WO2018225723A1 - Sealant for organic electroluminescent display element - Google Patents

Sealant for organic electroluminescent display element Download PDF

Info

Publication number
WO2018225723A1
WO2018225723A1 PCT/JP2018/021542 JP2018021542W WO2018225723A1 WO 2018225723 A1 WO2018225723 A1 WO 2018225723A1 JP 2018021542 W JP2018021542 W JP 2018021542W WO 2018225723 A1 WO2018225723 A1 WO 2018225723A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic
weight
compound
parts
sealing agent
Prior art date
Application number
PCT/JP2018/021542
Other languages
French (fr)
Japanese (ja)
Inventor
山本　拓也
七里　徳重
勝則 西出
信烈 梁
千鶴 金
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201880029518.4A priority Critical patent/CN110583098B/en
Priority to CN202210874228.8A priority patent/CN115232511B/en
Priority to JP2018530907A priority patent/JP7010824B2/en
Priority to KR1020197021823A priority patent/KR102658947B1/en
Publication of WO2018225723A1 publication Critical patent/WO2018225723A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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

Definitions

  • the present invention relates to a sealant for an organic EL display element that can provide an organic EL display element that is excellent in inkjet coating property, low outgassing property, adhesion to an inorganic material film, and excellent in reliability.
  • organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer.
  • organic EL organic electroluminescence
  • the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
  • Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method.
  • the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.
  • Patent Document 1 In the method of sealing with a silicon nitride film disclosed in Patent Document 1, organic light emission occurs when a silicon nitride film is formed due to unevenness on the surface of the organic EL display element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. The material layer or electrode may not be completely covered. If the coating with the silicon nitride film is incomplete, moisture will enter the organic light emitting material layer through the silicon nitride film. As a method for preventing moisture from entering into the organic light emitting material layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film. Patent Document 3 and Patent Document 4 Discloses a method of forming a resin film on an inorganic material film.
  • a method for forming a resin film there is a method in which a sealing agent is applied on a substrate using an inkjet method and then the sealing agent is cured. If such a coating method by the ink jet method is used, a resin film can be uniformly formed at high speed. However, when the sealant is made to have a low viscosity in order to be suitable for application by the ink jet method, outgas is generated, or the obtained organic EL display element is inferior in reliability, etc. There was a problem.
  • the present invention provides an organic EL display element sealant that can provide an organic EL display element that is excellent in inkjet coating property, low outgassing property, and adhesion to an inorganic material film, and that is excellent in reliability. With the goal.
  • the present invention 1 is an organic EL display device sealing agent containing a polymerizable compound and a polymerization initiator, wherein the polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound, and the polymerization In 100 parts by weight of the functional compound, the content of the monofunctional oxetane compound is 20 to 35 parts by weight, and the content of the polyfunctional oxetane compound is 25 to 40 parts by weight,
  • the sealant for organic EL display elements has a viscosity at 25 ° C. of 80 mPa ⁇ s or less and a surface tension at 25 ° C.
  • Invention 2 is a sealant for an organic EL display device containing a polymerizable compound and a polymerization initiator, wherein the polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound, and the polymerization In 100 parts by weight of the functional compound, the content of the monofunctional oxetane compound is 20 to 35 parts by weight, and the content of the polyfunctional oxetane compound is 25 to 40 parts by weight, It is the sealing agent for organic EL display elements used for application
  • the inventors of the present invention have a reason why the reliability of the organic EL display element obtained when the conventional sealant for organic EL display elements is used is due to the adhesiveness of the sealant to the inorganic material film. I thought it was inadequate. Therefore, the present inventors compounded the monofunctional oxetane compound and the polyfunctional oxetane compound as the polymerizable compound so as to have a specific content, respectively, and set the viscosity and the surface tension within a specific range, respectively. Considered to adjust.
  • an organic EL display element sealant that can provide an organic EL display element that is excellent in inkjet coating property, low outgassing property, and adhesion to an inorganic material film, and that is excellent in reliability. As a result, the present invention has been completed.
  • the sealing agent for organic EL display elements of the present invention contains a polymerizable compound.
  • the polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound.
  • the sealing agent for organic EL display elements of the present invention has low outgassing property and adhesion to an inorganic material film. It will be excellent.
  • Examples of the monofunctional oxetane compound include 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-3- (phenoxymethyl).
  • the lower limit of the content of the monofunctional oxetane compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the upper limit is 35 parts by weight.
  • the organic EL display element sealing agent of the present invention has excellent low outgassing property and adhesion to an inorganic material film. It will be excellent in reliability.
  • the preferable lower limit of the content of the monofunctional oxetane compound is 22 parts by weight, the preferable upper limit is 33 parts by weight, the more preferable lower limit is 25 parts by weight, and the more preferable upper limit is 30 parts by weight.
  • polyfunctional oxetane compound examples include 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane, xylylene bisoxetane, phenol novolac oxetane, oxetanyl silsesquioxane, 1,4-bis ((3-ethyl-3-oxetanylmethoxy) methyl) benzene, bis ((3-methyl-3-oxetanylmethoxy) methyl) ether, bis ((3-ethyl-3-oxetanylmethoxy) methyl) Ether, 1,4-bis ((3-methyl-3-oxetanylmethoxy) methyl) benzene, oligomers or copolymers thereof, and the like, calixarenes, calixresorcinarenes, cardo-type bisphenols , Poly (p-hydroxystyrene
  • a bifunctional oxetane compound is preferable, and 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane is more preferable from the viewpoint of ink jet coating property and the like.
  • the lower limit of the content of the polyfunctional oxetane compound in 100 parts by weight of the polymerizable compound is 25 parts by weight, and the upper limit is 40 parts by weight.
  • the sealing agent for organic EL display elements of the present invention is excellent in low outgassing and adhesion to an inorganic material film, and the resulting organic EL display element is It will be excellent in reliability.
  • the minimum with preferable content of the said polyfunctional oxetane compound is 28 weight part, a preferable upper limit is 38 weight part, and a more preferable upper limit is 35 weight part.
  • the obtained sealing agent for organic EL display elements is excellent in low outgassing and adhesion to an inorganic material film.
  • the organic EL display element to be obtained is superior in reliability.
  • the polymerizable compound preferably contains a cycloalkene oxide type alicyclic epoxy compound.
  • the sealing agent for organic EL display elements obtained will be excellent in low outgassing property and barrier property (moisture permeability prevention property) of hardened
  • coloring of the sealing agent by heat or light hardly occurs, and loss of EL emission or change in color tone due to absorption of the sealing agent can be reduced.
  • cycloalkene oxide type alicyclic epoxy compound is, for example, a structure in which a carbon-carbon double bond of cycloalkene is epoxidized as represented by the following formula (1) ( Hereinafter, it means a compound having a “cycloalkene oxide skeleton”.
  • R 1 to R 9 are a hydrogen atom, a halogen atom, or a hydrocarbon group that may contain an oxygen atom or a halogen atom, and may be the same or different. Also good. * Represents a binding position.
  • the preferable lower limit of the epoxy group equivalent of the cycloalkene oxide type alicyclic epoxy compound is 50 g / mol, and the preferable upper limit is 400 g / mol.
  • the epoxy group equivalent of the cycloalkene oxide type alicyclic epoxy compound is within this range, the cured product of the obtained sealing agent for organic EL display elements suppresses the occurrence of cracks due to heating or deformation, and the barrier. It becomes more excellent by the property.
  • the more preferable lower limit of the epoxy group equivalent of the cycloalkene oxide type alicyclic epoxy compound is 70 g / mol, and the more preferable upper limit is 300 g / mol.
  • the epoxy group equivalent of the said cycloalkene oxide type alicyclic epoxy compound is the weight (g) of cycloalkene oxide type alicyclic epoxy compound per 1 mol of epoxy groups contained in the cycloalkene oxide type alicyclic epoxy compound. Means.
  • the preferable lower limit of the molecular weight of the cycloalkene oxide type alicyclic epoxy compound is 150, and the preferable upper limit is 7000.
  • the resulting organic EL display element sealant is more excellent in the barrier properties of the cured product while suppressing generation of outgas.
  • the more preferable lower limit of the molecular weight of the cycloalkene oxide type alicyclic epoxy compound is 200, the more preferable upper limit is 5000, the still more preferable lower limit is 250, and the still more preferable upper limit is 1000.
  • the molecular weight of the cycloalkene oxide type alicyclic epoxy compound is the molecular weight obtained from the structural formula for the compound whose molecular structure is specified, but the compound having a wide distribution of polymerization degree and the modified site are not specified. About a compound, it may represent using a weight average molecular weight.
  • the above “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
  • the cycloalkene oxide type alicyclic epoxy compound may be a compound having only one cycloalkene oxide skeleton in the structure or in the repeating unit, or a compound having two or more cycloalkene oxide skeletons. However, a compound having two or more cycloalkene oxide skeletons is preferably used.
  • the organic EL display device sealing agent of the present invention is more excellent in light resistance, barrier properties, etc. It becomes.
  • cycloalkene oxide type alicyclic epoxy compound examples include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4,3 ′, 4′-diepoxy.
  • examples include bicyclohexane and bis (3,4-epoxycyclohexylmethyl) ether. Of these, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4,3 ′, 4′-diepoxybicyclohexane are used from the viewpoint of low outgassing properties and barrier properties of cured products. preferable.
  • mold alicyclic epoxy compound in 100 weight part of said polymeric compounds is 15 weight part, and a preferable upper limit is 30 weight part.
  • the content of the cycloalkene oxide type alicyclic epoxy compound is within this range, the obtained sealing agent for organic EL display elements is more excellent in low outgassing properties and cured product barrier properties.
  • mold alicyclic epoxy compound is 17 weight part, and a more preferable upper limit is 25 weight part.
  • the polymerizable compound preferably contains an alkyl polyol type epoxy compound.
  • the sealing agent for organic EL display elements obtained becomes a thing excellent in adhesiveness.
  • alkyl polyol type epoxy compound examples include neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene.
  • examples include glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, and trimethylolpropane triglycidyl ether. Of these, neopentyl glycol diglycidyl ether is preferable from the viewpoint of adhesion.
  • the preferable lower limit of the content of the alkyl polyol type epoxy compound in 100 parts by weight of the polymerizable compound is 5 parts by weight, and the preferable upper limit is 30 parts by weight.
  • the content of the alkyl polyol type epoxy compound is within this range, the obtained sealing agent for organic EL display elements is more excellent in adhesion.
  • the minimum with more preferable content of the said alkyl polyol type epoxy compound is 10 weight part, and a more preferable upper limit is 25 weight part.
  • the polymerizable compound is within the range not impairing the object of the present invention, and other than the monofunctional oxetane compound, the polyfunctional oxetane compound, the cycloalkene oxide type alicyclic epoxy compound, and the alkyl polyol type epoxy compound.
  • the polymerizable compound may be contained.
  • the other polymerizable compounds include other epoxy compounds other than the cycloalkene oxide type alicyclic epoxy compound and the alkyl polyol type epoxy compound, vinyl ether compounds, and the like.
  • Examples of the other epoxy compounds include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol O type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy. Resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, Phenol novolac type epoxy resin, ortho cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type Epoxy resins, naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
  • vinyl ether compound examples include benzyl vinyl ether, cyclohexane dimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol. Examples thereof include divinyl ether and tripropylene glycol divinyl ether.
  • the sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
  • a polymerization initiator a photocationic polymerization initiator or a thermal cationic polymerization initiator is preferably used.
  • the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
  • anion portion of the ionic photoacid-generating photocationic polymerization initiator examples include an anion portion of BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is at least And a phenyl group substituted with two or more fluorine or trifluoromethyl groups).
  • examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts having the above anion moiety, and (2,4-cyclohexane). And pentadien-1-yl) ((1-methylethyl) benzene) -Fe salt.
  • aromatic sulfonium salt examples include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetraflu
  • aromatic iodonium salt examples include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethy
  • aromatic diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
  • aromatic ammonium salt examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl)
  • Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
  • Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene.
  • nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.
  • Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Examples thereof include a photocationic polymerization initiator manufactured by 3M, a photocationic polymerization initiator manufactured by BASF, and a photocationic polymerization initiator manufactured by Rhodia. Examples of the photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd. include DTS-200. Examples of the cationic photopolymerization initiator manufactured by Union Carbide include UVI6990, UVI6974, and the like.
  • Examples of the photocation polymerization initiator manufactured by ADEKA include SP-150 and SP-170. Examples of the cationic photopolymerization initiator manufactured by 3M include FC-508, FC-512, and the like. Examples of the cationic photopolymerization initiator manufactured by BASF include IRGACURE261, IRGACURE290, and the like. Examples of the photocationic polymerization initiator manufactured by Rhodia include PI 2074.
  • the anion moiety is BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is substituted with at least two fluorine or trifluoromethyl groups
  • a sulfonium salt, a phosphonium salt, an ammonium salt, and the like are preferable.
  • sulfonium salt examples include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
  • Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
  • ammonium salt examples include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl).
  • thermal cationic polymerization initiators examples include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry, thermal cationic polymerization initiators manufactured by King Industries, and the like.
  • thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. examples include Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, and Sun-Aid SI-B4.
  • thermal cationic polymerization initiator manufactured by King Industries examples include CXC1612 and CXC1821.
  • the content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound.
  • the content of the polymerization initiator is 0.01 parts by weight or more, the obtained sealing agent for organic EL display elements is more excellent in curability.
  • the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained sealing agent for organic EL display elements does not become too fast, and the workability is improved, and the cured product is more uniform. It can be.
  • the minimum with more preferable content of the said polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for organic EL display elements of the present invention may contain a sensitizer.
  • the sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealing agent for organic EL display elements of the present invention.
  • sensitizer examples include thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4 ′ -Bis (dimethylamino) benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like.
  • thioxanthone compound include 2,4-diethylthioxanthone.
  • the content of the sensitizer is preferably 0.01 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the polymerizable compound.
  • the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited.
  • the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption.
  • the minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
  • the sealing agent for organic EL display elements of the present invention may contain a silane coupling agent.
  • the said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic EL display elements of this invention, a board
  • silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.
  • the content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the excess silane coupling agent from bleeding out.
  • the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for organic EL display elements of the present invention may further contain a surface modifier as long as the object of the present invention is not impaired.
  • a surface modifier By containing the surface modifier, the flatness of the coating film can be imparted to the organic EL display element sealant of the present invention.
  • the surface modifier include surfactants and leveling agents.
  • Examples of the surface modifier include silicone-based and fluorine-based ones.
  • Examples of commercially available surface modifiers include BYK-340, BYK-345 (both manufactured by Big Chemie Japan) and Surflon S-611 (manufactured by AGC Seimi Chemical).
  • the encapsulant for organic EL display elements of the present invention may contain a solvent for the purpose of adjusting the viscosity, but problems such as deterioration of the organic light emitting material layer and generation of outgas due to the remaining solvent. Therefore, it is preferable that the solvent is not contained or the solvent content is 0.05% by weight or less.
  • the sealing agent for organic EL display elements of this invention contains well-known various additives, such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, a ultraviolet absorber, antioxidant, as needed. May be.
  • Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a polymerizable compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. And a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
  • a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
  • the sealing agent for organic EL display elements of the present invention 1 has an upper limit of viscosity at 25 ° C. of 80 mPa ⁇ s.
  • the upper limit with the preferable viscosity of the sealing agent for organic EL display elements of this invention 1 is 60 mPa * s, and a more preferable upper limit is 20 mPa * s.
  • the minimum with a preferable viscosity of the sealing agent for organic EL display elements of this invention 1 is 5 mPa * s.
  • the said viscosity in this specification means the value measured on 25 degreeC and 100 rpm conditions using an E-type viscosity meter.
  • the preferable upper limit of the viscosity in 25 degreeC is 80 mPa * s.
  • the sealing agent for organic EL display elements of this invention 2 becomes more excellent by inkjet applicability
  • the more preferable upper limit of the viscosity of the sealing agent for organic EL display elements of the present invention 2 is 60 mPa ⁇ s, and the more preferable upper limit is 20 mPa ⁇ s.
  • the minimum with a preferable viscosity of the sealing agent for organic EL display elements of this invention 2 is 5 mPa * s.
  • the sealing agent for organic EL display elements of the present invention 1 has a lower limit of surface tension at 25 ° C. of 15 mN / m and an upper limit of 35 mN / m. When the surface tension is within this range, the organic EL display element sealant of the first aspect of the invention has excellent ink jet coating properties.
  • the preferable lower limit of the surface tension of the sealant for organic EL display elements of the present invention 1 is 20 mN / m, the preferable upper limit is 30 mN / m, the more preferable lower limit is 22 mN / m, and the more preferable upper limit is 28 mN / m.
  • the surface tension can be measured with a dynamic wettability tester at 25 ° C.
  • the sealing agent for organic EL display elements of this invention 2 the preferable minimum of the surface tension in 25 degreeC is 15 mN / m, and a preferable upper limit is 35 mN / m.
  • the organic EL display element sealant of the second aspect of the present invention is superior in ink jet coating properties.
  • the more preferable lower limit of the surface tension of the sealant for organic EL display elements of the present invention 2 is 20 mN / m
  • the more preferable upper limit is 30 mN / m
  • the still more preferable lower limit is 22 mN / m
  • the still more preferable upper limit is 28 mN / m.
  • the preferable lower limit of the total light transmittance of light at a wavelength of 380 to 800 nm of the cured product of the encapsulant for organic EL display elements of the present invention is 80%.
  • the total light transmittance is 80% or more, the obtained organic EL display element has superior optical characteristics.
  • a more preferable lower limit of the total light transmittance is 85%.
  • the total light transmittance can be measured using a spectrometer such as AUTOMATIC HAZE METER MODEL TC-III DPK (manufactured by Tokyo Denshoku).
  • cured material used for the measurement of the said light transmittance and the water vapor transmission rate and moisture content mentioned later can be obtained by irradiating 3000 mJ / cm ⁇ 2 > of ultraviolet rays with a wavelength of 365 nm using light sources, such as an LED lamp, for example. it can.
  • the transmittance at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours is preferably 85% or more at an optical path length of 20 ⁇ m.
  • the transmittance after irradiating the ultraviolet rays for 100 hours is 85% or more, the transparency is high, the loss of light emission is small, and the color reproducibility is excellent.
  • a more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and a more preferable lower limit is 95%.
  • the light source for irradiating the ultraviolet rays a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
  • the sealant for an organic EL display device of the present invention has a moisture permeability of 100 g / 100 ⁇ m when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208.
  • m is preferably 2 or less.
  • the moisture content of the cured product is preferably less than 0.5% when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours.
  • the moisture content of the cured product is less than 0.5%, the effect of preventing the deterioration of the organic light emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability. It becomes.
  • a more preferable upper limit of the moisture content of the cured product is 0.3%.
  • the method for measuring the moisture content include a method of obtaining by a Karl Fischer method in accordance with JIS K 7251, and a method of obtaining a weight increment after water absorption in accordance with JIS K 7209-2.
  • an organic EL display element using the sealing agent for organic EL display elements of the present invention for example, a step of applying the sealing agent for organic EL display elements of the present invention to a substrate by an inkjet method, And a method of curing the applied sealing agent for organic EL display elements by light irradiation and / or heating.
  • the organic EL display element sealant of the present invention may be applied to the entire surface of the substrate, or on a part of the substrate. It may be applied.
  • the shape of the sealing portion of the sealing agent for organic EL display elements of the present invention formed by coating is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air. A shape that completely covers the body may be formed, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which a partial opening is provided in the peripheral portion of the laminate. It may be formed.
  • the organic EL display sealant element of the present invention When curing the organic EL display element sealing agent of the present invention by light irradiation, the organic EL display sealant element of the present invention, 300 nm or more 400nm or less wavelength and 300 mJ / cm 2 or more 3000 mJ / cm 2 or less of It can be suitably cured by irradiating with an accumulated amount of light.
  • Examples of the light source used for the light irradiation include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, and a xenon.
  • a lamp, an LED lamp, a fluorescent lamp, sunlight, an electron beam irradiation apparatus, etc. are mentioned.
  • These light sources may be used independently and 2 or more types may be used together. These light sources are appropriately selected according to the absorption wavelength of the photocationic polymerization initiator.
  • Examples of the light irradiation means to the organic EL display element sealant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Any irradiation means may be used.
  • the cured product obtained by the step of curing the organic EL display element sealing agent by light irradiation and / or heating may be further coated with an inorganic material film.
  • the inorganic material forming the inorganic material layer can be a conventionally known, for example, silicon nitride (SiN x), silicon oxide (SiO x), and the like.
  • the inorganic material film may be a single layer or may be a laminate of a plurality of types of layers. Moreover, you may coat
  • the method for producing the organic EL display element comprises a step of bonding a base material (hereinafter also referred to as “one base material”) coated with the organic EL display element sealing agent of the present invention and the other base material.
  • the substrate on which the sealing agent for organic EL display elements of the present invention is applied (hereinafter also referred to as “one substrate”) may be a substrate on which a laminate having an organic light emitting material layer is formed. A base material on which the laminate is not formed may be used.
  • the present invention is applied to the one substrate so that the laminate can be protected from the outside air when the other substrate is bonded. What is necessary is just to apply
  • the sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.
  • the step of curing the organic EL display element sealant by light irradiation and / or heating may be performed before the step of bonding the one base material and the other base material, You may perform after the process of bonding a base material and said other base material.
  • the organic EL display of the present invention preferably has a pot life of 1 minute or longer after irradiation with light and / or heating until the curing reaction proceeds and adhesion becomes impossible. When the pot life is 1 minute or longer, higher adhesion strength can be obtained without excessive curing before the one base material and the other base material are bonded together.
  • a method of bonding the one base material and the other base material is not particularly limited, but it is preferable to bond them in a reduced-pressure atmosphere.
  • the preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa.
  • the degree of vacuum in the reduced-pressure atmosphere is within this range, the one base material and the other base material are not spent for a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Bubbles in the sealing agent for organic EL display elements of the present invention when the material is bonded can be more efficiently removed.
  • the sealing agent for organic EL display elements which can obtain the organic EL display element which is excellent in inkjet applicability
  • Examples 1 to 15, Comparative Examples 1 to 4 According to the blending ratios described in Tables 1 to 3, each material was stirred and mixed uniformly at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Primix, “Homodisper L type”). Sealants for organic EL display elements of Examples 1 to 15 and Comparative Examples 1 to 4 were prepared. About each sealing agent for organic EL display elements obtained in Examples and Comparative Examples, measurement was performed using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 100 rpm. Tables 1 to 3 show the measured viscosity and the surface tension measured at 25 ° C. using a dynamic wettability tester (Reska, “WET-6100”).
  • each of the sealing agents for organic EL display elements obtained in the examples and comparative examples is a liquid of 30 picoliters using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet). With a drop amount, 1000 drops were applied at a speed of 5 m / sec on a non-alkali glass (ASA 100, manufactured by Asahi Glass Co., Ltd.) washed with alkali at a pitch of 500 ⁇ m.
  • ASA 100 non-alkali glass
  • the diameter of the droplet on the alkali-free glass 10 minutes after the coating was measured, and “ ⁇ ” when the droplet diameter was 150 ⁇ m or more, and “when the droplet diameter was 50 ⁇ m or more and less than 150 ⁇ m” “ ⁇ ”, the case where the diameter of the droplet was less than 50 ⁇ m was evaluated as “ ⁇ ” and the wet spreading property was evaluated.
  • the peeling was 5% or less, “ ⁇ ”, when the peeling was more than 5% and 35% or less, “ ⁇ ”, and the peeling was more than 35% and 65% or less.
  • “ ⁇ ” the case where peeling exceeded 65% was evaluated as “x”, and the adhesion to the inorganic material film was evaluated.
  • this substrate is fixed to the substrate folder of the vacuum evaporation apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -NPD) is added to the unglazed crucible.
  • 200 mg of tris (8-quinolinolato) aluminum (Alq 3 ) was put in the crucible, and the pressure in the vacuum chamber was reduced to 1 ⁇ 10 ⁇ 4 Pa. Thereafter, the crucible containing ⁇ -NPD was heated, and ⁇ -NPD was deposited on the substrate at a deposition rate of 15 s / s to form a 600 ⁇ ⁇ hole transport layer.
  • the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 ⁇ at a deposition rate of 15 ⁇ / s.
  • the substrate on which the hole transport layer and the organic light-emitting material layer are formed is transferred to another vacuum vapor deposition apparatus.
  • 1.0 g was added.
  • the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 ⁇ 10 ⁇ 4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did.
  • the inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm ⁇ 10 mm was arranged was taken out.
  • a mask having an opening of 13 mm ⁇ 13 mm is installed so as to cover the entire laminated body of the substrate on which the obtained laminated body is arranged, and inorganic by plasma CVD method.
  • a material film A was formed.
  • SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
  • the formed inorganic material film A had a thickness of about 1 ⁇ m.
  • the sealing agent for organic EL display elements which can obtain the organic EL display element which is excellent in inkjet applicability

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Electroluminescent Light Sources (AREA)
  • Optics & Photonics (AREA)

Abstract

The purpose of the present invention is to provide a sealant for an organic electroluminescent display element, the sealant having exceptional inkjet applicability, low out-gassing properties, and adhesion with respect to an inorganic material film, and making it possible to obtain a highly reliable organic electroluminescent display element. The present invention is a sealant for an organic electroluminescent display element containing a polymerizable compound and a polymerization initiator, wherein: the polymerizable compound contains a monofunctional oxetane compound and a multifunctional oxetane compound; the monofunctional oxetane compound content is 20-35 parts by weight, and the multifunctional oxetane compound content is 25-40 parts by weight, in relation to 100 parts by weight of the polymerizable compound; the viscosity at 25°C is 80 mPa·s or less; and the surface tension at 25°C is 15-35 mN/m.

Description

有機ＥＬ表示素子用封止剤Sealant for organic EL display element
本発明は、インクジェット塗布性、低アウトガス性、及び、無機材料膜に対する密着性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤に関する。 The present invention relates to a sealant for an organic EL display element that can provide an organic EL display element that is excellent in inkjet coating property, low outgassing property, adhesion to an inorganic material film, and excellent in reliability.
有機エレクトロルミネッセンス（以下、「有機ＥＬ」ともいう）表示素子は、互いに対向する一対の電極間に有機発光材料層が挟持された積層体構造を有し、この有機発光材料層に一方の電極から電子が注入されるとともに他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して発光する。このように有機ＥＬ表示素子は自己発光を行うことから、バックライトを必要とする液晶表示素子等と比較して視認性がよく、薄型化が可能であり、しかも直流低電圧駆動が可能であるという利点を有している。 An organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer. When electrons are injected and holes are injected from the other electrode, the electrons and holes are combined in the organic light emitting material layer to emit light. Thus, since the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
有機ＥＬ表示素子を構成する有機発光材料層や電極は、水分や酸素等により特性が劣化しやすいという問題がある。従って、実用的な有機ＥＬ表示素子を得るためには、有機発光材料層や電極を大気と遮断して長寿命化を図る必要がある。特許文献１には、有機ＥＬ表示素子の有機発光材料層と電極とを、ＣＶＤ法により形成した窒化珪素膜と樹脂膜との積層膜により封止する方法が開示されている。ここで樹脂膜は、窒化珪素膜の内部応力による有機層や電極への圧迫を防止する役割を有する。 The organic light-emitting material layer and electrodes constituting the organic EL display element have a problem that the characteristics are easily deteriorated by moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to extend the life by blocking the organic light emitting material layer and the electrode from the atmosphere. Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method. Here, the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.
特許文献１に開示された窒化珪素膜で封止を行う方法では、有機ＥＬ表示素子の表面の凹凸や異物の付着、内部応力によるクラックの発生等により、窒化珪素膜を形成する際に有機発光材料層や電極を完全に被覆できないことがある。窒化珪素膜による被覆が不完全であると、水分が窒化珪素膜を通して有機発光材料層内に浸入してしまう。
有機発光材料層内への水分の浸入を防止するための方法として、特許文献２には、無機材料膜と樹脂膜とを交互に蒸着する方法が開示されており、特許文献３や特許文献４には、無機材料膜上に樹脂膜を形成する方法が開示されている。 In the method of sealing with a silicon nitride film disclosed in Patent Document 1, organic light emission occurs when a silicon nitride film is formed due to unevenness on the surface of the organic EL display element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. The material layer or electrode may not be completely covered. If the coating with the silicon nitride film is incomplete, moisture will enter the organic light emitting material layer through the silicon nitride film.
As a method for preventing moisture from entering into the organic light emitting material layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film. Patent Document 3 and Patent Document 4 Discloses a method of forming a resin film on an inorganic material film.
樹脂膜を形成する方法として、インクジェット法を用いて基材上に封止剤を塗布した後、該封止剤を硬化させる方法がある。このようなインクジェット法による塗布方法を用いれば、高速かつ均一に樹脂膜を形成することができる。しかしながら、インクジェット法による塗布に適したものとするために封止剤を低粘度となるようにした場合、アウトガスが発生したり、得られる有機ＥＬ表示素子が信頼性に劣るものとなったりする等の問題があった。 As a method for forming a resin film, there is a method in which a sealing agent is applied on a substrate using an inkjet method and then the sealing agent is cured. If such a coating method by the ink jet method is used, a resin film can be uniformly formed at high speed. However, when the sealant is made to have a low viscosity in order to be suitable for application by the ink jet method, outgas is generated, or the obtained organic EL display element is inferior in reliability, etc. There was a problem.
特開２０００－２２３２６４号公報JP 2000-223264 A 特表２００５－５２２８９１号公報JP 2005-522891 Gazette 特開２００１－３０７８７３号公報JP 2001-307873 A 特開２００８－１４９７１０号公報JP 2008-149710 A
本発明は、インクジェット塗布性、低アウトガス性、及び、無機材料膜に対する密着性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することを目的とする。 The present invention provides an organic EL display element sealant that can provide an organic EL display element that is excellent in inkjet coating property, low outgassing property, and adhesion to an inorganic material film, and that is excellent in reliability. With the goal.
本発明１は、重合性化合物と重合開始剤とを含有する有機ＥＬ表示素子用封止剤であって、上記重合性化合物は、単官能オキセタン化合物と多官能オキセタン化合物とを含有し、上記重合性化合物１００重量部中における、上記単官能オキセタン化合物の含有量が２０重量部以上３５重量部以下であり、かつ、上記多官能オキセタン化合物の含有量が２５重量部以上４０重量部以下であり、２５℃における粘度が８０ｍＰａ・ｓ以下であり、２５℃における表面張力が１５ｍＮ／ｍ以上３５ｍＮ／ｍ以下である有機ＥＬ表示素子用封止剤である。
本発明２は、重合性化合物と重合開始剤とを含有する有機ＥＬ表示素子用封止剤であって、上記重合性化合物は、単官能オキセタン化合物と多官能オキセタン化合物とを含有し、上記重合性化合物１００重量部中における、上記単官能オキセタン化合物の含有量が２０重量部以上３５重量部以下であり、かつ、上記多官能オキセタン化合物の含有量が２５重量部以上４０重量部以下であり、インクジェット法による塗布に用いられる有機ＥＬ表示素子用封止剤である。
以下に本発明を詳述する。なお、本発明１の有機ＥＬ表示素子用封止剤と本発明２の有機ＥＬ表示素子用封止剤とに共通する事項については、「本発明の有機ＥＬ表示素子用封止剤」として記載する。 The present invention 1 is an organic EL display device sealing agent containing a polymerizable compound and a polymerization initiator, wherein the polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound, and the polymerization In 100 parts by weight of the functional compound, the content of the monofunctional oxetane compound is 20 to 35 parts by weight, and the content of the polyfunctional oxetane compound is 25 to 40 parts by weight, The sealant for organic EL display elements has a viscosity at 25 ° C. of 80 mPa · s or less and a surface tension at 25 ° C. of 15 mN / m or more and 35 mN / m or less.
Invention 2 is a sealant for an organic EL display device containing a polymerizable compound and a polymerization initiator, wherein the polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound, and the polymerization In 100 parts by weight of the functional compound, the content of the monofunctional oxetane compound is 20 to 35 parts by weight, and the content of the polyfunctional oxetane compound is 25 to 40 parts by weight, It is the sealing agent for organic EL display elements used for application | coating by the inkjet method.
The present invention is described in detail below. In addition, about the matter common to the sealing agent for organic EL display elements of this invention 1 and the sealing agent for organic EL display elements of this invention 2, it describes as "the sealing agent for organic EL display elements of this invention". To do.
本発明者らは、従来の有機ＥＬ表示素子用封止剤を用いた際に得られる有機ＥＬ表示素子が信頼性に劣るものとなる原因が、該封止剤の無機材料膜に対する密着性が不充分であることにあると考えた。そこで本発明者らは、重合性化合物として単官能オキセタン化合物と多官能オキセタン化合物とをそれぞれ特定の含有量となるように配合し、かつ、粘度と表面張力とをそれぞれ特定の範囲となるように調整することを検討した。その結果、インクジェット塗布性、低アウトガス性、及び、無機材料膜に対する密着性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を得ることができることを見出し、本発明を完成させるに至った。 The inventors of the present invention have a reason why the reliability of the organic EL display element obtained when the conventional sealant for organic EL display elements is used is due to the adhesiveness of the sealant to the inorganic material film. I thought it was inadequate. Therefore, the present inventors compounded the monofunctional oxetane compound and the polyfunctional oxetane compound as the polymerizable compound so as to have a specific content, respectively, and set the viscosity and the surface tension within a specific range, respectively. Considered to adjust. As a result, it is possible to obtain an organic EL display element sealant that can provide an organic EL display element that is excellent in inkjet coating property, low outgassing property, and adhesion to an inorganic material film, and that is excellent in reliability. As a result, the present invention has been completed.
本発明の有機ＥＬ表示素子用封止剤は、重合性化合物を含有する。
上記重合性化合物は、単官能オキセタン化合物と多官能オキセタン化合物とを含有する。
上記単官能オキセタン化合物と上記多官能オキセタン化合物とをそれぞれ後述する含有量となるようにして用いることにより、本発明の有機ＥＬ表示素子用封止剤は、低アウトガス性及び無機材料膜に対する密着性に優れるものとなる。 The sealing agent for organic EL display elements of the present invention contains a polymerizable compound.
The polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound.
By using the monofunctional oxetane compound and the polyfunctional oxetane compound so as to have contents described later, the sealing agent for organic EL display elements of the present invention has low outgassing property and adhesion to an inorganic material film. It will be excellent.
上記単官能オキセタン化合物としては、例えば、３－エチル－３－（（２－エチルヘキシルオキシ）メチル）オキセタン、フェノキシメチルオキセタン、３－エチル－３－ヒドロキシメチルオキセタン、３－エチル－３－（フェノキシメチル）オキセタン、３－エチル－３－（（３－（トリエトキシシリル）プロポキシ）メチル）オキセタン、３－アリルオキシオキセタン、３－エチル－３－アリルオキシオキセタン、３－エチル－３－アクリロイルオキシメチルオキセタン、３－エチル－３－メタクリロキシメチルオキセタン、２－メチル－２－アリル－４－プロピルオキセタン、３－エチル－３－（４－アクリロイルオキシブチルオキシメチル）オキセタン、３－エチル－３－（３－アクリロイルオキシ－２，２－ジメチルプロピルオキシメチル）オキセタン、３－メチル－３－メトキシオキセタン、フェニルオキセタン、３－エチル－３－クロロメチルオキセタン、３－エチル－３－オキセタンメタノール、３－アミノ－３－ジメチルオキセタン等が挙げられる。なかでも、無機材料膜に対する密着性をより向上させる等の観点から、３－エチル－３－（（２－エチルヘキシルオキシ）メチル）オキセタンが好ましい。 Examples of the monofunctional oxetane compound include 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-3- (phenoxymethyl). ) Oxetane, 3-ethyl-3-((3- (triethoxysilyl) propoxy) methyl) oxetane, 3-allyloxyoxetane, 3-ethyl-3-allyloxyoxetane, 3-ethyl-3-acryloyloxymethyloxetane 3-ethyl-3-methacryloxymethyloxetane, 2-methyl-2-allyl-4-propyloxetane, 3-ethyl-3- (4-acryloyloxybutyloxymethyl) oxetane, 3-ethyl-3- (3 -Acryloyloxy-2,2-dimethylpropyloxy Methyl) oxetane, 3-methyl-3-methoxy oxetane, phenyl oxetane, 3-ethyl-3-chloromethyl oxetane, 3-ethyl-3-oxetane methanol, 3-amino-3-dimethyl-oxetane, and the like. Of these, 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane is preferable from the viewpoint of further improving the adhesion to the inorganic material film.
上記重合性化合物１００重量部中における上記単官能オキセタン化合物の含有量の下限は２０重量部、上限は３５重量部である。上記単官能オキセタン化合物の含有量がこの範囲であることにより、本発明の有機ＥＬ表示素子用封止剤は低アウトガス性及び無機材料膜に対する密着性に優れるものとなり、得られる有機ＥＬ表示素子が信頼性に優れるものとなる。上記単官能オキセタン化合物の含有量の好ましい下限は２２重量部、好ましい上限は３３重量部、より好ましい下限は２５重量部、より好ましい上限は３０重量部である。 The lower limit of the content of the monofunctional oxetane compound in 100 parts by weight of the polymerizable compound is 20 parts by weight, and the upper limit is 35 parts by weight. When the content of the monofunctional oxetane compound is within this range, the organic EL display element sealing agent of the present invention has excellent low outgassing property and adhesion to an inorganic material film. It will be excellent in reliability. The preferable lower limit of the content of the monofunctional oxetane compound is 22 parts by weight, the preferable upper limit is 33 parts by weight, the more preferable lower limit is 25 parts by weight, and the more preferable upper limit is 30 parts by weight.
上記多官能オキセタン化合物としては、例えば、３－エチル－３－（（（３－エチルオキセタン－３－イル）メトキシ）メチル）オキセタン、キシリレンビスオキセタン、フェノールノボラック型オキセタン、オキセタニルシルセスキオキサン、１，４－ビス（（３－エチル－３－オキセタニルメトキシ）メチル）ベンゼン、ビス（（３－メチル－３－オキセタニルメトキシ）メチル）エーテル、ビス（（３－エチル－３－オキセタニルメトキシ）メチル）エーテル、１，４－ビス（（３－メチル－３－オキセタニルメトキシ）メチル）ベンゼンや、これらのオリゴマー又は共重合体等の他、これらと、カリックスアレーン類、カリックスレゾルシンアレーン類、カルド型ビスフェノール類、ポリ（ｐ－ヒドロキシスチレン）、又は、シルセスキオキサン等の水酸基を有する樹脂とのエーテル化物等が挙げられる。なかでも、２官能オキセタン化合物が好ましく、インクジェット塗布性等の観点から、３－エチル－３－（（（３－エチルオキセタン－３－イル）メトキシ）メチル）オキセタンがより好ましい。 Examples of the polyfunctional oxetane compound include 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane, xylylene bisoxetane, phenol novolac oxetane, oxetanyl silsesquioxane, 1,4-bis ((3-ethyl-3-oxetanylmethoxy) methyl) benzene, bis ((3-methyl-3-oxetanylmethoxy) methyl) ether, bis ((3-ethyl-3-oxetanylmethoxy) methyl) Ether, 1,4-bis ((3-methyl-3-oxetanylmethoxy) methyl) benzene, oligomers or copolymers thereof, and the like, calixarenes, calixresorcinarenes, cardo-type bisphenols , Poly (p-hydroxystyrene) or silce Etherified products such as the resin having a hydroxyl group such as Kiokisan like. Among these, a bifunctional oxetane compound is preferable, and 3-ethyl-3-(((3-ethyloxetane-3-yl) methoxy) methyl) oxetane is more preferable from the viewpoint of ink jet coating property and the like.
上記重合性化合物１００重量部中における上記多官能オキセタン化合物の含有量の下限は２５重量部、上限は４０重量部である。上記多官能オキセタン化合物の含有量がこの範囲であることにより、本発明の有機ＥＬ表示素子用封止剤は低アウトガス性及び無機材料膜に対する密着性に優れるものとなり、得られる有機ＥＬ表示素子が信頼性に優れるものとなる。上記多官能オキセタン化合物の含有量の好ましい下限は２８重量部、好ましい上限は３８重量部、より好ましい上限は３５重量部である。 The lower limit of the content of the polyfunctional oxetane compound in 100 parts by weight of the polymerizable compound is 25 parts by weight, and the upper limit is 40 parts by weight. When the content of the polyfunctional oxetane compound is within this range, the sealing agent for organic EL display elements of the present invention is excellent in low outgassing and adhesion to an inorganic material film, and the resulting organic EL display element is It will be excellent in reliability. The minimum with preferable content of the said polyfunctional oxetane compound is 28 weight part, a preferable upper limit is 38 weight part, and a more preferable upper limit is 35 weight part.
上記単官能オキセタン化合物と上記多官能オキセタン化合物との含有割合は、重量比で、単官能オキセタン化合物：多官能オキセタン化合物＝５：３～５：９であることが好ましい。上記単官能オキセタン化合物と上記多官能オキセタン化合物との含有割合がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が低アウトガス性及び無機材料膜に対する密着性により優れるものとなり、得られる有機ＥＬ表示素子が信頼性により優れるものとなる。 The content ratio of the monofunctional oxetane compound and the polyfunctional oxetane compound is preferably a monofunctional oxetane compound: polyfunctional oxetane compound = 5: 3 to 5: 9 in terms of weight ratio. When the content ratio of the monofunctional oxetane compound and the polyfunctional oxetane compound is within this range, the obtained sealing agent for organic EL display elements is excellent in low outgassing and adhesion to an inorganic material film. The organic EL display element to be obtained is superior in reliability.
上記重合性化合物は、シクロアルケンオキサイド型脂環式エポキシ化合物を含有することが好ましい。
上記シクロアルケンオキサイド型脂環式エポキシ化合物を含有することにより、得られる有機ＥＬ表示素子用封止剤が低アウトガス性及び硬化物のバリア性（透湿防止性）により優れるものとなる。
また、上記シクロアルケンオキサイド型脂環式エポキシ化合物を含有することにより、熱や光による封止剤の着色が起こりにくく、封止剤の吸光によるＥＬ発光の損失や色調の変化を小さくできる。
なお、本明細書において、上記「シクロアルケンオキサイド型脂環式エポキシ化合物」は、例えば、下記式（１）に表されるような、シクロアルケンの炭素－炭素二重結合がエポキシ化した構造（以下、「シクロアルケンオキサイド骨格」ともいう）を有する化合物を意味する。 The polymerizable compound preferably contains a cycloalkene oxide type alicyclic epoxy compound.
By containing the said cycloalkene oxide type alicyclic epoxy compound, the sealing agent for organic EL display elements obtained will be excellent in low outgassing property and barrier property (moisture permeability prevention property) of hardened | cured material.
Moreover, by containing the said cycloalkene oxide type alicyclic epoxy compound, coloring of the sealing agent by heat or light hardly occurs, and loss of EL emission or change in color tone due to absorption of the sealing agent can be reduced.
In the present specification, the “cycloalkene oxide type alicyclic epoxy compound” is, for example, a structure in which a carbon-carbon double bond of cycloalkene is epoxidized as represented by the following formula (1) ( Hereinafter, it means a compound having a “cycloalkene oxide skeleton”.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
式（１）中、Ｒ１～Ｒ９は、水素原子、ハロゲン原子、又は、酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基であり、それぞれ同一であってもよいし、異なっていてもよい。＊は、結合位置を表す。 In the formula (1), R 1 to R 9 are a hydrogen atom, a halogen atom, or a hydrocarbon group that may contain an oxygen atom or a halogen atom, and may be the same or different. Also good. * Represents a binding position.
上記シクロアルケンオキサイド型脂環式エポキシ化合物のエポキシ基当量の好ましい下限は５０ｇ／ｍｏｌ、好ましい上限は４００ｇ／ｍｏｌである。上記シクロアルケンオキサイド型脂環式エポキシ化合物のエポキシ基当量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤の硬化物が、加熱や変形によるクラックを発生を抑制しつつ、バリア性により優れるものとなる。上記シクロアルケンオキサイド型脂環式エポキシ化合物のエポキシ基当量のより好ましい下限は７０ｇ／ｍｏｌ、より好ましい上限は３００ｇ／ｍｏｌである。
なお、上記シクロアルケンオキサイド型脂環式エポキシ化合物のエポキシ基当量は、シクロアルケンオキサイド型脂環式エポキシ化合物中に含まれるエポキシ基１ｍｏｌ当たりのシクロアルケンオキサイド型脂環式エポキシ化合物の重量（ｇ）を意味する。 The preferable lower limit of the epoxy group equivalent of the cycloalkene oxide type alicyclic epoxy compound is 50 g / mol, and the preferable upper limit is 400 g / mol. When the epoxy group equivalent of the cycloalkene oxide type alicyclic epoxy compound is within this range, the cured product of the obtained sealing agent for organic EL display elements suppresses the occurrence of cracks due to heating or deformation, and the barrier. It becomes more excellent by the property. The more preferable lower limit of the epoxy group equivalent of the cycloalkene oxide type alicyclic epoxy compound is 70 g / mol, and the more preferable upper limit is 300 g / mol.
In addition, the epoxy group equivalent of the said cycloalkene oxide type alicyclic epoxy compound is the weight (g) of cycloalkene oxide type alicyclic epoxy compound per 1 mol of epoxy groups contained in the cycloalkene oxide type alicyclic epoxy compound. Means.
上記シクロアルケンオキサイド型脂環式エポキシ化合物の分子量の好ましい下限は１５０、好ましい上限は７０００である。上記シクロアルケンオキサイド型脂環式エポキシ化合物の分子量がこの範囲であることにより、アウトガスの発生を抑制しつつ、得られる有機ＥＬ表示素子用封止剤が硬化物のバリア性により優れるものとなる。上記シクロアルケンオキサイド型脂環式エポキシ化合物の分子量のより好ましい下限は２００、より好ましい上限は５０００、更に好ましい下限は２５０、更に好ましい上限は１０００である。
なお、上記シクロアルケンオキサイド型脂環式エポキシ化合物の分子量は、分子構造が特定される化合物については、構造式から求められる分子量であるが、重合度の分布が広い化合物及び変性部位が不特定な化合物については、重量平均分子量を用いて表す場合がある。本明細書において、上記「重量平均分子量」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際に用いるカラムとしては、例えば、Ｓｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）等が挙げられる。 The preferable lower limit of the molecular weight of the cycloalkene oxide type alicyclic epoxy compound is 150, and the preferable upper limit is 7000. When the molecular weight of the cycloalkene oxide type alicyclic epoxy compound is within this range, the resulting organic EL display element sealant is more excellent in the barrier properties of the cured product while suppressing generation of outgas. The more preferable lower limit of the molecular weight of the cycloalkene oxide type alicyclic epoxy compound is 200, the more preferable upper limit is 5000, the still more preferable lower limit is 250, and the still more preferable upper limit is 1000.
The molecular weight of the cycloalkene oxide type alicyclic epoxy compound is the molecular weight obtained from the structural formula for the compound whose molecular structure is specified, but the compound having a wide distribution of polymerization degree and the modified site are not specified. About a compound, it may represent using a weight average molecular weight. In the present specification, the above “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
上記シクロアルケンオキサイド型脂環式エポキシ化合物は、構造中、又は、繰り返し単位内にシクロアルケンオキサイド骨格を１個だけ有する化合物であってもよく、２個以上のシクロアルケンオキサイド骨格を有する化合物であってもよいが、２個以上のシクロアルケンオキサイド骨格を有する化合物が好適に用いられる。上記シクロアルケンオキサイド型脂環式エポキシ化合物が２個以上のシクロアルケンオキサイド骨格を有する化合物である場合、本発明の有機ＥＬ表示素子用封止剤は、より耐光性やバリア性等に優れたものとなる。 The cycloalkene oxide type alicyclic epoxy compound may be a compound having only one cycloalkene oxide skeleton in the structure or in the repeating unit, or a compound having two or more cycloalkene oxide skeletons. However, a compound having two or more cycloalkene oxide skeletons is preferably used. When the cycloalkene oxide type alicyclic epoxy compound is a compound having two or more cycloalkene oxide skeletons, the organic EL display device sealing agent of the present invention is more excellent in light resistance, barrier properties, etc. It becomes.
上記シクロアルケンオキサイド型脂環式エポキシ化合物としては、具体的には例えば、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４，３’，４’－ジエポキシビシクロヘキサン、ビス（３，４－エポキシシクロヘキシルメチル）エーテル等が挙げられる。なかでも、低アウトガス性及び硬化物のバリア性の観点から、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４，３’，４’－ジエポキシビシクロヘキサンが好ましい。 Specific examples of the cycloalkene oxide type alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4,3 ′, 4′-diepoxy. Examples include bicyclohexane and bis (3,4-epoxycyclohexylmethyl) ether. Of these, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4,3 ′, 4′-diepoxybicyclohexane are used from the viewpoint of low outgassing properties and barrier properties of cured products. preferable.
上記重合性化合物１００重量部中における上記シクロアルケンオキサイド型脂環式エポキシ化合物の含有量の好ましい下限は１５重量部、好ましい上限は３０重量部である。上記シクロアルケンオキサイド型脂環式エポキシ化合物の含有量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が低アウトガス性及び硬化物のバリア性により優れるものとなる。上記シクロアルケンオキサイド型脂環式エポキシ化合物の含有量のより好ましい下限は１７重量部、より好ましい上限は２５重量部である。 The minimum with preferable content of the said cycloalkene oxide type | mold alicyclic epoxy compound in 100 weight part of said polymeric compounds is 15 weight part, and a preferable upper limit is 30 weight part. When the content of the cycloalkene oxide type alicyclic epoxy compound is within this range, the obtained sealing agent for organic EL display elements is more excellent in low outgassing properties and cured product barrier properties. The minimum with more preferable content of the said cycloalkene oxide type | mold alicyclic epoxy compound is 17 weight part, and a more preferable upper limit is 25 weight part.
上記重合性化合物は、アルキルポリオール型エポキシ化合物を含有することが好ましい。
上記アルキルポリオール型エポキシ化合物を含有することにより、得られる有機ＥＬ表示素子用封止剤が密着性により優れるものとなる。 The polymerizable compound preferably contains an alkyl polyol type epoxy compound.
By containing the said alkyl polyol type epoxy compound, the sealing agent for organic EL display elements obtained becomes a thing excellent in adhesiveness.
上記アルキルポリオール型エポキシ化合物としては、例えば、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、トリメチロ－ルプロパントリグリシジルエーテル等が挙げられる。なかでも、密着性の観点から、ネオペンチルグリコールジグリシジルエーテルが好ましい。 Examples of the alkyl polyol type epoxy compound include neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene. Examples include glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, and trimethylolpropane triglycidyl ether. Of these, neopentyl glycol diglycidyl ether is preferable from the viewpoint of adhesion.
上記重合性化合物１００重量部中における上記アルキルポリオール型エポキシ化合物の含有量の好ましい下限は５重量部、好ましい上限は３０重量部である。上記アルキルポリオール型エポキシ化合物の含有量がこの範囲であることにより、得られる有機ＥＬ表示素子用封止剤が密着性により優れるものとなる。上記アルキルポリオール型エポキシ化合物の含有量のより好ましい下限は１０重量部、より好ましい上限は２５重量部である。 The preferable lower limit of the content of the alkyl polyol type epoxy compound in 100 parts by weight of the polymerizable compound is 5 parts by weight, and the preferable upper limit is 30 parts by weight. When the content of the alkyl polyol type epoxy compound is within this range, the obtained sealing agent for organic EL display elements is more excellent in adhesion. The minimum with more preferable content of the said alkyl polyol type epoxy compound is 10 weight part, and a more preferable upper limit is 25 weight part.
上記重合性化合物は、本発明の目的を阻害しない範囲で、上記単官能オキセタン化合物、上記多官能オキセタン化合物、上記シクロアルケンオキサイド型脂環式エポキシ化合物、及び、上記アルキルポリオール型エポキシ化合物以外のその他の重合性化合物を含有してもよい。
上記その他の重合性化合物としては、上記シクロアルケンオキサイド型脂環式エポキシ化合物及び上記アルキルポリオール型エポキシ化合物以外のその他のエポキシ化合物や、ビニルエーテル化合物等が挙げられる。 The polymerizable compound is within the range not impairing the object of the present invention, and other than the monofunctional oxetane compound, the polyfunctional oxetane compound, the cycloalkene oxide type alicyclic epoxy compound, and the alkyl polyol type epoxy compound. The polymerizable compound may be contained.
Examples of the other polymerizable compounds include other epoxy compounds other than the cycloalkene oxide type alicyclic epoxy compound and the alkyl polyol type epoxy compound, vinyl ether compounds, and the like.
上記その他のエポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＯ型エポキシ樹脂、２，２’－ジアリルビスフェノールＡ型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ゴム変性型エポキシ樹脂、グリシジルエステル化合物等が挙げられる。 Examples of the other epoxy compounds include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol O type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy. Resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, Phenol novolac type epoxy resin, ortho cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type Epoxy resins, naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
上記ビニルエーテル化合物としては、例えば、ベンジルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ジシクロペンタジエンビニルエーテル、１，４－ブタンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、トリプロピレングリコールジビニルエーテル等が挙げられる。 Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexane dimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol. Examples thereof include divinyl ether and tripropylene glycol divinyl ether.
本発明の有機ＥＬ表示素子用封止剤は、重合開始剤を含有する。
上記重合開始剤としては光カチオン重合開始剤や熱カチオン重合開始剤が好適に用いられる。 The sealing agent for organic EL display elements of the present invention contains a polymerization initiator.
As the polymerization initiator, a photocationic polymerization initiator or a thermal cationic polymerization initiator is preferably used.
上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生型であってもよいし、非イオン性光酸発生型であってもよい。 The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
上記イオン性光酸発生型の光カチオン重合開始剤のアニオン部分としては、例えば、アニオン部分がＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）等が挙げられる。
上記イオン性光酸発生型の光カチオン重合開始剤としては、例えば、上記アニオン部分を有する、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ジアゾニウム塩、芳香族アンモニウム塩、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩等が挙げられる。 Examples of the anion portion of the ionic photoacid-generating photocationic polymerization initiator include an anion portion of BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (where X is at least And a phenyl group substituted with two or more fluorine or trifluoromethyl groups).
Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts having the above anion moiety, and (2,4-cyclohexane). And pentadien-1-yl) ((1-methylethyl) benzene) -Fe salt.
上記芳香族スルホニウム塩としては、例えば、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラフルオロボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリアリールスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、トリス（４－（４－アセチルフェニル）チオフェニル）スルホニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) Phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triarylsulfonium tetrakis (pentafluoro) Phenyl) borate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfo Nio) phenyl) sulfide bishexafluoroantimonate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfo O) phenyl) sulfide bistetrafluoroborate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfidetetrakis (pentafluorophenyl) borate, tris (4- (4-acetylphenyl) ) Thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like.
上記芳香族ヨードニウム塩としては、例えば、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロホスフェート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムヘキサフルオロアンチモネート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラフルオロボレート、４－メチルフェニル－４－（１－メチルエチル）フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Such as phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Can be mentioned.
上記芳香族ジアゾニウム塩としては、例えば、フェニルジアゾニウムヘキサフルオロホスフェート、フェニルジアゾニウムヘキサフルオロアンチモネート、フェニルジアゾニウムテトラフルオロボレート、フェニルジアゾニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
上記芳香族アンモニウム塩としては、例えば、１－ベンジル－２－シアノピリジニウムヘキサフルオロホスフェート、１－ベンジル－２－シアノピリジニウムヘキサフルオロアンチモネート、１－ベンジル－２－シアノピリジニウムテトラフルオロボレート、１－ベンジル－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロホスフェート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロアンチモネート、１－（ナフチルメチル）－２－シアノピリジニウムテトラフルオロボレート、１－（ナフチルメチル）－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) Examples include -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
上記（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩としては、例えば、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロホスフェート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロアンチモネート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラフルオロボレート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -Yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta Fluorophenyl) borate and the like.
上記非イオン性光酸発生型の光カチオン重合開始剤としては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドスルホネート等が挙げられる。 Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.
上記光カチオン重合開始剤のうち市販されているものとしては、例えば、みどり化学社製の光カチオン重合開始剤、ユニオンカーバイド社製の光カチオン重合開始剤、ＡＤＥＫＡ社製の光カチオン重合開始剤、３Ｍ社製の光カチオン重合開始剤、ＢＡＳＦ社製の光カチオン重合開始剤、ローディア社製の光カチオン重合開始剤等が挙げられる。
上記みどり化学社製の光カチオン重合開始剤としては、例えば、ＤＴＳ－２００等が挙げられる。
上記ユニオンカーバイド社製の光カチオン重合開始剤としては、例えば、ＵＶＩ６９９０、ＵＶＩ６９７４等が挙げられる。
上記ＡＤＥＫＡ社製の光カチオン重合開始剤としては、例えば、ＳＰ－１５０、ＳＰ－１７０等が挙げられる。
上記３Ｍ社製の光カチオン重合開始剤としては、例えば、ＦＣ－５０８、ＦＣ－５１２等が挙げられる。
上記ＢＡＳＦ社製の光カチオン重合開始剤としては、例えば、ＩＲＧＡＣＵＲＥ２６１、ＩＲＧＡＣＵＲＥ２９０等が挙げられる。
上記ローディア社製の光カチオン重合開始剤としては、例えば、ＰＩ２０７４等が挙げられる。 Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Examples thereof include a photocationic polymerization initiator manufactured by 3M, a photocationic polymerization initiator manufactured by BASF, and a photocationic polymerization initiator manufactured by Rhodia.
Examples of the photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd. include DTS-200.
Examples of the cationic photopolymerization initiator manufactured by Union Carbide include UVI6990, UVI6974, and the like.
Examples of the photocation polymerization initiator manufactured by ADEKA include SP-150 and SP-170.
Examples of the cationic photopolymerization initiator manufactured by 3M include FC-508, FC-512, and the like.
Examples of the cationic photopolymerization initiator manufactured by BASF include IRGACURE261, IRGACURE290, and the like.
Examples of the photocationic polymerization initiator manufactured by Rhodia include PI 2074.
上記熱カチオン重合開始剤としては、アニオン部分がＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－（但し、Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す）で構成される、スルホニウム塩、ホスホニウム塩、アンモニウム塩等が挙げられる。なかでも、スルホニウム塩、アンモニウム塩が好ましい。 As the thermal cationic polymerization initiator, the anion moiety is BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − (where X is substituted with at least two fluorine or trifluoromethyl groups A sulfonium salt, a phosphonium salt, an ammonium salt, and the like. Of these, sulfonium salts and ammonium salts are preferable.
上記スルホニウム塩としては、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
上記ホスホニウム塩としては、エチルトリフェニルホスホニウムヘキサフルオロアンチモネート、テトラブチルホスホニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
上記アンモニウム塩としては、例えば、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メトキシベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メトキシベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロホスフェート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロアンチモネート、ジメチルフェニル（４－メチルベンジル）アンモニウムヘキサフルオロテトラキス（ペンタフルオロフェニル）ボレート、メチルフェニルジベンジルアンモニウムヘキサフルオロホスフェート、メチルフェニルジベンジルアンモニウムヘキサフルオロアンチモネート、メチルフェニルジベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、フェニルトリベンジルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、ジメチルフェニル（３，４－ジメチルベンジル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルアニリニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルアニリニウムテトラフルオロボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルピリジニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルピリジニウムトリフルオロメタンスルホン酸等が挙げられる。 Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl). Borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl Dibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium Safluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N , N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl -N-benzylpyridinium trifluoromethanesulfonic acid and the like.
上記熱カチオン重合開始剤のうち市販されているものとしては、例えば、三新化学工業社製の熱カチオン重合開始剤、Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製の熱カチオン重合開始剤等が挙げられる。
上記三新化学工業社製の熱カチオン重合開始剤としては、例えば、サンエイドＳＩ－６０、サンエイドＳＩ－８０、サンエイドＳＩ－Ｂ３、サンエイドＳＩ－Ｂ３Ａ、サンエイドＳＩ－Ｂ４等が挙げられる。
上記Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製の熱カチオン重合開始剤としては、例えば、ＣＸＣ１６１２、ＣＸＣ１８２１等が挙げられる。 Examples of commercially available thermal cationic polymerization initiators include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry, thermal cationic polymerization initiators manufactured by King Industries, and the like.
Examples of the thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. include Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, and Sun-Aid SI-B4.
Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC1612 and CXC1821.
上記重合開始剤の含有量は、上記重合性化合物１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記重合開始剤の含有量が０．０１重量部以上であることにより、得られる有機ＥＬ表示素子用封止剤が硬化性により優れるものとなる。上記重合開始剤の含有量が１０重量部以下であることにより、得られる有機ＥＬ表示素子用封止剤の硬化反応が速くなり過ぎず、作業性により優れるものとなり、硬化物をより均一なものとすることができる。上記重合開始剤の含有量のより好ましい下限は０．０５重量部、より好ましい上限は５重量部である。 The content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the polymerization initiator is 0.01 parts by weight or more, the obtained sealing agent for organic EL display elements is more excellent in curability. When the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained sealing agent for organic EL display elements does not become too fast, and the workability is improved, and the cured product is more uniform. It can be. The minimum with more preferable content of the said polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
本発明の有機ＥＬ表示素子用封止剤は、増感剤を含有してもよい。上記増感剤は、上記重合開始剤の重合開始効率をより向上させて、本発明の有機ＥＬ表示素子用封止剤の硬化反応をより促進させる役割を有する。 The sealing agent for organic EL display elements of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealing agent for organic EL display elements of the present invention.
上記増感剤としては、例えば、チオキサントン化合物や、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、ベンゾフェノン、２，４－ジクロロベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド等が挙げられる。
上記チオキサントン化合物としては、例えば、２，４－ジエチルチオキサントン等が挙げられる。 Examples of the sensitizer include thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4 ′ -Bis (dimethylamino) benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone.
上記増感剤の含有量は、上記重合性化合物１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が３重量部である。上記増感剤の含有量が０．０１重量部以上であることにより、増感効果がより発揮される。上記増感剤の含有量が３重量部以下であることにより、吸収が大きくなり過ぎずに深部まで光を伝えることができる。上記増感剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は１重量部である。 The content of the sensitizer is preferably 0.01 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
本発明の有機ＥＬ表示素子用封止剤は、シランカップリング剤を含有してもよい。上記シランカップリング剤は、本発明の有機ＥＬ表示素子用封止剤と基板等との接着性を向上させる役割を有する。 The sealing agent for organic EL display elements of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the sealing agent for organic EL display elements of this invention, a board | substrate, etc.
上記シランカップリング剤としては、例えば、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤は単独で用いられてもよいし、２種以上が併用されてもよい。 Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like. These silane coupling agents may be used independently and 2 or more types may be used together.
上記シランカップリング剤の含有量は、上記重合性化合物１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記シランカップリング剤の含有量がこの範囲であることにより、余剰のシランカップリング剤がブリードアウトすることを抑制しつつ、接着性を向上させる効果により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は５重量部である。 The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable compound. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the excess silane coupling agent from bleeding out. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
本発明の有機ＥＬ表示素子用封止剤は、更に、本発明の目的を阻害しない範囲において、表面改質剤を含有してもよい。上記表面改質剤を含有することにより、本発明の有機ＥＬ表示素子用封止剤に塗膜の平坦性を付与することができる。
上記表面改質剤としては、例えば、界面活性剤やレベリング剤等が挙げられる。 The sealing agent for organic EL display elements of the present invention may further contain a surface modifier as long as the object of the present invention is not impaired. By containing the surface modifier, the flatness of the coating film can be imparted to the organic EL display element sealant of the present invention.
Examples of the surface modifier include surfactants and leveling agents.
上記表面改質剤としては、例えば、シリコーン系やフッ素系等のものが挙げられる。
上記表面改質剤のうち市販されているものとしては、例えば、ＢＹＫ－３４０、ＢＹＫ－３４５（いずれもビックケミー・ジャパン社製）、サーフロンＳ－６１１（ＡＧＣセイミケミカル社製）等が挙げられる。 Examples of the surface modifier include silicone-based and fluorine-based ones.
Examples of commercially available surface modifiers include BYK-340, BYK-345 (both manufactured by Big Chemie Japan) and Surflon S-611 (manufactured by AGC Seimi Chemical).
本発明の有機ＥＬ表示素子用封止剤は、粘度調整等を目的として溶剤を含有してもよいが、残存した溶剤により、有機発光材料層が劣化したりアウトガスが発生したりする等の問題が生じるおそれがあるため、溶剤を含有しない、又は、溶剤の含有量が０．０５重量％以下であることが好ましい。 The encapsulant for organic EL display elements of the present invention may contain a solvent for the purpose of adjusting the viscosity, but problems such as deterioration of the organic light emitting material layer and generation of outgas due to the remaining solvent. Therefore, it is preferable that the solvent is not contained or the solvent content is 0.05% by weight or less.
また、本発明の有機ＥＬ表示素子用封止剤は、必要に応じて、補強剤、軟化剤、可塑剤、粘度調整剤、紫外線吸収剤、酸化防止剤等の公知の各種添加剤を含有してもよい。 Moreover, the sealing agent for organic EL display elements of this invention contains well-known various additives, such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, a ultraviolet absorber, antioxidant, as needed. May be.
本発明の有機ＥＬ表示素子用封止剤を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、重合性化合物と、重合開始剤と、必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。 Examples of the method for producing the sealing agent for organic EL display elements of the present invention include a polymerizable compound using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll. And a method of mixing a polymerization initiator and an additive such as a silane coupling agent added if necessary.
本発明１の有機ＥＬ表示素子用封止剤は、２５℃における粘度の上限が８０ｍＰａ・ｓである。上記粘度が８０ｍＰａ・ｓ以下であることにより、本発明１の有機ＥＬ表示素子用封止剤は、インクジェット塗布性に優れるものとなる。本発明１の有機ＥＬ表示素子用封止剤の粘度の好ましい上限は６０ｍＰａ・ｓ、より好ましい上限は２０ｍＰａ・ｓである。
また、本発明１の有機ＥＬ表示素子用封止剤の粘度の好ましい下限は５ｍＰａ・ｓである。
なお、本明細書において上記粘度は、Ｅ型粘度計を用いて、２５℃、１００ｒｐｍの条件で測定される値を意味する。 The sealing agent for organic EL display elements of the present invention 1 has an upper limit of viscosity at 25 ° C. of 80 mPa · s. By the said viscosity being 80 mPa * s or less, the sealing agent for organic EL display elements of this invention 1 is excellent in inkjet applicability | paintability. The upper limit with the preferable viscosity of the sealing agent for organic EL display elements of this invention 1 is 60 mPa * s, and a more preferable upper limit is 20 mPa * s.
Moreover, the minimum with a preferable viscosity of the sealing agent for organic EL display elements of this invention 1 is 5 mPa * s.
In addition, the said viscosity in this specification means the value measured on 25 degreeC and 100 rpm conditions using an E-type viscosity meter.
本発明２の有機ＥＬ表示素子用封止剤は、２５℃における粘度の好ましい上限が８０ｍＰａ・ｓである。上記粘度が８０ｍＰａ・ｓ以下であることにより、本発明２の有機ＥＬ表示素子用封止剤は、インクジェット塗布性により優れるものとなる。本発明２の有機ＥＬ表示素子用封止剤の粘度のより好ましい上限は６０ｍＰａ・ｓ、更に好ましい上限は２０ｍＰａ・ｓである。
また、本発明２の有機ＥＬ表示素子用封止剤の粘度の好ましい下限は５ｍＰａ・ｓである。 As for the sealing agent for organic EL display elements of this invention 2, the preferable upper limit of the viscosity in 25 degreeC is 80 mPa * s. By the said viscosity being 80 mPa * s or less, the sealing agent for organic EL display elements of this invention 2 becomes more excellent by inkjet applicability | paintability. The more preferable upper limit of the viscosity of the sealing agent for organic EL display elements of the present invention 2 is 60 mPa · s, and the more preferable upper limit is 20 mPa · s.
Moreover, the minimum with a preferable viscosity of the sealing agent for organic EL display elements of this invention 2 is 5 mPa * s.
本発明１の有機ＥＬ表示素子用封止剤は、２５℃における表面張力の下限が１５ｍＮ／ｍ、上限が３５ｍＮ／ｍである。上記表面張力がこの範囲であることにより本発明１の有機ＥＬ表示素子用封止剤は、インクジェット塗布性に優れるものとなる。本発明１の有機ＥＬ表示素子用封止剤の表面張力の好ましい下限は２０ｍＮ／ｍ、好ましい上限は３０ｍＮ／ｍ、より好ましい下限は２２ｍＮ／ｍ、より好ましい上限は２８ｍＮ／ｍである。
なお、上記表面張力は、２５℃において動的濡れ性試験機により測定することができる。 The sealing agent for organic EL display elements of the present invention 1 has a lower limit of surface tension at 25 ° C. of 15 mN / m and an upper limit of 35 mN / m. When the surface tension is within this range, the organic EL display element sealant of the first aspect of the invention has excellent ink jet coating properties. The preferable lower limit of the surface tension of the sealant for organic EL display elements of the present invention 1 is 20 mN / m, the preferable upper limit is 30 mN / m, the more preferable lower limit is 22 mN / m, and the more preferable upper limit is 28 mN / m.
The surface tension can be measured with a dynamic wettability tester at 25 ° C.
本発明２の有機ＥＬ表示素子用封止剤は、２５℃における表面張力の好ましい下限が１５ｍＮ／ｍ、好ましい上限が３５ｍＮ／ｍである。上記表面張力がこの範囲であることにより、本発明２の有機ＥＬ表示素子用封止剤は、インクジェット塗布性により優れるものとなる。本発明２の有機ＥＬ表示素子用封止剤の表面張力のより好ましい下限は２０ｍＮ／ｍ、より好ましい上限は３０ｍＮ／ｍ、更に好ましい下限は２２ｍＮ／ｍ、更に好ましい上限は２８ｍＮ／ｍである。 As for the sealing agent for organic EL display elements of this invention 2, the preferable minimum of the surface tension in 25 degreeC is 15 mN / m, and a preferable upper limit is 35 mN / m. When the surface tension is within this range, the organic EL display element sealant of the second aspect of the present invention is superior in ink jet coating properties. The more preferable lower limit of the surface tension of the sealant for organic EL display elements of the present invention 2 is 20 mN / m, the more preferable upper limit is 30 mN / m, the still more preferable lower limit is 22 mN / m, and the still more preferable upper limit is 28 mN / m.
本発明の有機ＥＬ表示素子用封止剤の硬化物の波長３８０～８００ｎｍにおける光の全光線透過率の好ましい下限は８０％である。上記全光線透過率が８０％以上であることにより、得られる有機ＥＬ表示素子が光学特性により優れるものとなる。上記全光線透過率のより好ましい下限は８５％である。
上記全光線透過率は、例えば、ＡＵＴＯＭＡＴＩＣ　ＨＡＺＥ　ＭＥＴＥＲ　ＭＯＤＥＬ　ＴＣ－ＩＩＩ　ＤＰＫ（東京電色社製）等の分光計を用いて測定することができる。また、上記光線透過率、並びに、後述する透湿度及び含水率の測定に用いる硬化物は、例えば、ＬＥＤランプ等の光源を用いて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射することにより得ることができる。 The preferable lower limit of the total light transmittance of light at a wavelength of 380 to 800 nm of the cured product of the encapsulant for organic EL display elements of the present invention is 80%. When the total light transmittance is 80% or more, the obtained organic EL display element has superior optical characteristics. A more preferable lower limit of the total light transmittance is 85%.
The total light transmittance can be measured using a spectrometer such as AUTOMATIC HAZE METER MODEL TC-III DPK (manufactured by Tokyo Denshoku). Moreover, the hardened | cured material used for the measurement of the said light transmittance and the water vapor transmission rate and moisture content mentioned later can be obtained by irradiating 3000 mJ / cm < 2 > of ultraviolet rays with a wavelength of 365 nm using light sources, such as an LED lamp, for example. it can.
本発明の有機ＥＬ表示素子用封止剤は、硬化物に紫外線を１００時間照射した後の４００ｎｍにおける透過率が２０μｍの光路長にて８５％以上であることが好ましい。上記紫外線を１００時間照射した後の透過率が８５％以上であることにより、透明性が高く、発光の損失が小さくなり、かつ、色再現性により優れるものとなる。上記紫外線を１００時間照射した後の透過率のより好ましい下限は９０％、更に好ましい下限は９５％である。
上記紫外線を照射する光源としては、例えば、キセノンランプ、カーボンアークランプ等、従来公知の光源を用いることができる。 In the sealing agent for organic EL display elements of the present invention, the transmittance at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours is preferably 85% or more at an optical path length of 20 μm. When the transmittance after irradiating the ultraviolet rays for 100 hours is 85% or more, the transparency is high, the loss of light emission is small, and the color reproducibility is excellent. A more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and a more preferable lower limit is 95%.
As the light source for irradiating the ultraviolet rays, a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
本発明の有機ＥＬ表示素子用封止剤は、ＪＩＳ　Ｚ　０２０８に準拠して、硬化物を８５℃、８５％ＲＨの環境下に２４時間暴露して測定した１００μｍ厚での透湿度が１００ｇ／ｍ２以下であることが好ましい。上記透湿度が１００ｇ／ｍ２以下であることにより、硬化物中の水分による有機発光材料層の劣化を防止する効果により優れるものとなり、得られる有機ＥＬ表示素子が信頼性により優れるものとなる。 The sealant for an organic EL display device of the present invention has a moisture permeability of 100 g / 100 μm when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208. m is preferably 2 or less. When the moisture permeability is 100 g / m 2 or less, the effect of preventing deterioration of the organic light-emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability.
本発明の有機ＥＬ表示素子用封止剤は、硬化物を８５℃、８５％ＲＨの環境下に２４時間暴露したときに、硬化物の含水率が０．５％未満であることが好ましい。上記硬化物の含水率が０．５％未満であることにより、硬化物中の水分による有機発光材料層の劣化を防止する効果により優れるものとなり、得られる有機ＥＬ表示素子が信頼性により優れるものとなる。上記硬化物の含水率のより好ましい上限は０．３％である。
上記含水率の測定方法としては、例えば、ＪＩＳ　Ｋ　７２５１に準拠してカールフィッシャー法により求める方法や、ＪＩＳ　Ｋ　７２０９－２に準拠して吸水後の重量増分を求める等の方法が挙げられる。 In the encapsulant for organic EL display elements of the present invention, the moisture content of the cured product is preferably less than 0.5% when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours. When the moisture content of the cured product is less than 0.5%, the effect of preventing the deterioration of the organic light emitting material layer due to moisture in the cured product is excellent, and the obtained organic EL display element is excellent in reliability. It becomes. A more preferable upper limit of the moisture content of the cured product is 0.3%.
Examples of the method for measuring the moisture content include a method of obtaining by a Karl Fischer method in accordance with JIS K 7251, and a method of obtaining a weight increment after water absorption in accordance with JIS K 7209-2.
本発明の有機ＥＬ表示素子用封止剤を用いて有機ＥＬ表示素子を製造する方法としては、例えば、インクジェット法により、本発明の有機ＥＬ表示素子用封止剤を基材に塗布する工程と、塗布した有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程とを有する方法等が挙げられる。 As a method for producing an organic EL display element using the sealing agent for organic EL display elements of the present invention, for example, a step of applying the sealing agent for organic EL display elements of the present invention to a substrate by an inkjet method, And a method of curing the applied sealing agent for organic EL display elements by light irradiation and / or heating.
本発明の有機ＥＬ表示素子用封止剤を基材に塗布する工程において、本発明の有機ＥＬ表示素子用封止剤は、基材の全面に塗布してもよく、基材の一部に塗布してもよい。塗布により形成される本発明の有機ＥＬ表示素子用封止剤の封止部の形状としては、有機発光材料層を有する積層体を外気から保護しうる形状であれば特に限定されず、該積層体を完全に被覆する形状であってもよいし、該積層体の周辺部に閉じたパターンを形成してもよいし、該積層体の周辺部に一部開口部を設けた形状のパターンを形成してもよい。 In the step of applying the organic EL display element sealant of the present invention to the substrate, the organic EL display element sealant of the present invention may be applied to the entire surface of the substrate, or on a part of the substrate. It may be applied. The shape of the sealing portion of the sealing agent for organic EL display elements of the present invention formed by coating is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air. A shape that completely covers the body may be formed, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which a partial opening is provided in the peripheral portion of the laminate. It may be formed.
本発明の有機ＥＬ表示素子用封止剤を光照射により硬化させる場合、本発明の有機ＥＬ表示素子用封止剤は、３００ｎｍ以上４００ｎｍ以下の波長及び３００ｍＪ／ｃｍ２以上３０００ｍＪ／ｃｍ２以下の積算光量の光を照射することによって好適に硬化させることができる。 When curing the organic EL display element sealing agent of the present invention by light irradiation, the organic EL display sealant element of the present invention, 300 nm or more 400nm or less wavelength and 300 mJ / cm 2 or more 3000 mJ / cm 2 or less of It can be suitably cured by irradiating with an accumulated amount of light.
上記光照射に用いる光源としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、エキシマレーザ、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、ナトリウムランプ、ハロゲンランプ、キセノンランプ、ＬＥＤランプ、蛍光灯、太陽光、電子線照射装置等が挙げられる。これらの光源は、単独で用いられてもよく、２種以上が併用されてもよい。
これらの光源は、上記光カチオン重合開始剤の吸収波長に合わせて適宜選択される。 Examples of the light source used for the light irradiation include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, and a xenon. A lamp, an LED lamp, a fluorescent lamp, sunlight, an electron beam irradiation apparatus, etc. are mentioned. These light sources may be used independently and 2 or more types may be used together.
These light sources are appropriately selected according to the absorption wavelength of the photocationic polymerization initiator.
本発明の有機ＥＬ表示素子用封止剤への光の照射手段としては、例えば、各種光源の同時照射、時間差をおいての逐次照射、同時照射と逐次照射との組み合わせ照射等が挙げられ、いずれの照射手段を用いてもよい。 Examples of the light irradiation means to the organic EL display element sealant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Any irradiation means may be used.
上記有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程により得られる硬化物は、更に無機材料膜で被覆されていてもよい。
上記無機材料膜を構成する無機材料としては、従来公知のものを用いることができ、例えば、窒化珪素（ＳｉＮｘ）や酸化珪素（ＳｉＯｘ）等が挙げられる。上記無機材料膜は、１層からなるものであってもよく、複数種の層を積層したものであってもよい。また、上記無機材料膜と本発明の有機ＥＬ表示素子用封止剤からなる樹脂膜とを、交互に繰り返して上記積層体を被覆してもよい。 The cured product obtained by the step of curing the organic EL display element sealing agent by light irradiation and / or heating may be further coated with an inorganic material film.
As the inorganic material forming the inorganic material layer can be a conventionally known, for example, silicon nitride (SiN x), silicon oxide (SiO x), and the like. The inorganic material film may be a single layer or may be a laminate of a plurality of types of layers. Moreover, you may coat | cover the said laminated body by repeating alternately the said inorganic material film | membrane and the resin film which consists of the sealing agent for organic EL display elements of this invention.
上記有機ＥＬ表示素子を製造する方法は、本発明の有機ＥＬ表示素子用封止剤を塗布した基材（以下、「一方の基材」ともいう）と他方の基材とを貼り合わせる工程を有していてもよい。
本発明の有機ＥＬ表示素子用封止剤を塗布する基材（以下、「一方の基材」ともいう）は、有機発光材料層を有する積層体の形成されている基材であってもよく、該積層体の形成されていない基材であってもよい。
上記一方の基材が上記積層体の形成されていない基材である場合、上記他方の基材を貼り合わせた際に、上記積層体を外気から保護できるように上記一方の基材に本発明の有機ＥＬ表示素子用封止剤を塗布すればよい。即ち、他方の基材を貼り合わせた際に上記積層体の位置となる場所に全面的に塗布するか、又は、他方の基材を貼り合わせた際に上記積層体の位置となる場所が完全に収まる形状に、閉じたパターンの封止剤部を形成してもよい。 The method for producing the organic EL display element comprises a step of bonding a base material (hereinafter also referred to as “one base material”) coated with the organic EL display element sealing agent of the present invention and the other base material. You may have.
The substrate on which the sealing agent for organic EL display elements of the present invention is applied (hereinafter also referred to as “one substrate”) may be a substrate on which a laminate having an organic light emitting material layer is formed. A base material on which the laminate is not formed may be used.
When the one substrate is a substrate on which the laminate is not formed, the present invention is applied to the one substrate so that the laminate can be protected from the outside air when the other substrate is bonded. What is necessary is just to apply | coat the sealing agent for organic EL display elements. That is, apply the entire surface to the location of the laminate when the other substrate is bonded, or the location of the laminate is complete when the other substrate is bonded. The sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.
上記有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程は、上記一方の基材と上記他方の基材とを貼り合わせる工程の前に行なってもよいし、上記一方の基材と上記他方の基材とを貼り合わせる工程の後に行なってもよい。
上記有機ＥＬ表示素子用封止剤を光照射及び／又は加熱により硬化させる工程を、上記一方の基材と上記他方の基材とを貼り合わせる工程の前に行なう場合、本発明の有機ＥＬ表示素子用封止剤は、光照射及び／又は加熱してから硬化反応が進行して接着ができなくなるまでの可使時間が１分以上であることが好ましい。上記可使時間が１分以上であることにより、上記一方の基材と上記他方の基材とを貼り合わせる前に硬化が進行し過ぎることなく、より高い接着強度を得ることができる。 The step of curing the organic EL display element sealant by light irradiation and / or heating may be performed before the step of bonding the one base material and the other base material, You may perform after the process of bonding a base material and said other base material.
When the step of curing the organic EL display element sealant by light irradiation and / or heating is performed before the step of bonding the one base material and the other base material, the organic EL display of the present invention. The device sealant preferably has a pot life of 1 minute or longer after irradiation with light and / or heating until the curing reaction proceeds and adhesion becomes impossible. When the pot life is 1 minute or longer, higher adhesion strength can be obtained without excessive curing before the one base material and the other base material are bonded together.
上記一方の基材と上記他方の基材とを貼り合わせる工程において、上記一方の基材と上記他方の基材とを貼り合わせる方法は特に限定されないが、減圧雰囲気下で貼り合わせることが好ましい。
上記減圧雰囲気下の真空度の好ましい下限は０．０１ｋＰａ、好ましい上限は１０ｋＰａである。上記減圧雰囲気下の真空度がこの範囲であることにより、真空装置の気密性や真空ポンプの能力から真空状態を達成するのに長時間を費やすことなく、上記一方の基材と上記他方の基材とを貼り合わせる際の本発明の有機ＥＬ表示素子用封止剤中の気泡をより効率的に除去することができる。 In the step of bonding the one base material and the other base material, a method of bonding the one base material and the other base material is not particularly limited, but it is preferable to bond them in a reduced-pressure atmosphere.
The preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa. When the degree of vacuum in the reduced-pressure atmosphere is within this range, the one base material and the other base material are not spent for a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Bubbles in the sealing agent for organic EL display elements of the present invention when the material is bonded can be more efficiently removed.
本発明によれば、インクジェット塗布性、低アウトガス性、及び、無機材料膜に対する密着性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for organic EL display elements which can obtain the organic EL display element which is excellent in inkjet applicability | paintability, low outgas property, and the adhesiveness with respect to an inorganic material film | membrane, and is excellent in reliability is provided. can do.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１～１５、比較例１～４）
表１～３に記載された配合比に従い、各材料を、ホモディスパー型撹拌混合機（プライミクス社製、「ホモディスパーＬ型」）を用い、撹拌速度３０００ｒｐｍで均一に撹拌混合することにより、実施例１～１５、比較例１～４の各有機ＥＬ表示素子用封止剤を作製した。
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２」）を用いて、２５℃、１００ｒｐｍの条件において測定した粘度、及び、２５℃において動的濡れ性試験機（レスカ社製、「ＷＥＴ－６１００型」）により測定した表面張力を表１～３に示した。 (Examples 1 to 15, Comparative Examples 1 to 4)
According to the blending ratios described in Tables 1 to 3, each material was stirred and mixed uniformly at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Primix, “Homodisper L type”). Sealants for organic EL display elements of Examples 1 to 15 and Comparative Examples 1 to 4 were prepared.
About each sealing agent for organic EL display elements obtained in Examples and Comparative Examples, measurement was performed using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-22”) at 25 ° C. and 100 rpm. Tables 1 to 3 show the measured viscosity and the surface tension measured at 25 ° C. using a dynamic wettability tester (Reska, “WET-6100”).
＜評価＞
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤について以下の評価を行った。結果を表１～３に示した。 <Evaluation>
The following evaluation was performed about each sealing agent for organic EL display elements obtained by the Example and the comparative example. The results are shown in Tables 1-3.
（１）インクジェット塗布性
（１－１）インクジェット吐出性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤を、インクジェット吐出装置（マイクロジェット社製、「ＮａｎｏＰｒｉｎｔｅｒ５００」）を用いて、３０ピコリットルの液滴量にて、アルカリ洗浄した無アルカリガラス（旭硝子社製、「ＡＮ１００」）上に、５ｍ／秒の速度にて５００μｍピッチで１０００滴塗布した。
塗布できなかった液滴の数が０個であった場合を「◎」、塗布できなかった液滴の数が１個以上５個未満であった場合を「○」、塗布できなかった液滴の数が５個以上２０個未満であった場合を「△」、塗布できなかった液滴の数が２０個以上であった場合を「×」としてインクジェット吐出性を評価した。 (1) Inkjet applicability (1-1) Inkjet ejection properties Each of the organic EL display element sealants obtained in Examples and Comparative Examples was used with an inkjet ejection device (“NanoPrinter500” manufactured by Microjet Co., Ltd.). Then, 1000 drops were applied at a speed of 5 m / second at a pitch of 500 μm on alkali-washed non-alkali glass (“AN100” manufactured by Asahi Glass Co., Ltd.) with a drop volume of 30 picoliters.
When the number of droplets that could not be applied was 0, “０”, when the number of droplets that could not be applied was 1 or more and less than 5, “○”, droplets that could not be applied The ink jetting property was evaluated as “Δ” when the number of droplets was 5 or more and less than 20, and “X” when the number of droplets that could not be applied was 20 or more.
（１－２）濡れ広がり性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤を、インクジェット吐出装置（マイクロジェット社製、「ＮａｎｏＰｒｉｎｔｅｒ５００」）を用いて、３０ピコリットルの液滴量にて、アルカリ洗浄した無アルカリガラス（旭硝子社製、「ＡＮ１００」）上に、５ｍ／秒の速度にて５００μｍピッチで１０００滴塗布した。塗布から１０分後の無アルカリガラス上の液滴の直径を測定し、液滴の直径が１５０μｍ以上であった場合を「◎」、液滴の直径が５０μｍ以上１５０μｍ未満であった場合を「○」、液滴の直径が５０μｍ未満であった場合を「×」として濡れ広がり性を評価した。 (1-2) Wetting and spreading property Each of the sealing agents for organic EL display elements obtained in the examples and comparative examples is a liquid of 30 picoliters using an inkjet discharge device (“NanoPrinter500” manufactured by Microjet). With a drop amount, 1000 drops were applied at a speed of 5 m / sec on a non-alkali glass (ASA 100, manufactured by Asahi Glass Co., Ltd.) washed with alkali at a pitch of 500 μm. The diameter of the droplet on the alkali-free glass 10 minutes after the coating was measured, and “◎” when the droplet diameter was 150 μm or more, and “when the droplet diameter was 50 μm or more and less than 150 μm” “○”, the case where the diameter of the droplet was less than 50 μm was evaluated as “×” and the wet spreading property was evaluated.
（２）低アウトガス性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤の硬化物の加熱時に発生するアウトガスを以下に示すヘッドスペース法によるガスクロマトグラフにより測定した。
まず、各有機ＥＬ表示素子用封止剤１００ｍｇをアプリケーターにて３００μｍの厚さに塗工した後に、ＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して封止剤を硬化させた。次いで、得られた封止剤硬化物をヘッドスペース用バイアルに入れてバイアルを封止し、１００℃で３０分間加熱して、ヘッドスペース法により発生ガスを測定した。
発生したガスが３００ｐｐｍ未満であった場合を「◎」、３００ｐｐｍ以上５００ｐｐｍ未満であった場合を「○」、５００ｐｐｍ以上であった場合を「×」として低アウトガス性を評価した。 (2) Low outgassing property Outgas generated during heating of the cured product of the sealing agent for organic EL display elements obtained in the examples and comparative examples was measured by a gas chromatograph by the headspace method shown below.
First, 100 mg of each organic EL display element sealant was applied to a thickness of 300 μm with an applicator, and then the UV light with a wavelength of 365 nm was irradiated with 3000 mJ / cm 2 with an LED lamp to cure the sealant. Next, the obtained sealant cured product was put in a headspace vial, the vial was sealed, heated at 100 ° C. for 30 minutes, and the generated gas was measured by the headspace method.
The case where the generated gas was less than 300 ppm was evaluated as “◎”, the case where it was 300 ppm or more and less than 500 ppm as “◯”, and the case where it was 500 ppm or more as “x”, and the low outgassing property was evaluated.
（３）無機材料膜に対する密着性
膜厚３００ｎｍの窒化珪素膜が予め製膜されたガラス上に、実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤を、スピンコーターを用いて１０μｍの厚みに塗布した。次いで、ＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射し、更に１００℃で３０分間加熱して、有機ＥＬ表示素子用封止剤を硬化させ、樹脂膜を得た。
形成した樹脂膜に対しＪＩＳ　Ｋ　５６００－５－６に従い、切込み間隔１ｍｍのクロスカット試験を行った。クロスカット試験を行った際の、剥がれが５％以下であった場合を「◎」、剥がれが５％を超え３５％以下であった場合を「○」、剥がれが３５％を超え６５％以下であった場合を「△」、剥がれが６５％を超えた場合を「×」として無機材料膜に対する密着性を評価した。 (3) Adhesiveness to inorganic material film Each glass EL device sealing agent obtained in Examples and Comparative Examples is formed on a glass on which a silicon nitride film having a thickness of 300 nm is formed in advance using a spin coater. To a thickness of 10 μm. Next, ultraviolet light having a wavelength of 365 nm was irradiated with an LED lamp at 3000 mJ / cm 2 and further heated at 100 ° C. for 30 minutes to cure the organic EL display element sealant to obtain a resin film.
A cross-cut test with a cut interval of 1 mm was performed on the formed resin film in accordance with JIS K 5600-5-6. When the cross-cut test was performed, the peeling was 5% or less, “◎”, when the peeling was more than 5% and 35% or less, “◯”, and the peeling was more than 35% and 65% or less. In the case of “Δ”, the case where peeling exceeded 65% was evaluated as “x”, and the adhesion to the inorganic material film was evaluated.
（４）透明性
実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤を、スピンコーターを用いてガラス上に塗布した。次いで、ＬＥＤランプにて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して封止剤を硬化させ、厚さ１０μｍの試験片を作製した。得られた試験片について、分光計（東京電色社製、ＡＵＴＯＭＡＴＩＣ　ＨＡＺＥ　ＭＥＴＥＲ　ＭＯＤＥＬ　ＴＣ－ＩＩＩ　ＤＰＫ）を用いて、波長３８０～８００ｎｍにおける光のヘイズ値（曇価）を測定した。ヘイズ値が、０．３％以下であった場合を「◎」、０．３％を超え１％以下であった場合を「○」、１％を超えた場合を「×」として透明性を評価した。 (4) Transparency Each sealing agent for organic EL display elements obtained in Examples and Comparative Examples was applied on glass using a spin coater. Next, ultraviolet rays having a wavelength of 365 nm were irradiated with an LED lamp at 3000 mJ / cm 2 to cure the sealant, and a test piece having a thickness of 10 μm was produced. About the obtained test piece, the haze value (cloudiness value) of light at a wavelength of 380 to 800 nm was measured using a spectrometer (manufactured by Tokyo Denshoku Co., Ltd., AUTOMATIC HAZE METER MODEL TC-III DPK). When the haze value is 0.3% or less, “◎”, when it exceeds 0.3% and 1% or less, “◯”, when it exceeds 1%, “×”, and transparency. evaluated.
（５）有機ＥＬ表示素子の信頼性
（５－１）有機発光材料層を有する積層体が配置された基板の作製
ガラス基板（長さ２５ｍｍ、幅２５ｍｍ、厚さ０．７ｍｍ）にＩＴＯ電極を１０００Åの厚さで成膜したものを基板とした。上記基板をアセトン、アルカリ水溶液、イオン交換水、イソプロピルアルコールにてそれぞれ１５分間超音波洗浄した後、煮沸させたイソプロピルアルコールにて１０分間洗浄し、更に、ＵＶ－オゾンクリーナ（日本レーザー電子社製、「ＮＬ－ＵＶ２５３」）にて直前処理を行った。
次に、この基板を真空蒸着装置の基板フォルダに固定し、素焼きの坩堝にＮ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニルベンジジン（α－ＮＰＤ）を２００ｍｇ、別の素焼き坩堝にトリス（８－キノリノラト）アルミニウム（Ａｌｑ３）を２００ｍｇ入れ、真空チャンバー内を、１×１０－４Ｐａまで減圧した。その後、α－ＮＰＤの入った坩堝を加熱し、α－ＮＰＤを蒸着速度１５Å／ｓで基板に堆積させ、膜厚６００Åの正孔輸送層を成膜した。次いで、Ａｌｑ３の入った坩堝を加熱し、１５Å／ｓの蒸着速度で膜厚６００Åの有機発光材料層を成膜した。その後、正孔輸送層及び有機発光材料層が形成された基板を別の真空蒸着装置に移し、この真空蒸着装置内のタングステン製抵抗加熱ボートにフッ化リチウム２００ｍｇ、別のタングステン製ボートにアルミニウム線１．０ｇを入れた。その後、真空蒸着装置の蒸着器内を２×１０－４Ｐａまで減圧してフッ化リチウムを０．２Å／ｓの蒸着速度で５Å成膜した後、アルミニウムを２０Å／ｓの速度で１０００Å成膜した。窒素により蒸着器内を常圧に戻し、１０ｍｍ×１０ｍｍの有機発光材料層を有する積層体が配置された基板を取り出した。 (5) Reliability of organic EL display element (5-1) Fabrication of a substrate on which a laminate having an organic light emitting material layer is disposed An ITO electrode is placed on a glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm). A substrate having a thickness of 1000 mm was used as a substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.). The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum evaporation apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is added to the unglazed crucible. 200 mg of tris (8-quinolinolato) aluminum (Alq 3 ) was put in the crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa. Thereafter, the crucible containing α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 ｓ / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light-emitting material layer are formed is transferred to another vacuum vapor deposition apparatus. 1.0 g was added. After that, the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 × 10 −4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did. The inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.
（５－２）無機材料膜Ａによる被覆
得られた積層体が配置された基板の該積層体全体を覆うように、１３ｍｍ×１３ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ａを形成した。
プラズマＣＶＤ法は、原料ガスとしてＳｉＨ４ガス及び窒素ガスを用い、各々の流量をＳｉＨ４ガス１０ｓｃｃｍ、窒素ガス２００ｓｃｃｍとし、ＲＦパワーを１０Ｗ（周波数２．４５ＧＨｚ）、チャンバー内温度を１００℃、チャンバー内圧力を０．９Ｔｏｒｒとする条件で行った。
形成された無機材料膜Ａの厚さは、約１μｍであった。 (5-2) Coating with Inorganic Material Film A A mask having an opening of 13 mm × 13 mm is installed so as to cover the entire laminated body of the substrate on which the obtained laminated body is arranged, and inorganic by plasma CVD method. A material film A was formed.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film A had a thickness of about 1 μm.
（５－３）樹脂保護膜の形成
得られた基板に対し、実施例及び比較例で得られた各有機ＥＬ表示素子用封止剤を、インクジェット吐出装置（マイクロジェット社製、「ＮａｎｏＰｒｉｎｔｅｒ３００」）を使用して基板にパターン塗布した。
その後、ＬＥＤランプを用いて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して有機ＥＬ表示素子用封止剤を硬化させて樹脂保護膜を形成した。 (5-3) Formation of Resin Protective Film Each of the organic EL display element sealants obtained in Examples and Comparative Examples was applied to the obtained substrate using an inkjet discharge device (“NanoPrinter300” manufactured by Microjet Co., Ltd.). Was used to apply a pattern to the substrate.
Thereafter, an ultraviolet ray having a wavelength of 365 nm was irradiated with 3000 mJ / cm 2 using an LED lamp to cure the organic EL display element sealant to form a resin protective film.
（５－４）無機材料膜Ｂによる被覆
樹脂保護膜を形成した後、該樹脂保護膜の全体を覆うように、１２ｍｍ×１２ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ｂを形成して有機ＥＬ表示素子を得た。
プラズマＣＶＤ法は、上記「（５－２）無機材料膜Ａによる被覆」と同様の条件で行った。
形成された無機材料膜Ｂの厚さは、約１μｍであった。 (5-4) After forming the covering resin protective film with the inorganic material film B, a mask having an opening of 12 mm × 12 mm is installed so as to cover the entire resin protective film, and the inorganic material is formed by plasma CVD. Film B was formed to obtain an organic EL display element.
The plasma CVD method was performed under the same conditions as in the above “(5-2) Coating with inorganic material film A”.
The formed inorganic material film B had a thickness of about 1 μm.
（５－５）有機ＥＬ表示素子の発光状態
得られた有機ＥＬ表示素子を、温度８５℃、湿度８５％の環境下で１００時間暴露した後、３Ｖの電圧を印加し、有機ＥＬ表示素子の発光状態（ダークスポット及び画素周辺消光の有無）を目視で観察した。ダークスポットや周辺消光が無く均一に発光した場合を「◎」、ダークスポットや周辺消光はないものの輝度に僅かな低下が認められた場合を「○」、ダークスポットや周辺消光が認められた場合を「△」、非発光部が著しく拡大した場合を「×」として有機ＥＬ表示素子の発光状態を評価した。 (5-5) Light-Emitting State of Organic EL Display Element The obtained organic EL display element was exposed for 100 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, and then a voltage of 3 V was applied to The light emission state (the presence or absence of dark spots and pixel periphery quenching) was visually observed. "◎" when there is no dark spot or peripheral quenching, and "◎" when there is no dark spot or peripheral quenching, but "○" when there is a slight decrease in brightness, when dark spot or peripheral quenching is observed Was evaluated as “Δ” and the light emitting state of the organic EL display element was evaluated as “×” when the non-light emitting portion was significantly enlarged.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
本発明によれば、インクジェット塗布性、低アウトガス性、及び、無機材料膜に対する密着性に優れ、かつ、信頼性に優れる有機ＥＬ表示素子を得ることができる有機ＥＬ表示素子用封止剤を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for organic EL display elements which can obtain the organic EL display element which is excellent in inkjet applicability | paintability, low outgas property, and the adhesiveness with respect to an inorganic material film | membrane, and is excellent in reliability is provided. can do.

Claims (7)

  1. 重合性化合物と重合開始剤とを含有する有機ＥＬ表示素子用封止剤であって、
    前記重合性化合物は、単官能オキセタン化合物と多官能オキセタン化合物とを含有し、
    前記重合性化合物１００重量部中における、前記単官能オキセタン化合物の含有量が２０重量部以上３５重量部以下であり、かつ、前記多官能オキセタン化合物の含有量が２５重量部以上４０重量部以下であり、
    ２５℃における粘度が８０ｍＰａ・ｓ以下であり、２５℃における表面張力が１５ｍＮ／ｍ以上３５ｍＮ／ｍ以下である
    ことを特徴とする有機ＥＬ表示素子用封止剤。     An organic EL display element sealing agent containing a polymerizable compound and a polymerization initiator,
    The polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound,
    In 100 parts by weight of the polymerizable compound, the content of the monofunctional oxetane compound is 20 to 35 parts by weight, and the content of the polyfunctional oxetane compound is 25 to 40 parts by weight. Yes,
    A sealing agent for organic EL display elements, wherein a viscosity at 25 ° C. is 80 mPa · s or less and a surface tension at 25 ° C. is 15 mN / m or more and 35 mN / m or less.
  2. 重合性化合物と重合開始剤とを含有する有機ＥＬ表示素子用封止剤であって、
    前記重合性化合物は、単官能オキセタン化合物と多官能オキセタン化合物とを含有し、
    前記重合性化合物１００重量部中における、前記単官能オキセタン化合物の含有量が２０重量部以上３５重量部以下であり、かつ、前記多官能オキセタン化合物の含有量が２５重量部以上４０重量部以下であり、
    インクジェット法による塗布に用いられる
    ことを特徴とする有機ＥＬ表示素子用封止剤。     An organic EL display element sealing agent containing a polymerizable compound and a polymerization initiator,
    The polymerizable compound contains a monofunctional oxetane compound and a polyfunctional oxetane compound,
    In 100 parts by weight of the polymerizable compound, the content of the monofunctional oxetane compound is 20 to 35 parts by weight, and the content of the polyfunctional oxetane compound is 25 to 40 parts by weight. Yes,
    A sealing agent for organic EL display elements, which is used for coating by an ink jet method.
  3. 単官能オキセタン化合物と多官能オキセタン化合物との含有割合が、重量比で、単官能オキセタン化合物：多官能オキセタン化合物＝５：３～５：９であることを特徴とする請求項１又は２記載の有機ＥＬ表示素子用封止剤。 The content ratio of the monofunctional oxetane compound and the polyfunctional oxetane compound is, as a weight ratio, monofunctional oxetane compound: polyfunctional oxetane compound = 5: 3 to 5: 9, Sealant for organic EL display elements.
  4. 重合性化合物は、シクロアルケンオキサイド型脂環式エポキシ化合物を含有することを特徴とする請求項１、２又は３記載の有機ＥＬ表示素子用封止剤。 4. The encapsulant for organic EL display elements according to claim 1, wherein the polymerizable compound contains a cycloalkene oxide type alicyclic epoxy compound.
  5. 重合性化合物１００重量部中におけるシクロアルケンオキサイド型脂環式エポキシ化合物の含有量が１５重量部以上３０重量部以下であることを特徴とする請求項４記載の有機ＥＬ表示素子用封止剤。 The sealing agent for organic EL display elements according to claim 4, wherein the content of the cycloalkene oxide type alicyclic epoxy compound in 100 parts by weight of the polymerizable compound is 15 parts by weight or more and 30 parts by weight or less.
  6. 重合性化合物は、アルキルポリオール型エポキシ化合物を含有することを特徴とする請求項１、２、３、４又は５記載の有機ＥＬ表示素子用封止剤。 The encapsulant for an organic EL display element according to claim 1, wherein the polymerizable compound contains an alkyl polyol type epoxy compound.
  7. 重合性化合物１００重量部中におけるアルキルポリオール型エポキシ化合物の含有量が５重量部以上３０重量部以下であることを特徴とする請求項６記載の有機ＥＬ表示素子用封止剤。 7. The sealant for an organic EL display device according to claim 6, wherein the content of the alkyl polyol type epoxy compound in 100 parts by weight of the polymerizable compound is 5 parts by weight or more and 30 parts by weight or less.
PCT/JP2018/021542 2017-06-07 2018-06-05 Sealant for organic electroluminescent display element WO2018225723A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201880029518.4A CN110583098B (en) 2017-06-07 2018-06-05 Sealing agent for organic EL display element
CN202210874228.8A CN115232511B (en) 2017-06-07 2018-06-05 Sealing agent for organic EL display element
JP2018530907A JP7010824B2 (en) 2017-06-07 2018-06-05 Encapsulant for organic EL display elements
KR1020197021823A KR102658947B1 (en) 2017-06-07 2018-06-05 Encapsulant for organic EL display elements

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017112727 2017-06-07
JP2017-112727 2017-06-07

Publications (1)

Publication Number Publication Date
WO2018225723A1 true WO2018225723A1 (en) 2018-12-13

Family

ID=64566134

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/021542 WO2018225723A1 (en) 2017-06-07 2018-06-05 Sealant for organic electroluminescent display element

Country Status (4)

Country Link
JP (1) JP7010824B2 (en)
KR (1) KR102658947B1 (en)
CN (2) CN110583098B (en)
WO (1) WO2018225723A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019244780A1 (en) * 2018-06-20 2019-12-26 三井化学株式会社 Sealing agent for display element and cured product thereof
WO2022191232A1 (en) * 2021-03-10 2022-09-15 三井化学株式会社 Ultraviolet-curing resin composition for organic el sealant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005320434A (en) * 2004-05-10 2005-11-17 Nitto Denko Corp Ultraviolet-curable resin composition
JP2010209126A (en) * 2009-03-06 2010-09-24 Sumitomo Chemical Co Ltd Photosetting adhesive composition, polarizing plate and production method of the same, optical member, and liquid crystal display
JP2014019800A (en) * 2012-07-19 2014-02-03 Nippon Kayaku Co Ltd Energy ray-curable resin composition and cured body
JP2014225380A (en) * 2013-05-16 2014-12-04 積水化学工業株式会社 Sealant for organic electroluminescent display element and manufacturing method of organic electroluminescent display element
WO2016170693A1 (en) * 2015-04-22 2016-10-27 ユニ・チャーム株式会社 Absorbent article

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5463084A (en) * 1992-02-18 1995-10-31 Rensselaer Polytechnic Institute Photocurable silicone oxetanes
JP3817081B2 (en) 1999-01-29 2006-08-30 パイオニア株式会社 Manufacturing method of organic EL element
EP1138739B1 (en) * 1999-08-12 2006-10-11 Mitsui Chemicals, Inc. Photocurable resin composition for sealing material and method of sealing
JP2001307873A (en) 2000-04-21 2001-11-02 Toppan Printing Co Ltd Organic electroluminescence display element and its manufacturing method
US8808457B2 (en) 2002-04-15 2014-08-19 Samsung Display Co., Ltd. Apparatus for depositing a multilayer coating on discrete sheets
CN100404578C (en) * 2003-08-12 2008-07-23 三井化学株式会社 Photo-curable resin composition and sealing agent for flat panel display using the same
JP4590997B2 (en) * 2004-09-15 2010-12-01 コニカミノルタホールディングス株式会社 Substrate film for display and organic electroluminescence device
JP2008149710A (en) 2006-11-22 2008-07-03 Fujifilm Corp Manufacturing method of barrier laminate, barrier laminate, barrier film substrate, and organic el element
JP2010143982A (en) * 2008-12-17 2010-07-01 Chisso Corp Photo-curable ink for inkjet
JP5736033B2 (en) * 2010-04-29 2015-06-17 ハンツマン・アドヴァンスト・マテリアルズ・（スイッツランド）・ゲーエムベーハー Curable composition
KR101422659B1 (en) * 2011-05-12 2014-07-23 한국생산기술연구원 Novel oxetane compound, method for preparing thereof, composite sheet for display device comprising the same
JP6363508B2 (en) * 2012-11-28 2018-07-25 日本化薬株式会社 Resin composition and cured product thereof (1)
KR102226349B1 (en) * 2013-10-30 2021-03-10 세키스이가가쿠 고교가부시키가이샤 Sealing agent for organic el display elements

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005320434A (en) * 2004-05-10 2005-11-17 Nitto Denko Corp Ultraviolet-curable resin composition
JP2010209126A (en) * 2009-03-06 2010-09-24 Sumitomo Chemical Co Ltd Photosetting adhesive composition, polarizing plate and production method of the same, optical member, and liquid crystal display
JP2014019800A (en) * 2012-07-19 2014-02-03 Nippon Kayaku Co Ltd Energy ray-curable resin composition and cured body
JP2014225380A (en) * 2013-05-16 2014-12-04 積水化学工業株式会社 Sealant for organic electroluminescent display element and manufacturing method of organic electroluminescent display element
WO2016170693A1 (en) * 2015-04-22 2016-10-27 ユニ・チャーム株式会社 Absorbent article

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019244780A1 (en) * 2018-06-20 2019-12-26 三井化学株式会社 Sealing agent for display element and cured product thereof
JPWO2019244780A1 (en) * 2018-06-20 2021-03-11 三井化学株式会社 Sealant for display elements and its cured product
JP7078720B2 (en) 2018-06-20 2022-05-31 三井化学株式会社 Sealant for display elements and its cured product
WO2022191232A1 (en) * 2021-03-10 2022-09-15 三井化学株式会社 Ultraviolet-curing resin composition for organic el sealant

Also Published As

Publication number Publication date
CN110583098A (en) 2019-12-17
CN115232511B (en) 2023-11-24
KR102658947B1 (en) 2024-04-18
CN110583098B (en) 2022-07-26
KR20200018388A (en) 2020-02-19
CN115232511A (en) 2022-10-25
JPWO2018225723A1 (en) 2020-04-09
JP7010824B2 (en) 2022-01-26

Similar Documents

Publication Publication Date Title
JP6404494B2 (en) Sealant for organic EL display element
JP2017228414A (en) Sealant for organic electroluminescent display element
JP6427283B2 (en) Sealing agent for organic EL display element and method of manufacturing sealing agent for organic EL display element
JP2022027778A (en) Organic el display element sealing agent
JP7007272B2 (en) Encapsulant for organic EL display elements
JP6404496B2 (en) Sealant for organic EL display element
JP7010824B2 (en) Encapsulant for organic EL display elements
JP2023029649A (en) Sealant for organic EL display element
JP6427282B2 (en) Sealant for organic EL display elements
WO2019198470A1 (en) Sealant for organic electroluminescent display element
WO2018131553A1 (en) Sealant for organic electroluminescent display element
JP2019029355A (en) Sealing agent for organic EL display element

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018530907

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18812944

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197021823

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18812944

Country of ref document: EP

Kind code of ref document: A1