＭｇＡｇ／ＩＺＯ）：１０ｎｍ／１００ｎｍ
　ＩＴＯは酸化インジウムスズであり、ＨＩＬはＨｏｌｅ　Ｉｎｊｅｃｔｉｏｎ　Ｌａｙｅｒであり、α－ＮＰＤはＮ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ジナフチルベンジジンであり、Ｉｒ（ｐｐｙ）３はイリジウム錯体［トリス（２－フェニルピリジン）イリジウム］であり、ＣＢＰは４，４’－Ｎ，Ｎ’－ジカルバゾール－ビフェニルであり、ＢＡｌｑはビス（２－メチル－８－キノリノラト）（ｐ－フェニルフェノラト）アルミニウムであり、Ａｌｑ３はトリス（８－ヒドロキシキノリノラト）アルミニウムであり、ＬｉＦはフッ化リチウムであり、ＩＺＯは酸化インジウム亜鉛である。
　次に、窒素雰囲気下にて富士フイルム社製のインクジェット装置（品番：ＤＭＰ２８５０）を用いて、２ｍｍ×２ｍｍの有機ＥＬ素子を覆うように封止剤を打滴し、厚み１０μｍの塗膜を得た。その後、窒素雰囲気下で、波長３９５ｎｍの光を発光するＬＥＤランプ（ＨＯＹＡ社製ＵＶ－ＬＥＤ　ＬＩＧＨＴ　ＳＯＵＲＣＥ　Ｈ－４ＭＬＨ２００－Ｖ１）により、積算光量１，５００ｍＪ／ｃｍ２となるように、波長３９５ｎｍの光を塗膜に照射した。これにより硬化膜を得た。得られた硬化膜の全体を覆うように、１０ｍｍ×１０ｍｍの開口部を有するマスク（覆い）を設置し、プラズマＣＶＤ法にてＳｉＮ膜を形成した。形成されたＳｉＮ（無機物膜）の厚さは約１μｍであった。これにより、有機ＥＬ素子の封止体を得た。
　得られた封止体を、３０ｍｍ×３０ｍｍ×２５μｍｔの透明な基材レス両面テープを用いて、３０ｍｍ×３０ｍｍ×０．７ｍｍｔの無アルカリガラス（Ｃｏｒｎｉｎｇ社製　Ｅａｇｌｅ　ＸＧ）と貼り合わせた。これにより、評価用の有機ＥＬ表示装置を作製した。
・信頼性試験
　評価用の有機ＥＬ表示装置を、８５℃、８５％ＲＨの高温高湿環境下に５００時間静置した。この高温高湿処理の前後で、評価用の有機ＥＬ表示装置に電流を流し、発光面を撮影した。撮影された画像（高温高湿処理前の画像及び高温高湿処理後の画像）を、イノテック社の画像解析ソフト「Ｑｕｉｃｋ　Ｇｒａｉｎ」で解析し、発光面積を求めた。そして、高温高湿処理の前後での発光面積減少率（％）を算出した。 (Reliability evaluation of organic EL display device (organic EL reliability))
- Production of organic EL display device for evaluation A 30 mm square glass substrate with an ITO electrode (700 μm thick) was cleaned using acetone and isopropanol, respectively. Thereafter, the following compounds were sequentially deposited into a thin film using a vacuum evaporation method to form an anode, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. A substrate having a 2 mm square organic EL element was obtained. The structure of each layer is as follows.
Anode (ITO): 150nm
Hole injection layer (polymer HIL): 60nm
Hole transport layer (α-NPD): 30nm
Light-emitting layer (Ir(ppy) 3 +CBP [6%]): 30 nm
Hole blocking layer (BAlq): 10nm
Electron transport layer (Alq 3 ): 30 nm
Electron injection layer (LiF): 0.8nm
Cathode (MgAg/IZO): 10nm/100nm
ITO is indium tin oxide, HIL is Hole Injection Layer, α-NPD is N,N'-diphenyl-N,N'-dinaphthylbenzidine, and Ir(ppy) 3 is an iridium complex [tris(2 -phenylpyridine)iridium], CBP is 4,4'-N,N'-dicarbazole-biphenyl, and BAlq is bis(2-methyl-8-quinolinolato)(p-phenylphenolato)aluminum. , Alq 3 is tris(8-hydroxyquinolinolato)aluminum, LiF is lithium fluoride, and IZO is indium zinc oxide.
Next, using a Fujifilm inkjet device (product number: DMP2850) under a nitrogen atmosphere, droplets of sealant were applied to cover the 2 mm x 2 mm organic EL element to obtain a coating film with a thickness of 10 μm. Ta. After that, in a nitrogen atmosphere, light with a wavelength of 395 nm was emitted using an LED lamp (UV-LED LIGHT SOURCE H-4MLH200-V1 manufactured by HOYA) so that the cumulative light amount was 1,500 mJ/cm 2 . was irradiated onto the coating film. A cured film was thus obtained. A mask (cover) having an opening of 10 mm x 10 mm was placed so as to cover the entire cured film, and a SiN film was formed by plasma CVD. The thickness of the formed SiN (inorganic film) was about 1 μm. Thereby, a sealed body of an organic EL element was obtained.
The obtained sealed body was bonded to a 30 mm x 30 mm x 0.7 mm thick alkali-free glass (Eagle XG manufactured by Corning) using a 30 mm x 30 mm x 25 μm thick transparent base material-less double-sided tape. In this way, an organic EL display device for evaluation was manufactured.
- Reliability test The organic EL display device for evaluation was left standing in a high temperature and high humidity environment of 85° C. and 85% RH for 500 hours. Before and after this high-temperature, high-humidity treatment, a current was applied to the organic EL display device for evaluation, and the light-emitting surface was photographed. The photographed images (images before high-temperature, high-humidity treatment and images after high-temperature, high-humidity treatment) were analyzed using Innotek's image analysis software "Quick Grain" to determine the luminescent area. Then, the luminescent area reduction rate (%) before and after the high temperature and high humidity treatment was calculated.
（実施例１～２、比較例１）
　表１に示すラジカル重合性化合物を、表１に示す組成で混合し、６０℃、８００Ｐａの環境下で表１に示す時間、脱気処理を行った。次いで、表１に示す組成で各成分を混合し、封止剤を作成した。得られた封止剤について、上記の測定及び評価を行った。結果を表１に示す。 (Examples 1-2, Comparative Example 1)
The radically polymerizable compounds shown in Table 1 were mixed in the composition shown in Table 1, and deaeration treatment was performed in an environment of 60° C. and 800 Pa for the time shown in Table 1. Next, each component was mixed with the composition shown in Table 1 to create a sealant. The above measurements and evaluations were performed on the obtained sealant. The results are shown in Table 1.
（実施例３～４、比較例２）
　表２に示すラジカル重合性化合物を、表２に示す組成で混合し、６０℃、８００Ｐａの環境下で表２に示す時間、脱気処理を行った。次いで、表２に示す組成で各成分を混合し、封止剤を作成した。得られた封止剤について、上記の測定及び評価を行った。結果を表２に示す。 (Examples 3-4, Comparative Example 2)
The radical polymerizable compounds shown in Table 2 were mixed in the composition shown in Table 2, and deaeration treatment was performed in an environment of 60° C. and 800 Pa for the time shown in Table 2. Next, each component was mixed with the composition shown in Table 2 to create a sealant. The above measurements and evaluations were performed on the obtained sealant. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Claims (5)

  1. 　ラジカル重合性化合物と、光重合開始剤と、安定ラジカルを有する安定ラジカル型化合物と、を含有し、
    　酸価が０．０１～０．１５（ｍｇＫＯＨ／ｇ）である、有機エレクトロルミネッセンス素子用封止剤。     Contains a radically polymerizable compound, a photopolymerization initiator, and a stable radical type compound having a stable radical,
    A sealing agent for organic electroluminescent devices having an acid value of 0.01 to 0.15 (mgKOH/g).
  2. 　前記安定ラジカルがニトロキシドラジカルである、請求項１に記載の封止剤。 The encapsulant according to claim 1, wherein the stable radical is a nitroxide radical.
  3. 　請求項１又は２に記載の封止剤の硬化体を含む、封止材。 A sealing material comprising a cured product of the sealant according to claim 1 or 2.
  4. 　有機エレクトロルミネッセンス素子と、
    　前記有機エレクトロルミネッセンス素子を封止する、請求項３に記載の封止材と、
    を備える、有機エレクトロルミネッセンス表示装置。     an organic electroluminescent element,
    The sealing material according to claim 3, which seals the organic electroluminescent element.
    An organic electroluminescent display device comprising:
  5. 　請求項１又は２に記載の封止剤の製造方法であって、
    　前記封止剤の酸価が０．０１～０．１５（ｍｇＫＯＨ／ｇ）となるように、ラジカル重合性化合物の少なくとも一部を、１０～１００℃、１０００Ｐａ以下の環境下で脱気処理する前処理工程と、
    　前記ラジカル重合性化合物と、光重合開始剤と、安定ラジカルを有する安定ラジカル型化合物と、を混合して、前記封止剤を得る混合工程と、
    を含む、有機エレクトロルミネッセンス素子用封止剤の製造方法。     A method for manufacturing a sealant according to claim 1 or 2, comprising:
    At least a portion of the radically polymerizable compound is degassed in an environment of 10 to 100°C and 1000 Pa or less so that the acid value of the sealant is 0.01 to 0.15 (mgKOH/g). a pretreatment step;
    A mixing step of obtaining the sealant by mixing the radically polymerizable compound, a photopolymerization initiator, and a stable radical-type compound having a stable radical;
    A method for producing a sealant for an organic electroluminescent device, comprising:
PCT/JP2023/010936 2022-03-25 2023-03-20 Sealing agent and sealing material for organic electroluminescent elements, organic electroluminescent display device, and method for producing sealing agent for organic electroluminescent elements WO2023182283A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010044870A (en) * 2008-08-08 2010-02-25 Nippon Shokubai Co Ltd Sealing layer forming material for flat panel display, sealing layer for flat panel display, and flat panel display
US20120059143A1 (en) * 2010-09-07 2012-03-08 Basf Se Preparing polyester alcohols
JP2013213182A (en) * 2011-10-07 2013-10-17 Fujifilm Corp Sealing agent for semiconductor light-emitting device, sealing material for semiconductor light-emitting device using the same, and semiconductor light-emitting device
JP2014127266A (en) * 2012-12-25 2014-07-07 Furukawa Electric Co Ltd:The Transparent resin composition for organic electroluminescent element encapsulation, resin sheet for organic electroluminescent element encapsulation and image display device
JP2014182905A (en) * 2013-03-19 2014-09-29 Furukawa Electric Co Ltd:The Transparent resin composition for encapsulation of organic electroluminescent element, resin sheet for encapsulation of organic electroluminescent element, and image display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010044870A (en) * 2008-08-08 2010-02-25 Nippon Shokubai Co Ltd Sealing layer forming material for flat panel display, sealing layer for flat panel display, and flat panel display
US20120059143A1 (en) * 2010-09-07 2012-03-08 Basf Se Preparing polyester alcohols
JP2013213182A (en) * 2011-10-07 2013-10-17 Fujifilm Corp Sealing agent for semiconductor light-emitting device, sealing material for semiconductor light-emitting device using the same, and semiconductor light-emitting device
JP2014127266A (en) * 2012-12-25 2014-07-07 Furukawa Electric Co Ltd:The Transparent resin composition for organic electroluminescent element encapsulation, resin sheet for organic electroluminescent element encapsulation and image display device
JP2014182905A (en) * 2013-03-19 2014-09-29 Furukawa Electric Co Ltd:The Transparent resin composition for encapsulation of organic electroluminescent element, resin sheet for encapsulation of organic electroluminescent element, and image display device

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